WO2007014849A2 - Two photon or multi photon phthalocyanine based absorption material for optical data storage - Google Patents
Two photon or multi photon phthalocyanine based absorption material for optical data storage Download PDFInfo
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- WO2007014849A2 WO2007014849A2 PCT/EP2006/064392 EP2006064392W WO2007014849A2 WO 2007014849 A2 WO2007014849 A2 WO 2007014849A2 EP 2006064392 W EP2006064392 W EP 2006064392W WO 2007014849 A2 WO2007014849 A2 WO 2007014849A2
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- WIPO (PCT)
- Prior art keywords
- alkyl
- alkoxy
- halogen
- alkylthio
- formula
- Prior art date
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- 238000010521 absorption reaction Methods 0.000 title claims abstract description 28
- 230000003287 optical effect Effects 0.000 title claims abstract description 27
- 238000013500 data storage Methods 0.000 title claims abstract description 15
- 239000000463 material Substances 0.000 title claims abstract description 14
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 title claims abstract description 13
- -1 amino, nitro, phenyl Chemical group 0.000 claims description 48
- 150000001875 compounds Chemical class 0.000 claims description 48
- 125000000217 alkyl group Chemical group 0.000 claims description 36
- 229910052736 halogen Inorganic materials 0.000 claims description 29
- 150000002367 halogens Chemical class 0.000 claims description 29
- 125000003545 alkoxy group Chemical group 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 22
- 125000004414 alkyl thio group Chemical group 0.000 claims description 20
- 125000003118 aryl group Chemical group 0.000 claims description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 14
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 230000005284 excitation Effects 0.000 claims description 13
- 229910052727 yttrium Inorganic materials 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- 238000003860 storage Methods 0.000 claims description 7
- 125000005110 aryl thio group Chemical group 0.000 claims description 6
- 125000004104 aryloxy group Chemical group 0.000 claims description 6
- 125000004429 atom Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 230000000977 initiatory effect Effects 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 230000001235 sensitizing effect Effects 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical group [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 3
- 239000013590 bulk material Substances 0.000 claims description 3
- 229910052805 deuterium Inorganic materials 0.000 claims description 3
- 238000012377 drug delivery Methods 0.000 claims description 3
- 238000011275 oncology therapy Methods 0.000 claims description 3
- 238000002428 photodynamic therapy Methods 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000003513 alkali Chemical group 0.000 claims description 2
- 125000002837 carbocyclic group Chemical group 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 230000009466 transformation Effects 0.000 claims description 2
- 238000012505 colouration Methods 0.000 claims 3
- 229910052804 chromium Inorganic materials 0.000 claims 2
- 150000002431 hydrogen Chemical class 0.000 claims 2
- 150000004696 coordination complex Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- 239000010410 layer Substances 0.000 description 24
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000000975 dye Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 0 *#Cc(c(C#*)c(c(N)c1N)N)c1N Chemical compound *#Cc(c(C#*)c(c(N)c1N)N)c1N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZDOLIEFMOFUAHC-UHFFFAOYSA-N anthracene-2,3-dinitrile Chemical compound C1=CC=C2C=C(C=C(C(C#N)=C3)C#N)C3=CC2=C1 ZDOLIEFMOFUAHC-UHFFFAOYSA-N 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 229910052594 sapphire Inorganic materials 0.000 description 3
- 239000010980 sapphire Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 235000002639 sodium chloride Nutrition 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- HGVNXEVNBBVJGZ-UHFFFAOYSA-N O1C2=C(N(C3=CC=CC=C13)C1=CC=C(C3=CC(C#N)=C(C#N)C=C3C3=CC=C(N4C5=CC=CC=C5OC5=C4C=CC=C5)C=C3)C=C1)C=CC=C2 Chemical compound O1C2=C(N(C3=CC=CC=C13)C1=CC=C(C3=CC(C#N)=C(C#N)C=C3C3=CC=C(N4C5=CC=CC=C5OC5=C4C=CC=C5)C=C3)C=C1)C=CC=C2 HGVNXEVNBBVJGZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 230000001427 coherent effect Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- KNBYJRSSFXTESR-UHFFFAOYSA-N naphthalene-2,3-dicarbonitrile Chemical compound C1=CC=C2C=C(C#N)C(C#N)=CC2=C1 KNBYJRSSFXTESR-UHFFFAOYSA-N 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
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- 150000004032 porphyrins Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- WKBPZYKAUNRMKP-UHFFFAOYSA-N 1-[2-(2,4-dichlorophenyl)pentyl]1,2,4-triazole Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(CCC)CN1C=NC=N1 WKBPZYKAUNRMKP-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- LFIZIBRVAJXLJR-UHFFFAOYSA-N 3-(2,4-dimethylpentan-3-yloxy)benzene-1,2-dicarbonitrile Chemical compound CC(C)C(C(C)C)OC1=CC=CC(C#N)=C1C#N LFIZIBRVAJXLJR-UHFFFAOYSA-N 0.000 description 1
- RXXCIBALSKQCAE-UHFFFAOYSA-N 3-methylbutoxymethylbenzene Chemical class CC(C)CCOCC1=CC=CC=C1 RXXCIBALSKQCAE-UHFFFAOYSA-N 0.000 description 1
- KHXKYJYWAPRBDH-UHFFFAOYSA-L 3h-dithiole-3-carboxylate;nickel(2+) Chemical compound [Ni+2].[O-]C(=O)C1SSC=C1.[O-]C(=O)C1SSC=C1 KHXKYJYWAPRBDH-UHFFFAOYSA-L 0.000 description 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
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- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
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- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000006547 cyclononyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
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- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
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- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- VWBWQOUWDOULQN-UHFFFAOYSA-N nmp n-methylpyrrolidone Chemical compound CN1CCCC1=O.CN1CCCC1=O VWBWQOUWDOULQN-UHFFFAOYSA-N 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JRCNNGRDCFZVPA-UHFFFAOYSA-N pentadecylazanium;chloride Chemical compound Cl.CCCCCCCCCCCCCCCN JRCNNGRDCFZVPA-UHFFFAOYSA-N 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 description 1
- 229920006391 phthalonitrile polymer Polymers 0.000 description 1
- 125000001557 phthalyl group Chemical group C(=O)(O)C1=C(C(=O)*)C=CC=C1 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 description 1
- KKVTYAVXTDIPAP-UHFFFAOYSA-M sodium;methanesulfonate Chemical compound [Na+].CS([O-])(=O)=O KKVTYAVXTDIPAP-UHFFFAOYSA-M 0.000 description 1
- DZXBHDRHRFLQCJ-UHFFFAOYSA-M sodium;methyl sulfate Chemical compound [Na+].COS([O-])(=O)=O DZXBHDRHRFLQCJ-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003419 tautomerization reaction Methods 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 150000007970 thio esters Chemical class 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
- G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
- G11B7/249—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing organometallic compounds
- G11B7/2492—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing organometallic compounds neutral compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/06—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide
- C09B47/067—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile
- C09B47/0675—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile having oxygen or sulfur linked directly to the skeleton
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/30—Metal-free phthalocyanines
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
- G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
- G11B7/246—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes
- G11B7/248—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes porphines; azaporphines, e.g. phthalocyanines
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B2007/0003—Recording, reproducing or erasing systems characterised by the structure or type of the carrier
- G11B2007/0009—Recording, reproducing or erasing systems characterised by the structure or type of the carrier for carriers having data stored in three dimensions, e.g. volume storage
Definitions
- the present application pertains to a method of 3 dimensional optical volume addressing, useful e.g. for optical data storage, wherein a photochromic effect is achieved in a suitable phthalocyanine by 2 photon absorption, to corresponding uses and optical data storage media including bulk and multilayer material, as well as to novel phthalocyanine compounds.
- JP-A-2005-029726 and JP-A-2005-037658 disclose an unresonant multi photon absorption material containing a sensitizing dye or emission color element, including some symmetrical phthalocyanines, for three-dimensional photoshaping, three-dimensional display or three- dimensional optical recording purposes.
- layers e.g. up to 10000 layers, or 1 to 1000 or 2-100 layers; especially about 100 to 1000 layers).
- a method of writing and recording of information may comprise the following steps:
- bits of information are written in the bulk of the disk containing a multitude of data layers by using near-resonance two-photon excitation of T2 form (T ⁇ Ti transformation).
- one bit may be written by one non-amplified femtosecond pulse of the Ti: Sa laser, focused down to a diffraction-limited volume with a large numerical aperture objective. The non-changed voxels are considered as "0".
- bits are read out with near resonant excitation and confocal scheme of collection of fluorescence (e.g. via 1 PA with a cw diode laser) of form Ti.
