JP4201339B2 - 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 - Google Patents
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 Download PDFInfo
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- 150000004032 porphyrins Chemical class 0.000 title claims description 45
- 238000000926 separation method Methods 0.000 title description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 23
- 239000001257 hydrogen Substances 0.000 claims description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 17
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 15
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzenecarbonitrile Natural products N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims description 13
- 239000011941 photocatalyst Substances 0.000 claims description 12
- 108010059332 Photosynthetic Reaction Center Complex Proteins Proteins 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 230000002194 synthesizing effect Effects 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 3
- JFDZBHWFFUWGJE-KWCOIAHCSA-N benzonitrile Chemical group N#[11C]C1=CC=CC=C1 JFDZBHWFFUWGJE-KWCOIAHCSA-N 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- -1 dichloro-substituted phenyl Chemical class 0.000 description 29
- 230000027756 respiratory electron transport chain Effects 0.000 description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 8
- 125000001072 heteroaryl group Chemical group 0.000 description 8
- 230000003993 interaction Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 125000004076 pyridyl group Chemical group 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- 238000006276 transfer reaction Methods 0.000 description 5
- 230000001052 transient effect Effects 0.000 description 5
- 238000004577 artificial photosynthesis Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000005281 excited state Effects 0.000 description 3
- 238000003473 flash photolysis reaction Methods 0.000 description 3
- 125000005647 linker group Chemical group 0.000 description 3
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 3
- 230000001443 photoexcitation Effects 0.000 description 3
- 125000000168 pyrrolyl group Chemical group 0.000 description 3
- 125000005493 quinolyl group Chemical group 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 2
- 238000005684 Liebig rearrangement reaction Methods 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 125000005956 isoquinolyl group Chemical group 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 150000004033 porphyrin derivatives Chemical class 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001254 matrix assisted laser desorption--ionisation time-of-flight mass spectrum Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
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- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
