JP4000310B2 - 光エネルギー変換触媒 - Google Patents
光エネルギー変換触媒 Download PDFInfo
- Publication number
- JP4000310B2 JP4000310B2 JP2003344760A JP2003344760A JP4000310B2 JP 4000310 B2 JP4000310 B2 JP 4000310B2 JP 2003344760 A JP2003344760 A JP 2003344760A JP 2003344760 A JP2003344760 A JP 2003344760A JP 4000310 B2 JP4000310 B2 JP 4000310B2
- Authority
- JP
- Japan
- Prior art keywords
- pynim
- zntpp
- benzonitrile
- energy conversion
- complex
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000003054 catalyst Substances 0.000 title claims description 23
- 238000006243 chemical reaction Methods 0.000 title claims description 13
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims description 77
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 150000004032 porphyrins Chemical class 0.000 claims description 11
- YIYFFLYGSHJWFF-UHFFFAOYSA-N [Zn].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Zn].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 YIYFFLYGSHJWFF-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 description 17
- 230000027756 respiratory electron transport chain Effects 0.000 description 15
- 238000000926 separation method Methods 0.000 description 12
- 239000003495 polar organic solvent Substances 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 238000000862 absorption spectrum Methods 0.000 description 9
- 230000001052 transient effect Effects 0.000 description 8
- 238000002835 absorbance Methods 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 6
- 238000001362 electron spin resonance spectrum Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 150000005838 radical anions Chemical class 0.000 description 3
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 2
- NUKYPUAOHBNCPY-UHFFFAOYSA-N 4-aminopyridine Chemical compound NC1=CC=NC=C1 NUKYPUAOHBNCPY-UHFFFAOYSA-N 0.000 description 2
- 0 CC(C1)C(/C(/c2ccccc2)=C(/CC2)\*(*)/C2=C(\C(C=C2)=N/C2=C2/P(C)=C)/c3ccccc3)=N/C1=C(/*=C)\c1ccc2[n]1 Chemical compound CC(C1)C(/C(/c2ccccc2)=C(/CC2)\*(*)/C2=C(\C(C=C2)=N/C2=C2/P(C)=C)/c3ccccc3)=N/C1=C(/*=C)\c1ccc2[n]1 0.000 description 2
- NYHXQUAJSMJFLI-UHFFFAOYSA-N CCCCCCn1c(=O)c2ccc3c4c(ccc(c24)c1=O)c(=O)n(-c1ccncc1)c3=O Chemical group CCCCCCn1c(=O)c2ccc3c4c(ccc(c24)c1=O)c(=O)n(-c1ccncc1)c3=O NYHXQUAJSMJFLI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229960001701 chloroform Drugs 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229960004979 fampridine Drugs 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- YTVNOVQHSGMMOV-UHFFFAOYSA-N naphthalenetetracarboxylic dianhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=C2C(=O)OC(=O)C1=C32 YTVNOVQHSGMMOV-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- -1 tetramethyl semiquinone radical Chemical compound 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- OQNGCCWBHLEQFN-UHFFFAOYSA-N chloroform;hexane Chemical compound ClC(Cl)Cl.CCCCCC OQNGCCWBHLEQFN-UHFFFAOYSA-N 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000004992 fast atom bombardment mass spectroscopy Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000003818 flash chromatography Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- KIQQAJNFBLKFPO-UHFFFAOYSA-N magnesium;porphyrin-22,23-diide Chemical compound [Mg+2].[N-]1C(C=C2[N-]C(=CC3=NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 KIQQAJNFBLKFPO-UHFFFAOYSA-N 0.000 description 1