- data can be erased by
- temperature is preferably kept in the lower range as explained for step (a).
- Preparation of the metastable tautomer can be performed with the same laser beam used for writing and reading, e.g. if the laser wavelength is shifted to coincide with the absorption band of the stable form. This does not imply using a second 2PA laser, but may require the wavelength of the same laser to be shifted or filtered accordingly.
- Data layers may be located in separated layers of the recording material, or especially in the bulk of the recording material by application of the appropriate addresssing technique during writing; in the latter case, the data storage medium preferably contains only one bulk layer of the recording material.
- Layer structure and writing/reading device may also be, for example, as described in WO 99/23650.
- Phthalo- or naphthocyanines or aza-analogues thereof especially useful in the present invention basically consist of 4 phthalic moieties of the formula:
- the groups attached at the peripheral carbon skeleton can be, for example, -CHO, -
- CO-KW rad i ca i > -CH 2 OH or -COOH, or unsubstituted or substituted formyl, hydroxymethyl or carboxyl groups which may be prepared from -CHO, -CO-KW ra dicai, -CH 2 OH or -COOH by methods known per se.
- Substituted formyl or carbonyl groups are typically their acetals, oximes or hydrazones.
- Substituted hydroxymethyl groups are typically -CH 2 -00C-KW ra dicai or -CH 2 -O-KWradicai-
- Substituted carboxyl groups are typically esters or thioesters, such as
- each KW ra dicai being any saturated, unsaturated or aromatic unsubstituted or substituted hydrocarbon radical, for example CrC 2O alkyl, CrC 20 cycloalkyl, CrC 2O alkenyl, CrC 20 cycloalkenyl, CrC 2O alkynyl, CrC 20 cycloalkynyl, C 6 -Ci 8 aryl or C 7 -Ci 8 aralkyl.
- Further substituents may be chosen in accordance with/in analogy to compounds of formula I of WO98/14520 (see pages 3/4 therein).
- Gi, G 2 , G 3 , G 4 , Y and Y' independently are H, OH, halogen, nitro, COOG 9 , Ci-C 22 alkyl, C r C 22 alkoxy, C r C 22 alkylthio, C 4 -Ci 2 cycloalkyl, C 4 - Ci 2 cycloalkoxy, C 4 -Ci 2 cycloalkylthio, aryl, aryloxy, arylthio, wherein each alkyl or alkoxy or alkylthio or aryl or aryloxy or arylthio moiety may be substituted by OH, halogen, amino, nitro, phenyl, phenoxy, carboxy; and wherein each aryl or aryloxy or arylthio moiety may further be substituted by alkyl or alkoxy; and wherein each alkyl or alkoxy or alkylthio moiety containing 2 or more carbon
- Preferred are compounds wherein at least 1 moiety contains 2 vicinal substituents on the phenyl ring linked to a 4-membered bridge (CH) x N y , where x is 2 or 3 or 4, x is O or 1 or 2 and x+y 4, to form an annellated aromatic ring (moiety Nc).
- Aromatic CH moieties in each unit may be substituted, the final compounds thus being of the types Pc 3 Nc, Pc 2 Nc 2 , PcNc 3 or Nc 4 .
- phthalonaphthocyanines of the class Pc 3 Nc are of special technical importance.
- Gi, G 2 , G 3 , G 4 , Gii, Gi2, Gi 3 , G i4 , G 2 i, G 22 , G 23 and G 24 are H, OH, halogen, COOG 9 , C r C 22 alkyl, C r C 22 alkoxy, C r C 22 alkylthio, C 4 -Ci 2 cycloalkyl, C 4 -Ci 2 cycloalkoxy, wherein each alkyl or alkoxy or alkylthio moiety may be substituted by OH, halogen, amino, nitro, phenyl, phenoxy, carboxy; and wherein each alkyl or alkoxy or alkylthio moiety containing 2 or more carbon atoms may be interrupted in the carbon chain by O, NH, CO, COO, CONH, OCOO, OCONH, NHCONH; or a vicinal pair of residues G 3 and G 4 , Gi 3 and Gi 4 and/or G 23
- the central protons may conveniently be replaced completely or partially by heavier atoms such as deuterium, or alkaline (e.g. Li, Na), or replaced completely by a suitable divalent metal ion such as Zn, Mg, Pd on treatment with the appropriate reagents such as deuterated acid or salt, usually in solution.
- these modified compounds are of the formulae I' or I"
- D stands for deuterium or an alkali atom such as Li or Na, and one of the residues D may still be unmodified hydrogen;
- M is a divalent metal atom, for example selected from Mg, Zn, Pd; and all other symbols have the meaning as defined above for formula I.
- Preferred are, for examples, compounds of the formula I or I', or unsymmetrical (see below) compounds of the formula I".
- unsymmetrical compounds i.e. generally those deviating from C 4 -symmetry, especially wherein the compound deviates from C 4 - and C 2 - symmetry (axes perpendicular to the azaporphyrine ring system).
- each alkyl or alkoxy or alkylthio moiety may be substituted by OH, halogen, amino, nitro, phenyl, phenoxy, carboxy; and wherein each alkyl or alkoxy or alkylthio moiety containing 2 or more carbon atoms may be interrupted in the carbon chain by O, NH, CO, COO, CONH, OCOO, OCONH, NHCONH.
- Halogen is chloro, bromo, fluoro or iodo, preferably chloro or bromo on aryl or heteroaryl or fluoro on alkyl.
- Alkyl is, for example, Ci-d 2 alkyl inter alia comprising methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-methyl-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, n-hexyl, heptyl, n-octyl, 1,1,3,3-tetramethylbutyl, 2-ethylhexyl, nonyl, decyl, undecyl or dodecyl.
- Ci-d 2 alkyl inter alia comprising methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-methyl-butyl, n-pentyl, 2-pentyl
- Ci-C 22 Alkyl is straight-chain or branched alkyl radicals, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, isoamyl or tert-amyl, heptyl, octyl, isooctyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl or eicosyl.
- alkyl radicals such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, isoamyl or tert-amyl, heptyl, oc
- Ci -C 22 AI kylthio is straight-chain or branched alkylthio radicals, such as methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, sec-butylthio, tert-butylthio, amylthio, heptylthio, octyl- thio, isooctylthio, nonylthio, decylthio, undecylthio, dodecylthio, tetradecylthio, pentadecylthio, hexadecylthio, heptadecylthio, octadecylthio or eicosylthio.
- alkylthio radicals such as methylthio, ethylthio, n-propylthio, isopropylthio, n
- Cycloalkyl includes, for example, cyclopentyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, and preferably cyclohexyl.
- aryl Whenever aryl is mentioned, this means mostly C 6 -Ci 2 aryl, preferably phenyl or naphthyl, especially phenyl.
- Aralkyl is usually the alkyl as defined, which is substituted by the above aryl; preferred is Cy-Cuphenylalkyl.
- Alk(yl)aryl is the above aryl substituted by alkyl; preferred is phenyl mono-, di- or trisubstituted by C r C 4 alkyl.
- Hydrocarbon moieties interrupted by a heterofunctional group denotes a moiety which can be interrupted by one or more of these groups, one group in each case being inserted, in general into one carbon- carbon bond.
- both tautomers show very strong and narrow 1 PA S 0 ⁇ Si (Qi) band in near-IR region, which provides the opportunity to use strong resonance enhancement of 2PA, when exciting in the very vicinity of this band, e.g. using a commercially available femtosecond Ti:sapphire lasers.
- the invention further relates to an optical data storage medium comprising a substrate and at least one recording layer, the recording layer containing a compound of the formula I, I' or I".
- present invention also relates to the use of a compound as initially described as a recording dye in an optical data storage medium, and to a corresponding method of data storage.
- the recording medium according to the invention in addition to comprising the compounds of formula I, I' and/or I", may additionally comprise salts, for example ammonium chloride, pentadecylammonium chloride, sodium chloride, sodium iodide, sodium sulfate, sodium hydrogen sulfate, sodium methyl sulfate, sodium methylsulfonate, sodium tosylate, sodium acetate, sodium hexafluorophosphate, cobalt(II) acetate or cobalt(II) chloride, the ions of which may, for example, originate from the components used.
- salts for example ammonium chloride, pentadecylammonium chloride, sodium chloride, sodium iodide, sodium sulfate, sodium hydrogen sulfate, sodium methyl sulfate, sodium methylsulfonate, sodium tosylate, sodium acetate, sodium hexafluorophosphate, cobalt(II)
- the compounds of formula I, F and/or I" may also be used in combination with the known dyes such as known in the art especially for recording media based on 2 photon absorption.
- the substrate which acts as support for the layer(s) applied thereto, is advantageously semi- transparent (T > 10%) or preferably transparent (T>90%).
- the support can be from 0.01 to 10 mm thick, preferably from 0.1 to 5 mm thick.
- each layer may range from about 0.1 to about 50 micron 1), preferably from 0.5 to 30 ⁇ m, especially from about 3 to 10 ⁇ m, e.g. about 5 such as 2 - 7 ⁇ m.
- the linear absorption of the recording layer is advantageously low (optical density typically below 1 , absorption preferably below 0.01 , e.g. about 10 ⁇ 4 - 10 ⁇ 3 ) at the absorption maximum (2PA).
- Each recording layer may comprise thinner sub-layers, such as grooves or tracks, where the recording material is present.
- a protective layer can, if desired, serve also as adhesion promoter for a second substrate layer applied thereto, which is preferably from 0.1 to 5 mm thick and consists of the same material as the support substrate.
- Suitable substrates are, for example, glass, minerals, ceramics and thermosetting or thermoplastic plastics.
- Preferred supports are glass and homo- or co-polymeric plastics.
- Suitable plastics are, for example, thermoplastic polycarbonates, polyamides, polyesters, polyacrylates and polymethacrylates, polyurethanes, polyolefins, polyvinyl chloride, polyvinylidene fluoride, polyimides, thermosetting polyesters and epoxy resins.
- the substrate can be in pure form or may also comprise customary additives, for example UV absorbers or dyes, as proposed e.g. in JP 04/167 239 to provide light-stabilisation for the recording layer.
- the dye added to the support substrate may have an absorption maximum hypsochromically shifted relative to the dye of the recording layer by at least 10 nm, preferably by at least 20 nm.
- the dye added to the support substrate may also have an absorption maximum hypsochromically shifted relative to the dye of the recording layer by at least 10 nm, preferably by at least 20 nm.
- known stabilisers in customary amounts, for example a nickel dithiolate described in JP 04/025 493 as light stabiliser.
- chromophores for example those having an absorption maximum at from 300 to 1000 nm
- UV absorbers and/or other stabilisers for example those having an absorption maximum at from 300 to 1000 nm
- stabilisers for example those having an absorption maximum at from 300 to 1000 nm
- 1 O 2 - for example those having an absorption maximum at from 300 to 1000 nm
- triplet- or luminescence-quenchers for example melting-point reducers
- decomposition accelerators for example film-formers.
- the recording layer comprises a compound of formula I, I' and/or I" or a mixture of such compounds advantageously in an amount sufficient to provide a substantial two-photon absorption in a layer, while playing no substantial influence or at least only a low influence on the refractive index, for example from about 0.1 % to about 10% by weight, or up to 20% by weight, preferably about 1% by weight such as 0.5 to 5%, based on the total recording layer.
- the present phthalocyanines may generally be used for three-dimensional (3D) volume addressing including purposes other than optical information storage, wherein these properties are useful; many examples for such applications are described in WO97/09043 or the publications initially mentioned, such as photodynamic therapy (especially cancer therapy), or 2 photon initiation of reactions (e.g. polymerization or coloration reactions, modulation of index of refraction, emission of light).
- 3D three-dimensional
- 2 photodynamic therapy especially cancer therapy
- 2 photon initiation of reactions e.g. polymerization or coloration reactions, modulation of index of refraction, emission of light.
- Further applications wherein the effect of the invention may advantageously be exploited include the following ones: security printing - insertion of a 3D invisible image which only appears when IR lasers are used - optical effects; smart systems for tagging etc. (information storage for control and for reading); 3D microstructured phase fabrication in a stable polymer host matrix; 3D photoshaping composition; stereolithography
- Compounds of the formula A may be obtained by condensation of a suitable aromatic dicarbonitrile educt, e.g. of the formula where G r G 4 is as defined above, in presence of a base. Reactions are usually carried out in a solvent, which may be identical with the base. Suitable solvents are, for example, aromatic or aliphatic hydrocarbons, alcohols, ethers, or mixtures thereof.
- bases may be used, for example, alcoholates such as Li-, Na-, K-alkoholates, where the alkohol may inter alia be selected from Ci-C 8 hydroxyalkanes or Ci-C 8 alkoxy-C 2 -C 8 hydroxyalkanes; further bases suitable include alkaline sulphides such as Li or Na sulphides, or non-nucleophilic amines such as DBU, DBN and the like. Reactions are often carried out in the range from room temperature to reflux temperature of the solvent or, for example, in the range 20 - 100 0 C. Reactions may be carried out using a protective atmosphere under normal, reduced or increased pressure, e.g. under argon or nitrogen atmosphere.
- a protective atmosphere under normal, reduced or increased pressure, e.g. under argon or nitrogen atmosphere.
- the ratio of dicarbonitrile educts major component: minor component is preferably around 9 : 1, e.g. in the range (7 - 9.5) : (3 - 0.5).
- Room temperature depicts a temperature in the range 20-25°C. Percentages are by weight unless otherwise indicated.
- the resulting green solution is cooled to room temperature, 1 L of acetic acid is added drop by drop within 1 h, and the solution is stirred for 30 min.
- the solution is evaporated, the residue is dissolved in CH 2 CI 2 , 100 g of silica gel is added, and the slurry evaporated.
- the fractions containing the desired product are collected, evaporated, and subjected to a second chromatography. Yield: 1.05 g (4.2%) of 4 as a green powder.
- Example 4 The following compounds are prepared according to the procedure given in example 1 from appropriately substituted benzene-, naphthalene- and/or anthracene-2,3-dicarbonitriles obtained in analogy to compounds (1), (2) or (3): Pc 3 Nc (8):
- Linear absorption spectra are measured with a Lambda 900 Perkin Elmer spectrophotometer.
- the laser system comprises a Ti: sapphire femtosecond oscillator (Coherent Mira 900) pumped by 5W CW frequencydoubled Nd:YAG laser (Coherent Verdi), and a 1-kHz repetition rate Ti:sapphire femtosecond regenerative amplifier (CPA-1000, Clark MXR).
- the pulses from the amplifier are down converted with an optical parametric amplifier, OPA (TOPAS, Quantronix), whose output can be continuously tuned from 1100 to 2000 nm.
- OPA optical parametric amplifier
- the OPA output pulse energy is 100 - 200 microJ (5 - 10 microJ after frequency doubling of idler), and pulse duration is 100 fs.
- the second harmonic of the OPA idler beam selected from fundamental signal and idler with color filter, is used for two-photon excitation.
- the excitation laser beam is slightly focused and directed to the sample.
- the fluorescence emission originating from two-photon excitation is collected with a spherical mirror, and focused on the entrance slit of an imaging grating spectrometer (Jobin Yvon Triax 550).
- An imaging grating spectrometer Jobin Yvon Triax 550
- a small part of the beam intensity is reflected with a glass, placed before the sample, to the reference detector (Molectron).
- Nonlinear 2PA spectrum is obtained by tuning the wavelength of frequency-doubled OPA output and measuring the intensity of the resulting two-photon excited fluorescence.
- the tuning of OPA and data collection is computercontrolled with a LabView routine, which automatically normalized the fluorescence signal intensity to the square of the excitation intensity, taken from reference channel.
- One of the conjugated porphyrin dimers (yPyyPy), studied therein is used as a reference sample.
- the TPA spectrum is then plotted as the ⁇ 2 value versus excitation frequency.
- the power density of excitation is recalculated to photon density per second per square centimeter.
- Figure 1 shows the long-wavelength part of 1PA spectrum of (4) in dichloromethane solution.
- the solid line represents the best fit of the lowest-frequency (Q1) band to the Voigt function.
- the corresponding Gaussian and Lorentzian widths, as well as the maximum 1 PA cross section value are presented in Table 1.
- FIG. 1 shows the limits of laser frequency range, where the 2PA spectrum is measured in solution.
- the high-frequency boundary (right arrow) corresponds to the point, where the power dependence of fluorescence signal starts to decline from quadratic as a result of non-negligible 1 PA contribution.
- Dashed arrow indicates a frequency of Ti-Saphhire amplifier (790 nm) used for two-photon excitation of (4) in polyethylene film at 77K. Due to much narrower Q 1 band, less contribution of one-photon hot-band absorption, and higher excitation power, the power law is quadratic and the 2PA cross section may be detected in these very strong resonance enhancement conditions.
- Figure 2 demonstrates the 2PA spectrum of (4) in dichloromethane solution at room temperature (open circles).
- An open square represents the datum obtained in polyethylene film at 77K.