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 150000005837 radical ions Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- GAJNYDMQZMSRDH-UHFFFAOYSA-N zinc 5,10,15,20-tetraphenyl-21,23-dihydroporphyrin Chemical compound [Zn++].c1cc2nc1c(-c1ccccc1)c1ccc([nH]1)c(-c1ccccc1)c1ccc(n1)c(-c1ccccc1)c1ccc([nH]1)c2-c1ccccc1 GAJNYDMQZMSRDH-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Description
で表される亜鉛(II)テトラフェニルポルフィリン(以下、ZnTPP という)などの亜鉛ポルフィリン、マグネシウムポルフィリンなどが挙げられる。これらの中では、ZnTPP が好ましい。
で表されるように、超分子錯体(ZnTPP-PyNIm) が生成し、この生成した超分子錯体は、5℃において、CS状態の寿命が880 μs と非常に長いという特徴を有する。
ナフタレン-1,4,5,8- テトラカルボン酸二無水物10mmol(10mmol)、4-アミノピリジン1.88g(20mmol) およびヘキシルアミン1.01g(10mmol) を乾燥させたN,N-ジメチルホルムアミド400mL に25℃で溶解させた後、攪拌下、窒素ガス雰囲気中で90℃の温度で12時間加熱した。
MALDI-TOF MS m/z 428(M+ H+ )
25℃のベンゾニトリルにZnTPP (2.7×10-6M)を溶解させ、得られた溶液に種々の濃度のPyNIm(0〜8.6 ×10-3M)を添加した後、その溶液の紫外−可視光スペクトルを調べた。その結果を図1(a) に示す。なお、図1(a) において、矢印は、PyNIm の濃度が増大する方向を意味する。
[ZnTPP]0/(A0-A) =1/(εc −εp )+(K[PyNIm](εc - εp ))-1 (2)
(式中、A0およびA は、それぞれ、PyNIm の非存在下または存在下における波長431nm でのZnTPP の吸光度、εp およびεc は、それぞれ、PyNIm の非存在下または存在下における波長431nm でのモル吸光係数を示す)
で与えられ、[ZnTPP]0/(A0-A) と[PyNIm] -1とが直線関係にあることが予測される。
2.7 ×10-6M のZnTPP ベンゾニトリル溶液に、PyNIm を0〜4.3 ×10-3M の範囲内の種々の濃度となるように添加し、波長600 〜700nm における蛍光強度を測定した。その結果を図2に示す。図2において、矢印は、PyNIm の濃度の増大とともに蛍光強度が変化する方向を示す。
ZnTPP 1.0 ×10-4M およびPyNIm 8.6 ×10-3M のベンゾニトリル溶液の還元電位をサイクリック・ボルタモメトリーにより、測定した。
ZnTPP (5.4×10-6M)およびPyNIm (8.6×10-3M)の脱気されたベンゾニトリル溶液に波長431nm のレーザーで励起させて20μs 経過した後、25℃でその溶液について過渡吸収スペクトルをナノセカンドレーザー光分解により調べた。その結果を図3に示す。また、図3の上部には、波長620nm における吸光度の減衰に対する一次プロットを示す。
25℃における超分子錯体([ZnTPP]-[PyNIm]錯体)のCS状態の寿命を620nm における吸光度変化を測定することによって決定した。その結果、そのCS状態の寿命は、25℃において、630 μs であった。これよりも長い寿命(880μs)は、5℃で得られた。この寿命は、共有結合的または非共有結合的に結合している電子供与体−電子受容体系の化合物の溶液において、これまでに報告されているCS状態のなかでもっとも寿命が長い。
ZnTPP(5.4 ×10-6M)および PyNIm(7.8×10-3M)の脱気されたベンゾニトリル溶液のESR スペクトルを、-100℃で高圧水銀灯を用いて光励起下で測定した。その結果を図6(a) に示す。
Claims (3)
- 金属ポルフィリンおよびピリジルナフタレンジイミドをベンゾニトリルに溶解してなる光エネルギー変換触媒。
- 金属ポルフィリンが、亜鉛ポルフィリンである請求項1記載の光エネルギー変換触媒。
- 金属ポルフィリンの量が、ピリジルナフタレンジイミド1モルあたり0.001 〜1モルである請求項1または2記載の光エネルギー変換触媒。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2003344760A JP4000310B2 (ja) | 2003-10-02 | 2003-10-02 | 光エネルギー変換触媒 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2003344760A JP4000310B2 (ja) | 2003-10-02 | 2003-10-02 | 光エネルギー変換触媒 |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2005111297A JP2005111297A (ja) | 2005-04-28 |
JP4000310B2 true JP4000310B2 (ja) | 2007-10-31 |
Family
ID=34538286
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2003344760A Expired - Fee Related JP4000310B2 (ja) | 2003-10-02 | 2003-10-02 | 光エネルギー変換触媒 |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP4000310B2 (ja) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4201339B2 (ja) | 2004-03-10 | 2008-12-24 | 独立行政法人科学技術振興機構 | パイ電子系拡張ビオローゲン誘導体とポルフィリンとの超分子錯体を用いる光電荷分離 |
-
2003
- 2003-10-02 JP JP2003344760A patent/JP4000310B2/ja not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
JP2005111297A (ja) | 2005-04-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Accorsi et al. | 1, 10-Phenanthrolines: versatile building blocks for luminescent molecules, materials and metal complexes | |
Cárdenas et al. | Synthesis, X-ray structure, and electrochemical and excited-state properties of multicomponent complexes made of a [Ru (tpy) 2] 2+ unit covalently linked to a [2]-catenate moiety. Controlling the energy-transfer direction by changing the catenate metal ion | |
Campagna et al. | Syntheses, absorption spectra, luminescence properties, and electrochemical behavior of mono-and binuclear ruthenium (II) complexes of isomeric bis (2-pyridyl) pyrazines | |