- the Voigt fitting of the whole profile is done approximately due to deficiency of data near the maximum.
- the solid curve shown in Fig. 2, is a best fit obtained for the spectral shape of 2PA in liquid solution, with the assumption that the maximum of the band coincides with the experimentally determined center of one-photon Q 1 -transition.
- the corresponding best fit values of Gaussian and Lorentzian widths are presented in Table 1.
- the maximum 2PA cross section, found as an extrapolation of the Voigt fit to the central frequency is extremely large (- 7.2 x 10 4 GM).
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- Optical Record Carriers And Manufacture Thereof (AREA)
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- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
A non-resonant multi-photon absorption material, e.g. for optical data storage, is described wherein a photochromic effect is achieved in a defined volume by 2 photon or multi-photon absorption of a suitable phthalocyanine.
Description
Optical data storage
The present application pertains to a method of 3 dimensional optical volume addressing, useful e.g. for optical data storage, wherein a photochromic effect is achieved in a suitable phthalocyanine by 2 photon absorption, to corresponding uses and optical data storage media including bulk and multilayer material, as well as to novel phthalocyanine compounds.
JP-A-2005-029726 and JP-A-2005-037658 disclose an unresonant multi photon absorption material containing a sensitizing dye or emission color element, including some symmetrical phthalocyanines, for three-dimensional photoshaping, three-dimensional display or three- dimensional optical recording purposes.
It has been found that, surprisingly, using a certain phthalocyanine, especially an unsymmetric one selected, for example, from naphthocyanines, phthalonaphthocyanines or aza-analogues thereof, enhances the 2 photon absorption (PA) cross section by several orders of magnitude. Cross sections thus realized are, for example, of the range σ2 ~ 103 - 104 GM (1GM = 10~50 cm4 s per photon) when approaching the long-wavelength side of the first S0 → Si (Qi) transition.
Besides the enhanced 2PA, especially in the near-infrared range (wavelengths, for example, in the range 1200 - 800 nm, especially about 1100 to about 880 nm), these compounds show further advantageous properties such as
(b) 2PA-induced switching between tautomers in the named range of wavelengths,
(c) low 1 PA in the same range, especially at the same wavelength, which enables 2PA storage in an arbitrary number of layers (e.g. up to 10000 layers, or 1 to 1000 or 2-100 layers; especially about 100 to 1000 layers).
These properties are important for a practical multi-layer optical information storage (OIS) scheme. Based on these findings of the invention, a method of writing and recording of information may comprise the following steps:
(a) preparation of the metastable tautomer (T∑form) in advance by illuminating the recording medium containing the instant phthalocyanine resonantly with Qi-band of Ti tautomer. This is preferably done at lowered temperatures, e.g. at temperatures between about 5OK and room
temperature (e.g. 300K), preferably between about 7OK and 273K. For some specific applications, the process is carried out at about 75-80K, e.g. using liquid nitrogen as coolant.
(b) The bits of information ("1") are written in the bulk of the disk containing a multitude of data layers by using near-resonance two-photon excitation of T2 form (T∑→ Ti transformation). In some specific applications, one bit may be written by one non-amplified femtosecond pulse of the Ti: Sa laser, focused down to a diffraction-limited volume with a large numerical aperture objective. The non-changed voxels are considered as "0".
(c) The bits are read out with near resonant excitation and confocal scheme of collection of fluorescence (e.g. via 1 PA with a cw diode laser) of form Ti.
In a further type of application, data can be erased by
(d) illuminating the material, e.g. the whole sample, in resonance with Ti tautomer absorption, or by increasing the temperature and repeating step (1), thus realizing a rewritable, high density 3 dimensional optical data medium. While bulk data erasion on the whole disk at once has a number of advantages (e.g. high speed, low error rate), for certain applications bit-wise erasion is preferred.
When carrying out steps (b) and (c), temperature is preferably kept in the lower range as explained for step (a).
Preparation of the metastable tautomer (e.g. as in above step a) can be performed with the same laser beam used for writing and reading, e.g. if the laser wavelength is shifted to coincide with the absorption band of the stable form. This does not imply using a second 2PA laser, but may require the wavelength of the same laser to be shifted or filtered accordingly.
Data layers may be located in separated layers of the recording material, or especially in the bulk of the recording material by application of the appropriate adressing technique during writing; in the latter case, the data storage medium preferably contains only one bulk layer of the recording material. Thus, in many cases, data storage will be accomplished in a bulk material, wherein single bits are located in defined spaces of the 3-dimensional structure adressed in a 2 beam technique as previously described in literature. Layer structure and writing/reading device may also be, for example, as described in WO 99/23650.
Phthalo- or naphthocyanines or aza-analogues thereof especially useful in the present invention basically consist of 4 phthalic moieties of the formula:
(Pc; R standing for H or an organic residue, where 2 vicinal R may be interconnected to form a 3-10 membered bridging group, such as a C4-bridging group completing an annellated benzene ring), whose N- and pyrrolic bonds are linked together to form the well known azaporphyrine ring and conforming, for example, to the formula A
The groups attached at the peripheral carbon skeleton can be, for example, -CHO, -
CO-KWradicai> -CH2OH or -COOH, or unsubstituted or substituted formyl, hydroxymethyl or carboxyl groups which may be prepared from -CHO, -CO-KWradicai, -CH2OH or -COOH by methods known per se. Substituted formyl or carbonyl groups are typically their acetals, oximes or hydrazones. Substituted hydroxymethyl groups are typically -CH2-00C-KWradicai or -CH2-O-KWradicai- Substituted carboxyl groups are typically esters or thioesters, such as
-OO-KWradicai or -COS-KWradicai> each KWradicai being any saturated, unsaturated or aromatic unsubstituted or substituted hydrocarbon radical, for example CrC2Oalkyl, CrC20cycloalkyl, CrC2Oalkenyl, CrC20cycloalkenyl, CrC2Oalkynyl, CrC20cycloalkynyl, C6-Ci8aryl or C7-Ci8aralkyl. Further substituents may be chosen in accordance with/in analogy to compounds of formula I of WO98/14520 (see pages 3/4 therein).
Preferably in the above formula A, Gi, G2, G3, G4, Y and Y' independently are H, OH, halogen, nitro, COOG9, Ci-C22alkyl, CrC22alkoxy, CrC22alkylthio, C4-Ci2cycloalkyl, C4- Ci2cycloalkoxy, C4-Ci2cycloalkylthio, aryl, aryloxy, arylthio, wherein each alkyl or alkoxy or alkylthio or aryl or aryloxy or arylthio moiety may be substituted by OH, halogen, amino, nitro, phenyl, phenoxy, carboxy; and wherein each aryl or aryloxy or arylthio moiety may further be substituted by alkyl or alkoxy; and wherein each alkyl or alkoxy or alkylthio moiety containing 2 or more carbon atoms may be interrupted in the carbon chain by O, NH, S, CO, COO, CONH, OCOO, OCONH, NHCONH; G5 and G6 indepently are H, OH, halogen, CrCi2alkyl, CrCi2alkoxy; G9 is H, Ci-C22alkyl, C4-Ci2cycloalkyl, wherein each alkyl may be substituted by OH, halogen, amino, nitro, phenyl, phenoxy, carboxy; and wherein each alkyl or alkoxy moiety containing 2 or more carbon atoms may be interrupted in the carbon chain by O, NH, CO, COO, CONH, OCOO, OCONH, NHCONH; and wherein 2 vicinal substituents on a phenyl ring, preferably G3, G4, and more preferably Y, Y', optionally may be linked to form a 4-membered bridge (CH)xNy, where x is 2 or 3 or 4, y is O or 1 or 2 and x+y =4, to form an annellated aromatic ring.
Preferred bridging group is -Xi=C(G7)-C(G8)=X2-, where G7, G8, Xi and X2 are as defined below for the formula I.
Preferred are compounds wherein at least 1 moiety contains 2 vicinal substituents on the phenyl ring linked to a 4-membered bridge (CH)xNy, where x is 2 or 3 or 4, x is O or 1 or 2 and x+y =4, to form an annellated aromatic ring (moiety Nc). Aromatic CH moieties in each unit may be substituted, the final compounds thus being of the types Pc3Nc, Pc2Nc2, PcNc3 or Nc4. Of special technical importance are phthalonaphthocyanines of the class Pc3Nc.
Compounds useful in the material and process of the invention are often of the formula I
wherein
Gi, G2, G3, G4, Gii, Gi2, Gi3, Gi4, G2i, G22, G23 and G24, independently, are H, OH, halogen, COOG9, CrC22alkyl, CrC22alkoxy, CrC22alkylthio, C4-Ci2cycloalkyl, C4-Ci2cycloalkoxy, wherein each alkyl or alkoxy or alkylthio moiety may be substituted by OH, halogen, amino, nitro, phenyl, phenoxy, carboxy; and wherein each alkyl or alkoxy or alkylthio moiety containing 2 or more carbon atoms may be interrupted in the carbon chain by O, NH, CO, COO, CONH, OCOO, OCONH, NHCONH; or a vicinal pair of residues G3 and G4, Gi3 and Gi4 and/or G23 and G24 together form the annellating group -Xi=C(G7)-C(G8)=X2- while further residues d and G2, Gn and Gi2, G2i and G22 attached to the same phenyl ring are as defined for G5 and G6 below; G5 and G6 indepently are H, OH, halogen, CrCi2alkyl, CrCi2alkoxy; G7 and G8 indepently are H, OH, halogen, COOG9, CrC22alkyl, CrC22alkoxy, CrC22alkylthio, C4-Ci2cycloalkyl, C4-Ci2cycloalkoxy, wherein each alkyl or alkoxy or alkylthio moiety may be substituted by OH, halogen, amino, nitro, phenyl, phenoxy, carboxy; and wherein each alkyl or alkoxy or alkylthio moiety containing 2 or more carbon atoms may be interrupted in the carbon chain by O, NH, CO, COO, CONH, OCOO, OCONH, NHCONH; or G7 and G8 together with the carbon atoms they are bonding to may be bridged together to form an annellated carbocyclic 6-membered aromatic ring, which is unsubstituted or substituted by OH, halogen, COOG9, CrC22alkyl, CrC22alkoxy, CrC22alkylthio, C4- Ci2cycloalkyl, C4-Ci2cycloalkoxy, wherein each alkyl or alkoxy or alkylthio moiety may be substituted by OH, halogen, amino, nitro, phenyl, phenoxy, carboxy; and wherein each alkyl or alkoxy or alkylthio moiety containing 2 or more carbon atoms may be interrupted in the carbon chain by O, NH, CO, COO, CONH, OCOO, OCONH, NHCONH;
G9 is H, CrC22alkyl, C4-Ci2cycloalkyl, wherein each alkyl may be substituted by OH, halogen, amino, nitro, phenyl, phenoxy, carboxy; and wherein each alkyl or alkoxy moiety containing 2 or more carbon atoms may be interrupted in the carbon chain by O, NH, CO, COO, CONH, OCOO, OCONH, NHCONH; Xi and X2 indepently are CH or N.
In analogy to other azaporphyrine-type ring systems, the central protons (hydrogen atoms) may conveniently be replaced completely or partially by heavier atoms such as deuterium, or alkaline (e.g. Li, Na), or replaced completely by a suitable divalent metal ion such as Zn, Mg, Pd on treatment with the appropriate reagents such as deuterated acid or salt, usually in solution. These modified compounds are of the formulae I' or I"
M is a divalent metal atom, for example selected from Mg, Zn, Pd; and all other symbols have the meaning as defined above for formula I. Preferred are, for examples, compounds of the formula I or I', or unsymmetrical (see below) compounds of the formula I".
Especially useful in the present invention are unsymmetrical compounds, i.e. generally those deviating from C4-symmetry, especially wherein the compound deviates from C4- and C2- symmetry (axes perpendicular to the azaporphyrine ring system).
These compounds are thus preferred for use in 3 dimensional information storage media or recording media based on 2-photon absorption. Different tautomeric forms of these compounds may be formulated, especially with respect of the positioning of the symmetry breaking group and the bonding of the central atom(s). All these tautomeric forms are to be understood as falling under the above structures I, I' or I".
Of specific interest therefore are compounds, for example of the formula I, I', or I", wherein the vicinal substituents Gi3 and Gi4 are non-annellated (compound classes Pc3Nc, Pc2Nc2, PcNc3) and, independently, are selected from H, OH, halogen, COOG9, CrC22alkyl, Cr C22alkoxy, CrC22alkylthio, C4-Ci2cycloalkyl, C4-Ci2cycloalkoxy, wherein each alkyl or alkoxy or alkylthio moiety may be substituted by OH, halogen, amino, nitro, phenyl, phenoxy, carboxy; and wherein each alkyl or alkoxy or alkylthio moiety containing 2 or more carbon atoms may be interrupted in the carbon chain by O, NH, CO, COO, CONH, OCOO, OCONH, NHCONH.
More preferred as well are compounds of the formula I, I', or I" wherein all 3 phthalyl moieties contain substituents G3 and G4, Gi3 and Gi4, G23 and G24, in each case together forming the annellating group -Xi=C(G7)-C(G8)=X2- (compound class Nc4), while the compound deviates from C4, especially from C4 and C2-symmetry as explained above; examples of such compounds are those of the formula A containing an odd number of any of the residues Gi, G2, G7, G8 different from hydrogen and/or an odd number of any of Xi or X2 different from ther rest of moieties Xi and X2 in the compound.
These compounds are a further subject of the invention, with the exception of compounds of the formula I wherein one of each of Gi or G2, Gn or Gi2, and G2i or G22 is Ci-d2alkoxy while the other is hydrogen, each of G3, G4, G5, G6, Gi3, Gi4, G23, G24 is hydrogen, and G7 and G8 are Ci-d2alkoxy or CrC22alkylthio or both of G7 and G8 are hydrogen or the bridging group -CH=CH-CH=CH-.
Preferred compounds thereof are those of formula I, I' or I" wherein at least one of G3 and G4, Gi3 and Gi4, G23 and G24, together form the annellating group -Xi=C(G7)-C(G8)=X2- and at least one of Gi, G2, G5, G6, G7, G8, Gn, Gi2, G2i, G22 is different from hydrogen, or wherein Xi is nitrogen.
Halogen is chloro, bromo, fluoro or iodo, preferably chloro or bromo on aryl or heteroaryl or fluoro on alkyl.
Alkyl is, for example, Ci-d2alkyl inter alia comprising methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-methyl-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, n-hexyl, heptyl, n-octyl, 1,1,3,3-tetramethylbutyl, 2-ethylhexyl, nonyl, decyl, undecyl or dodecyl.
Ci-C22Alkyl is straight-chain or branched alkyl radicals, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, isoamyl or tert-amyl, heptyl, octyl, isooctyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl or eicosyl.
Ci -C22AI kylthio is straight-chain or branched alkylthio radicals, such as methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, sec-butylthio, tert-butylthio, amylthio, heptylthio, octyl- thio, isooctylthio, nonylthio, decylthio, undecylthio, dodecylthio, tetradecylthio, pentadecylthio, hexadecylthio, heptadecylthio, octadecylthio or eicosylthio.
C4-Ci2Cycloalkyl includes, for example, cyclopentyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, and preferably cyclohexyl.
Whenever aryl is mentioned, this means mostly C6-Ci2aryl, preferably phenyl or naphthyl, especially phenyl. Aralkyl is usually the alkyl as defined, which is substituted by the above
aryl; preferred is Cy-Cuphenylalkyl. Alk(yl)aryl is the above aryl substituted by alkyl; preferred is phenyl mono-, di- or trisubstituted by CrC4alkyl.
Groups which may be unsubstituted or substituted by selected radicals such as C6-Ci2aryl or Cs-C^cycloalkyl, like a phenyl or a cyclohexyl ring, are preferably unsubstituted or mono-, di- or tri-substituted, especially preferred are these groups unsubstituted or mono- or disubstituted.
Hydrocarbon moieties interrupted by a heterofunctional group (such as alkyl interrupted by - O- or -COO-, which includes -OCO-) denotes a moiety which can be interrupted by one or more of these groups, one group in each case being inserted, in general into one carbon- carbon bond. Hetero-hetero bonds, for example 0-0, generally do not occure (except within the functional group as specified). If an interrupted alkyl is additionally substituted, the substituents are generally not α to the heteroatom.
As known from J. Phys. Chem. A 101 , 6204 (1997), the nonsymmetrical substitution allows for rather good spectral separation of two tautomeric forms in polymer films. Furthermore, both tautomers show very strong and narrow 1 PA S0 → Si (Qi) band in near-IR region, which provides the opportunity to use strong resonance enhancement of 2PA, when exciting in the very vicinity of this band, e.g. using a commercially available femtosecond Ti:sapphire lasers.
Thus, the invention further relates to an optical data storage medium comprising a substrate and at least one recording layer, the recording layer containing a compound of the formula I, I' or I".
Correspondingly, present invention also relates to the use of a compound as initially described as a recording dye in an optical data storage medium, and to a corresponding method of data storage.