Verma et al. | Photophysical properties of ligand localized excited state in ruthenium (ii) polypyridyl complexes: A combined effect of electron donor–acceptor ligand | |
Bhaumik et al. | Luminescent bis-tridentate ruthenium (II) and osmium (II) complexes based on terpyridyl-imidazole ligand: synthesis, structural characterization, photophysical, electrochemical, and solvent dependence studies | |
Vinogradov et al. | Electrostatic core shielding in dendritic polyglutamic porphyrins | |
Zhou et al. | Fullerene polypyridine ligands: synthesis, ruthenium complexes, and electrochemical and photophysical properties | |
WO2012122605A1 (en) | Iridium based complex for water splitting | |
Murata et al. | Syntheses, photophysical properties, and reactivities of novel bichromophoric Pd complexes composed of Ru (II)–polypyridyl and naphthyl moieties | |
Aliprandi et al. | Chiral Amplification by Self‐Assembly of Neutral Luminescent Platinum (II) Complexes | |
Ahmed | Photochromism of dihydroindolizines Part VI: synthesis and photochromic behavior of a novel type of IR‐absorbing photochromic compounds based on highly conjugated dihydroindolizines | |
Busche et al. | Novel RuII Complexes with Bispidine‐Based Bridging Ligands: Luminescence Sensing and Photocatalytic Properties | |
Girardot et al. | Novel ruthenium (II) and zinc (II) complexes for two-photon absorption related applications | |
Takeda et al. | Synthesis and characterization of novel flavin-linked porphyrins. Mechanism for flavin-catalyzed inter-and intramolecular 2e/1e electron-transfer reactions | |
JP3953037B2 (ja) | 多数の人工光合成反応中心を有する亜鉛ポルフィリンデンドリマーとピリジルナフタレンジイミドとの超分子錯体 | |
JP4000310B2 (ja) | 光エネルギー変換触媒 | |
Garlaschelli et al. | Fullerene ylidene malonate supramolecular triads | |
Hettegger et al. | Chemistry of the redox series from hexahydroxybenzene to cyclohexanehexaone | |
Coronado et al. | Fast redox-triggered shuttling motions in a copper rotaxane based on a phenanthroline–terpyridine conjugate | |
Laemmel et al. | Macrocyclic Complexes of [Ru (N‐N) 2] 2+ Units [N‐N= 1, 10 Phenanthroline or 4‐(p‐Anisyl)‐1, 10‐Phenanthroline]: Synthesis and Photochemical Expulsion Studies | |
Senthan et al. | Synthesis, luminescence, and electrochemical studies of a new series of octanuclear ruthenium (II) complexes of tolylterpyridine appended calixresorcarenes | |
Kleineweischede et al. | Synthesis, spectroscopic and electrochemical studies of a series of transition metal complexes with amino-or bis (bromomethyl)-substituted dppz-ligands: Building blocks for fullerene-based donor–bridge–acceptor dyads | |
Stewart et al. | Host-guest complexation. 40. Synthesis and complexation of macrocyclic hosts containing cyclic ureas, anisyls, and steric barriers | |
CN115093572B (zh) | 一种多吡啶环金属铱超分子材料、制备方法及应用 | |
JP4201339B2 (ja) | パイ電子系拡張ビオローゲン誘導体とポルフィリンとの超分子錯体を用いる光電荷分離 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20070413 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20070417 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20070614 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20070802 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20070813 |
|
R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100817 Year of fee payment: 3 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110817 Year of fee payment: 4 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120817 Year of fee payment: 5 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130817 Year of fee payment: 6 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
LAPS | Cancellation because of no payment of annual fees |