The recording medium according to the invention, in addition to comprising the compounds of formula I, I' and/or I", may additionally comprise salts, for example ammonium chloride, pentadecylammonium chloride, sodium chloride, sodium iodide, sodium sulfate, sodium hydrogen sulfate, sodium methyl sulfate, sodium methylsulfonate, sodium tosylate, sodium
acetate, sodium hexafluorophosphate, cobalt(II) acetate or cobalt(II) chloride, the ions of which may, for example, originate from the components used.
The compounds of formula I, F and/or I" may also be used in combination with the known dyes such as known in the art especially for recording media based on 2 photon absorption.
The substrate, which acts as support for the layer(s) applied thereto, is advantageously semi- transparent (T > 10%) or preferably transparent (T>90%). The support can be from 0.01 to 10 mm thick, preferably from 0.1 to 5 mm thick.
Especially in case that a multitude of recording layers is used, the thickness of each layer may range from about 0.1 to about 50 micron 1), preferably from 0.5 to 30 μm, especially from about 3 to 10 μm, e.g. about 5 such as 2 - 7 μm. The linear absorption of the recording layer is advantageously low (optical density typically below 1 , absorption preferably below 0.01 , e.g. about 10~4 - 10~3) at the absorption maximum (2PA). Each recording layer may comprise thinner sub-layers, such as grooves or tracks, where the recording material is present.
A protective layer can, if desired, serve also as adhesion promoter for a second substrate layer applied thereto, which is preferably from 0.1 to 5 mm thick and consists of the same material as the support substrate.
Suitable substrates are, for example, glass, minerals, ceramics and thermosetting or thermoplastic plastics. Preferred supports are glass and homo- or co-polymeric plastics. Suitable plastics are, for example, thermoplastic polycarbonates, polyamides, polyesters, polyacrylates and polymethacrylates, polyurethanes, polyolefins, polyvinyl chloride, polyvinylidene fluoride, polyimides, thermosetting polyesters and epoxy resins. The substrate can be in pure form or may also comprise customary additives, for example UV absorbers or dyes, as proposed e.g. in JP 04/167 239 to provide light-stabilisation for the recording layer. In the latter case it may be advantageous for the dye added to the support substrate to have an absorption maximum hypsochromically shifted relative to the dye of the recording layer by at least 10 nm, preferably by at least 20 nm.
For a further increase in stability it is also possible, if desired, to add known stabilisers in customary amounts, for example a nickel dithiolate described in JP 04/025 493 as light stabiliser.
Further customary constituents are possible, for example other chromophores (for example those having an absorption maximum at from 300 to 1000 nm), UV absorbers and/or other stabilisers, 1O2-, triplet- or luminescence-quenchers, melting-point reducers, decomposition accelerators or any other additives that have already been described in optical recording media, for example film-formers.
The recording layer comprises a compound of formula I, I' and/or I" or a mixture of such compounds advantageously in an amount sufficient to provide a substantial two-photon absorption in a layer, while playing no substantial influence or at least only a low influence on the refractive index, for example from about 0.1 % to about 10% by weight, or up to 20% by weight, preferably about 1% by weight such as 0.5 to 5%, based on the total recording layer.
Due to their unique properties regarding 2 photon absorption, the present phthalocyanines may generally be used for three-dimensional (3D) volume addressing including purposes other than optical information storage, wherein these properties are useful; many examples for such applications are described in WO97/09043 or the publications initially mentioned, such as photodynamic therapy (especially cancer therapy), or 2 photon initiation of reactions (e.g. polymerization or coloration reactions, modulation of index of refraction, emission of light). Further applications wherein the effect of the invention may advantageously be exploited include the following ones: security printing - insertion of a 3D invisible image which only appears when IR lasers are used - optical effects; smart systems for tagging etc. (information storage for control and for reading); 3D microstructured phase fabrication in a stable polymer host matrix; 3D photoshaping composition; stereolithography; 3D display; optical limiting; optical memory applications; microfabrication; rational drug delivery.
General preparation procedure
Compounds of the formula A may be obtained by condensation of a suitable aromatic dicarbonitrile educt, e.g. of the formula
where GrG4 is as defined above, in presence of a base. Reactions are usually carried out in a solvent, which may be identical with the base. Suitable solvents are, for example, aromatic or aliphatic hydrocarbons, alcohols, ethers, or mixtures thereof. As bases may be used, for example, alcoholates such as Li-, Na-, K-alkoholates, where the alkohol may inter alia be selected from Ci-C8hydroxyalkanes or Ci-C8alkoxy-C2-C8hydroxyalkanes; further bases suitable include alkaline sulphides such as Li or Na sulphides, or non-nucleophilic amines such as DBU, DBN and the like. Reactions are often carried out in the range from room temperature to reflux temperature of the solvent or, for example, in the range 20 - 100 0C. Reactions may be carried out using a protective atmosphere under normal, reduced or increased pressure, e.g. under argon or nitrogen atmosphere.
In order to obtain a certain class of asymmetric product, e.g. of the classes Pc3Nc, Pc3An, Nc3An, Nc3Pc, An3Pc, An3Nc, the ratio of dicarbonitrile educts major component: minor component is preferably around 9 : 1, e.g. in the range (7 - 9.5) : (3 - 0.5).
Purification and separation of isomers may be achieved by techniques commonly known such as liquid chromatography.
Compounds containing substituted aromatic rings (e.g. corresponding to formula A wherein at least one of GrG6and Y and Y' is different from hydrogen and at least one pair of Gi, G2, or G3, G4, or G5, G6, or Y, Y' on the same phenyl ring are not identical) usually are obtained as mixtures of 4 isomers, one thereof conforming to the C4-symmetry. Isomers may be separated using conventional techniques such as chromatography, or may be used as mixtures.
The following examples are for illustrative purposes only and are not to be construed to limit the instant invention in any manner whatsoever. Room temperature depicts a temperature in the range 20-25°C. Percentages are by weight unless otherwise indicated. Abbreviations used in the examples or elsewhere:
M concentration in moles per litre Pc building block based on a phthalonitrile Nc building block based on a naphthalene-2,3-dicarbonitrile Ac building block based on an anthracene-2,3-dicarbonitrile NMP N-methyl-2-pyrrolidone λmax linear absorption maximum (nm)
Preparation examples according to J. Phys. Chem. A 101 , 6204 (1997) Starting Materials 3-(2,4-Dimethyl-3-pentoxy)phthalonitrile (1), βJ-Dimethoxy-naphthalene^S-dicarbonitrile (2), and Anthracene-2,3-dicarbonitrile (3) are prepared according to the above reference.
Example 1
Pc3Nc (4). In a 3.5 L three-necked round-bottomed flask, equipped with a stirrer, a reflux condenser, and a thermometer, are charged 1.8 L of methoxyethanol and heated under nitrogen to 50 * C. Lithium powder [19.2 g (2.7 mol)] is added in small portions within 4 h keeping the temperature at 50 ° C. 1 [60.5 g (0.25 mol)] and 4.9 g (0.0275 mol) of naphthalene-2,3-dicarbonitrile are added, and the resulting solution is heated with reflux for 18 h. The resulting green solution is cooled to room temperature, 1 L of acetic acid is added drop by drop within 1 h, and the solution is stirred for 30 min. The solution is evaporated, the residue is dissolved in CH2CI2, 100 g of silica gel is added, and the slurry evaporated. The green powder is placed on top of a column with 500 g of silica gel, and the symmetrical side product (Rf = 0.73) and the product (Rf = 0.57) are eluted with hexane/ethyl acetate 10:1. The fractions containing the desired product are collected, evaporated, and subjected to a second chromatography. Yield: 1.05 g (4.2%) of 4 as a green powder. TLC (hexane/ethyl acetate 10:1): Rf = 0.57. UV (NMP): JW = 757/715 nm. PD-MS (PD-MS = plasma desorption mass spectrometry): (M + H)+ = 907.5.
Example 2
Pc3Nc(OCH3)2 (5). In the same manner, 9.2 g (38.15 mmol) of 1 and 1 g (4.19 mmol) of 2 are reacted. The crude product is purified twice with column chromatography (hexane/ethyl acetate = 7:3) to yield 0.15 g (1.5%) 5 as a green powder. TLC (hexane/ethyl acetate 7:3): Rf = 0.69. UV (NMP): ;w = 757/718 nm. PD-MS: (M + H)+ = 969.9.
Pc3Nc(SC12H25)2 (6). In the same manner, 21.2 g (87.50 mmol) of 1 and 5.62 g (9.71 mmol) of 6,7-dodecylthionaphthalene-2,3-dicarbonitrile15 are reacted. The crude product is purified
twice with column chromatography (hexane/ethyl acetate 7:1) to yield 0.61 g (4.8%) of 6 as a green powder. TLC (hexane/ethyl acetate 7:1): Rf = 0.75. UV (NMP): A018x = 760/724 nm. PD- MS: (M + H)+ = 1309.1.
Example 3 Pc3An (7). In the same manner, 9.55 g (39.43 mmol) of 1 and 1 g (4.38 mmol) of 3 are reacted. The crude product is purified with column chromatography (hexane/ethyl acetate 7:3). The fractions containing the desired product are evaporated, and the residue is dissolved in 15 mL toluene and added drop by drop to 300 ml. of methanol. The precipitated product is isolated by filtration and dried at 60 * C/125 Torr overnight to yield 0.15 g (1.5%) 7 as a green powder. TLC (hexane/ethyl acetate 9:1): Rf = 0.49. UV (NMP): ;w = 783/735/708 nm. MALDI-MS (MALDI-MS = matrix-assisted laser desorption/ionization mass spectrometry): (M + H)+ = 958.8.
The chemical structure of the more stable tautomer (configuration of protons) of mixed Pc3Nc1S (4-7) of examples 1-3 is given by the formula:
(5) R = OCH3
(7) R = -CH=CH-CH=CH-
Example 4 The following compounds are prepared according to the procedure given in example 1 from appropriately substituted benzene-, naphthalene- and/or anthracene-2,3-dicarbonitriles obtained in analogy to compounds (1), (2) or (3):
Pc3Nc (8):
Nc4 (9):
PcNc3 (10):
Pc4 (H):
Pc4 (12):
(λmax (NMP) = 742/716 nm)
Pc4 (13):
(λmax (NMP) = 740/714 nm)
Pc4 (14):
( λmax (NMP) = 738/710 nm)
Pc4 (15):
( λmax (NMP) = 711/678 nm)
As noted further above, separation of isomers is achieved by column chromatography.
Compounds as described above, either in form of a selected isomer as described in example 1 , or as mixture, are used in the application experiments described further below either in solution or incorporated into a polymer film, especially a polyethylene film, which is prepared according to the method described in J. Phys. Chem. A 101, 6204 (1997).
Application example 1
Experimental Setup and Methods: Linear absorption spectra are measured with a Lambda 900 Perkin Elmer spectrophotometer. The laser system comprises a Ti: sapphire femtosecond oscillator (Coherent Mira 900) pumped by 5W CW frequencydoubled Nd:YAG laser (Coherent Verdi), and a 1-kHz repetition rate Ti:sapphire femtosecond regenerative amplifier (CPA-1000, Clark MXR). The pulses from the amplifier are down converted with an optical parametric amplifier, OPA (TOPAS, Quantronix), whose output can be continuously tuned from 1100 to 2000 nm. The OPA output pulse energy is 100 - 200
microJ (5 - 10 microJ after frequency doubling of idler), and pulse duration is 100 fs. The second harmonic of the OPA idler beam, selected from fundamental signal and idler with color filter, is used for two-photon excitation.
The excitation laser beam is slightly focused and directed to the sample. The fluorescence emission originating from two-photon excitation is collected with a spherical mirror, and focused on the entrance slit of an imaging grating spectrometer (Jobin Yvon Triax 550). A small part of the beam intensity is reflected with a glass, placed before the sample, to the reference detector (Molectron).
Nonlinear 2PA spectrum is obtained by tuning the wavelength of frequency-doubled OPA output and measuring the intensity of the resulting two-photon excited fluorescence. The tuning of OPA and data collection is computercontrolled with a LabView routine, which automatically normalized the fluorescence signal intensity to the square of the excitation intensity, taken from reference channel.
Absolute TPA cross section is measured at λΘX = 930 nm by using the relative fluorescence method described in J. Phys. Chem. B 109, 7223-7236, (2005). One of the conjugated porphyrin dimers (yPyyPy), studied therein is used as a reference sample.
The TPA spectrum is then plotted as the σ2 value versus excitation frequency. For this representation, the power density of excitation is recalculated to photon density per second per square centimeter.
One- and two-photon absorption spectroscopy of non-symmetrical phthalo-naphthalocyanine
Pc3Nc (4):
Figure 1 shows the long-wavelength part of 1PA spectrum of (4) in dichloromethane solution. The solid line represents the best fit of the lowest-frequency (Q1) band to the Voigt function. The corresponding Gaussian and Lorentzian widths, as well as the maximum 1 PA cross section value are presented in Table 1.
Vertical arrows in Fig. 1 show the limits of laser frequency range, where the 2PA spectrum is measured in solution. The high-frequency boundary (right arrow) corresponds to the point, where the power dependence of fluorescence signal starts to decline from quadratic as a result of non-negligible 1 PA contribution. Dashed arrow indicates a frequency of Ti-Saphhire amplifier (790 nm) used for two-photon excitation of (4) in polyethylene film at 77K. Due
to much narrower Q1 band, less contribution of one-photon hot-band absorption, and higher excitation power, the power law is quadratic and the 2PA cross section may be detected in these very strong resonance enhancement conditions. Figure 2 demonstrates the 2PA spectrum of (4) in dichloromethane solution at room temperature (open circles). An open square represents the datum obtained in polyethylene film at 77K. The Voigt fitting of the whole profile is done approximately due to deficiency of data near the maximum.
The solid curve, shown in Fig. 2, is a best fit obtained for the spectral shape of 2PA in liquid solution, with the assumption that the maximum of the band coincides with the experimentally determined center of one-photon Q 1 -transition. The corresponding best fit values of Gaussian and Lorentzian widths are presented in Table 1. The maximum 2PA cross section, found as an extrapolation of the Voigt fit to the central frequency is extremely large (- 7.2 x 104 GM).
The results show that (4) provides an extremely high intrinsic femtosecond 2PA cross section (10~47- 10~46) in the excitation region of 800 - 950 nm.
Table 1. One- and two-photon absorption properties (in dichloromethane) and photo- tautomerization quantum efficiency (in PVB film)) of two tautomeric forms of Pc3Nc
λmax - 1 PA peak wavelength,
δi,2 - Gaussian widths of 1PA and 2PA profiles,
Ti - Lorentzian widths of 1 PA and 2PA profiles,
TR - radiative lifetime,
φT - quantum efficiency of tautomerziation.
•Calculated from the oscillator strength value;
"measured in PVB film at 1OK (from J. Phys. Chem. A 101, 6202-6213 (1997)).
Application example 2
Experimental method generally is as described in example 1 ; absolute 2 photon absorption (2PA) cross section is measured at λΘX=897 nm using relative fluorescence [see M. Drobizhev, Y, Stepanenko, Y. Dzenis, A. Karotki, A. Rebane, P.N. Taylor, H. L. Anderson, "Extremely strong near-IR two-photon absorption in conjugated porphyrin dimers: Quantitative description with three-essential-states model", J. Phys. Chem. B 109, 7223- 7236 (2005), or patent applications mentioned above].
Measured cross-section values, concentrations, linear extinction coefficients, quantum yields, stable switching temperature and FOM (for maximum measured cross-sections) are summarized in Table 2; compound numbers are those of compounds listed in the above preparation examples.
Summarizing the data, it is concluded that the compounds (7) and (13) are the most promising from the point of view of 2PA cross-section. The highest temperature stability is found for compounds (11) and (5), (12). Compound (11) is also found preferable in regard of quantum yields.
Claims
1. A method of optical data storage including recording and reading of information comprising the steps
(a) preparation of the metastable tautomer (T∑form) of a suitable phthalocyanine as the recording dye by illuminating the recording medium containing the phthalocyanine resonantly with Qi-band of Ti tautomer;
(b) writing the bits of information into the bulk of the disk, e.g. containing a multitude of data layers, by using near-resonance two-photon excitation of T∑form (T∑→ Ti transformation of the recording dye); and
(c) reading out the bits with near resonant excitation and confocal scheme of collection of fluorescence of form Ti.
2. Method of claim 1 , further comprising the step of data erasing by (d) illuminating the recording medium in resonance with Ti tautomer absorption, or by increasing the temperature and repeating step (a), thus realizing a rewritable, high density 3 dimensional optical data medium.
3. Method of claim 1, where in steps (a), (b) and (c), the temperature is preferably kept in the range from 50 to 300K.
4. Method of any of claims 1-3, wherein the phthalocyanine in the recording medium conforms to formula A
G9 is H, CrC22alkyl, C4-Ci2cycloalkyl, wherein each alkyl may be substituted by OH, halogen, amino, nitro, phenyl, phenoxy, carboxy; and wherein each alkyl or alkoxy moiety containing 2 or more carbon atoms may be interrupted in the carbon chain by O, NH, CO, COO, CONH, OCOO, OCONH, NHCONH; and wherein 2 vicinal substituents on a phenyl ring, preferably G3, G4, and more preferably Y, Y', optionally may be linked to form a 4-membered bridge (CH)xNy, where x is 2 or 3 or 4, y is O or 1 or 2 and x+y =4, to form an annellated aromatic ring.
5. Non-resonant multi-photon absorption material containing a compound of the formula I, I' and/or I"
or a tautomeric or mesomeric form thereof, wherein
Gi, G2, G3, G4, Gii, Gi2, Gi3, Gi4, G2i, G22, G23 and G24, independently, are H, OH, halogen, COOG9, CrC22alkyl, CrC22alkoxy, CrC22alkylthio, C4-Ci2cycloalkyl, C4-Ci2cycloalkoxy, wherein each alkyl or alkoxy or alkylthio moiety may be substituted by OH, halogen, amino, nitro, phenyl, phenoxy, carboxy; and wherein each alkyl or alkoxy or alkylthio moiety containing 2 or more carbon atoms may be interrupted in the carbon chain by O, NH, CO, COO, CONH, OCOO, OCONH, NHCONH; or a vicinal pair of residues G3 and G4, Gi3 and Gi4 and/or G23 and G24 together form the annellating group -Xi=C(G7)-C(G8)=X2- while further residues d and G2, Gn and Gi2, G2i and G22 attached to the same phenyl ring are as defined for G5 and G6 below; G5 and G6 indepently are H, OH, halogen, CrCi2alkyl, CrCi2alkoxy; G7 and G8 indepently are H, OH, halogen, COOG9, Ci-C22alkyl, Ci-C22alkoxy, Ci-C22alkylthio, C4-Ci2cycloalkyl, C4-Ci2cycloalkoxy, wherein each alkyl or alkoxy or alkylthio moiety may be substituted by OH, halogen, amino, nitro, phenyl, phenoxy, carboxy; and wherein each alkyl or alkoxy or alkylthio moiety containing 2 or more carbon atoms may be interrupted in the carbon chain by O, NH, CO, COO, CONH, OCOO, OCONH, NHCONH; or G7 and G8 together with the carbon atoms they are bonding to may be bridged together to form an annellated carbocyclic 6-membered aromatic ring, which is unsubstituted or substituted by OH, halogen, COOG9, CrC22alkyl, CrC22alkoxy, CrC22alkylthio, C4- Ci2cycloalkyl, C4-Ci2cycloalkoxy, wherein each alkyl or alkoxy or alkylthio moiety may be substituted by OH, halogen, amino, nitro, phenyl, phenoxy, carboxy; and wherein each alkyl or alkoxy or alkylthio moiety containing 2 or more carbon atoms may be interrupted in the carbon chain by O, NH, CO, COO, CONH, OCOO, OCONH, NHCONH; G9 is H, CrC22alkyl, C4-Ci2cycloalkyl, wherein each alkyl may be substituted by OH, halogen, amino, nitro, phenyl, phenoxy, carboxy; and wherein each alkyl or alkoxy moiety containing 2 or more carbon atoms may be interrupted in the carbon chain by O, NH, CO, COO, CONH, OCOO, OCONH, NHCONH; Xi and X2 indepently are CH or N;
D stands for deuterium or an alkali atom such as Li or Na, and one of the residues D may still be unmodified hydrogen; and M is a divalent metal atom, for example selected from Mg, Zn, Pd.
6. Material of claim 5 which is an optical data storage medium comprising a substrate and at least one recording layer, the recording layer containing the compound of the formula I, I' and/or I".
7. Material of claim 5 comprising the compound of the formula I, I' and/or I" as sensitizing dye or light emission element, and at least one further component suitable for initiation of a chemical reaction, polymerization reaction, colouration, refractive index modulation.
8. Method for the 3 dimensional optical addressing in a bulk material by 2 photon absorption of a suitable phthalocyanine as the sensitizing dye, especially a phthalocyanine deviating from C4-symmetry.
9. Method of claim 8 for optical information storage, photodynamic therapy such as cancer therapy, initiation of a chemical reaction, polymerization, colouration, refractive index modulation, light emission, photoshaping, rational drug delivery.
10. Method of claim 8 for optical data storage, wherein data writing is achieved by 2 photon absorption of a suitable phthalocyanine as the recording dye, especially a phthalocyanine deviating from C4-symmetry.
11. Method of claim 9, wherein the recording dye is a compound of formula AJJ' and/or I" as described in claims 4 or 5.
12. Method of claim 8, wherein the recording dye is a compound of formula A, I, I' and/or I" as described in claims 4 or 5.
13. Use of a phthalocyanine compound, especially deviating from C4-symmetry, for optical data storage in a bulk material or a multitude of recording layers by 2 photon absorption.
14. Use of a compound of formula I, I' and/or I" as described in claim 5 as a non-resonant sensitizing dye or light emission element, especially for optical information storage, photodynamic therapy, cancer therapy, refractive index modulation, light emission, photoshaping, rational drug delivery, or for the initiation of a chemical reaction such as polymerization, colouration.
15. Use of a compound of formula I, I' and/or I" according to claim 14 as a recording dye for optical data storage.
16. A compound of formula I or I' or I" according to claim 5, or a tautomeric or mesomeric form thereof, deviating from C4, especially from C4 and C2-symmetry relative to the axis perpendicular to the ring plane, wherein Gi3 and Gi4, independently, are H, OH, halogen, COOG9, CrC22alkyl, CrC22alkoxy, Ci-C22alkylthio, C4-Ci2cycloalkyl, C4-Ci2cycloalkoxy, where each alkyl or alkoxy or alkylthio moiety may be substituted by OH, halogen, amino, nitro, phenyl, phenoxy, carboxy; and wherein each alkyl or alkoxy or alkylthio moiety containing 2 or more carbon atoms may be interrupted in the carbon chain by O, NH, CO, COO, CONH, OCOO, OCONH, NHCONH; or wherein each of the vicinal substituents G3 and G4, Gi3 and Gi4, G23 and G24, in each case together form an annellating group -Xi=C(G7)-C(G8)=X2-; with the exception of compounds of the formula I wherein
(a) one of each pair d or G2, Gn or Gi2, and G2i or G22 is Ci-d2alkoxy while the other is hydrogen,
(b) each of G3, G4, G5, G6, Gi3, Gi4, G23, G24 is hydrogen, and
(c) any of G7 and G8 are Ci-d2alkoxy or CrC22alkylthio or both of G7 and G8 are hydrogen or the bridging group -CH=CH-CH=CH-.
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| US60/708,544 | 2005-08-16 | ||
| US73434105P | 2005-11-07 | 2005-11-07 | |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100546065C (en) * | 2007-05-24 | 2009-09-30 | 同济大学 | A kind of asymmetric phthalocyanine material and preparation method thereof |
| US8330726B2 (en) | 2003-05-19 | 2012-12-11 | Xiroku, Inc. | Position detection apparatus using area image sensor |
| JP2022123689A (en) * | 2021-02-12 | 2022-08-24 | 東洋インキＳｃホールディングス株式会社 | Near-infrared absorbing dye, near-infrared absorbing composition, and optical filter |
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| JP2001520637A (en) * | 1995-09-06 | 2001-10-30 | ザ・リサーチ・ファンデーション・オブ・ステート・ユニバーシティ・オブ・ニューヨーク | Two-photon upconverting dyes and applications |
| AU1582199A (en) * | 1997-10-31 | 1999-05-24 | Omd Devices Llc | Multi-layered photochromic optical data disk |
| US7771915B2 (en) * | 2003-06-27 | 2010-08-10 | Fujifilm Corporation | Two-photon absorbing optical recording material and two-photon absorbing optical recording and reproducing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8330726B2 (en) | 2003-05-19 | 2012-12-11 | Xiroku, Inc. | Position detection apparatus using area image sensor |
| CN100546065C (en) * | 2007-05-24 | 2009-09-30 | 同济大学 | A kind of asymmetric phthalocyanine material and preparation method thereof |
| JP2022123689A (en) * | 2021-02-12 | 2022-08-24 | 東洋インキＳｃホールディングス株式会社 | Near-infrared absorbing dye, near-infrared absorbing composition, and optical filter |
| JP7182049B2 (en) | 2021-02-12 | 2022-12-02 | 東洋インキＳｃホールディングス株式会社 | Near-infrared absorbing dye, near-infrared absorbing composition, and optical filter |
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