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Description
J.Phys.Chem.A 2002,106,3243−3252
拡張ビオローゲンとポルフィリンとにより形成される超分子錯体であって、該拡張ビオローゲンが、以下の一般式1で表され:
Het1およびHet2は独立してヘテロアリールであり、該ヘテロアリールは、それぞれ、その環中にヘテロ原子として窒素原子を含み、Het1の窒素原子はR1に結合しており、Het2の窒素原子はR2に結合しており、
nは2または3である、
超分子錯体。
上記項1に記載の超分子錯体であって、前記拡張ビオローゲンが以下の式V−1〜V−6のいずれかから選択される、超分子錯体:
上記項1に記載の超分子錯体であって、前記ポルフィリンが、その5位、10位、15位および20位に、フェニル基もしくは置換フェニル基を有する、超分子錯体。
上記項1に記載の超分子錯体であって、前記ポルフィリンが以下のP−1〜P−4から選択される、超分子錯体。
上記項1に記載の超分子錯体を合成する方法であって、前記拡張ビオローゲンと前記ポルフィリンとを溶媒中で混合する工程を包含する、方法。
上記項8に記載の方法であって、前記溶媒がベンゾニトリルである、方法。
上記項1に記載の超分子錯体からなる人工光合成反応中心用材料。
上記項1に記載の超分子錯体と、白金触媒とを含む、水素発生光触媒。
水素を合成する方法であって、上記項1に記載の超分子錯体と白金触媒とを含む水素発生光触媒の存在下で、水に光を照射する工程を包含する、方法。
光を電流に変換するための素子であって、導電性基材上に積層された超分子錯体を有し、該超分子錯体が、上記項1に記載された超分子錯体である、素子。
本発明に用いられるポルフィリンは、非置換のポルフィリンであってもよく、ポルフィリンとしての性能を損なわない範囲で任意の置換基を有するものであってもよい。例えば、ポルフィリン中の5位、10位、15位、および20位、すなわちピロール環とピロール環との間のメチン基の炭素原子において、置換基としてアルキル、アリールまたはアルキル置換アリールもしくはハロゲン置換アリールを有することができる。この置換基は、好ましくはフェニルまたは置換フェニルであり、より好ましくはフェニルまたはアルキル置換フェニルもしくはハロゲン置換フェニルであり、さらに好ましくは、フェニルまたはジアルキル置換フェニルもしくはジクロロ置換フェニルであり、特に好ましくはフェニルまたは3,5−ジターシャリーブチルフェニルもしくは2,6−ジクロロフェニルである。なお、ポルフィリンの5位、10位、15位、および20位はすべて同じ置換基を有することが好ましいが、必要に応じて、2〜4種類の置換基を5位、10位、15位、および20位の4ヶ所に導入してもよい。
本発明に使用される拡張ビオローゲンとは、アルキル置換ヘテロアリールとアルキル置換ヘテロアリールとがπ電子の共役系を形成し得る連結基により連結されてその2つのヘテロアリール環および連結基が合わせて1つのπ電子共役系を形成する化合物であり、以下の一般式で示される。
nは2または3である。1つの好ましい実施態様においてnは2である。
本発明の方法に用いる溶媒としては、原料となるポルフィリンと拡張ビオローゲンを溶解できる限り、特に限定されない。好ましくは、ベンゾニトリルである。
ポルフィリンと拡張ビオローゲンとは、適切な溶媒中で混合することにより、超分子錯体を形成することができる。
本発明の超分子錯体は、光誘起電子移動反応を行うことができる。超分子錯体の光誘起電子移動反応は、後述する実施例に説明する方法などにより確認することができる。
本明細書中において光エネルギー変換材料とは、光を電気エネルギーに変換する材料をいう。光エネルギー変換材料は、太陽電池、フォトセンサーなどの素子に使用可能であり、それらの素子について公知の製造方法において本発明の材料を用いることにより、優れた性能を有する素子を製造することができる。
本発明の超分子錯体は、人工光合成反応中心用材料として使用可能である。従来から、電子供与体分子と電子受容体分子とを共有結合させた人工光合成反応中心用材料が知られているが、そのような従来の人工光合成反応中心用材料と同様に本発明の超分子錯体を人工光合成反応中心として使用することができる。
本発明の超分子錯体は、水素発生光触媒に利用することができる。従来から、水還元触媒と、ポルフィリン誘導体とを組み合わせた水素発生光触媒が知られているが、その従来の触媒のポルフィリン誘導体の代わりに本発明の超分子錯体を使用することにより、本発明の水素発生光触媒を得ることができる。例えば、ガラスなどの基板上に白金触媒を積層し、さらにその上に超分子錯体を積層することにより、水素発生光触媒とすることができる。
本発明の超分子錯体は、水素合成方法に利用することができる。例えば、超分子錯体と白金触媒とを含む水素発生光触媒の存在下で、水に光を照射することにより、水が還元された水素を発生することができる。
本発明の超分子錯体は、従来公知の光を電流に変換する素子のための材料として有効に使用され得る。例えば、光電変換素子のための材料として使用可能である。素子の構成としては、従来公知の任意の構成が採用可能である。例えば、導電性基板上に超分子錯体を積層すれば、光を電流に変換する素子を得ることができる。
π電子系拡張ビオローゲンとして、ブタジエン骨格でπ系を広げたBHV2+を用いた。また、比較のために、ブタジエン骨格を有さないビオローゲン(HV2+)を用いた。
超分子錯体BHV2+−(P−1)+における光誘起電子移動の発生は、図2に示されるように、ナノ秒レーザーフラッシュ光分解を使用してPhCN中において、ポルフィリン−BHV2+π−錯体の一過性の吸収スペクトルにより確認された。図2において観測された一過性の吸収帯は、PhCN中のポルフィリンラジカルカチオンに起因する吸収帯とBHV2+の吸収帯との重ね合わせと一致する。従って、図2の一過性の吸収スペクトルは、超分子錯体におけるポルフィリンの一重項励起状態からBHV2+への光誘起電子移動による、ポルフィリン−BHV2+π−錯体のCS状態の形成を明らかに示す。
Claims (9)
- 請求項1に記載の超分子錯体であって、前記拡張ビオローゲンが式V−2で示される、超分子錯体。
- 請求項1に記載の超分子錯体であって、前記R1およびR2がC6H13である、超分子錯体。
- 請求項1に記載の超分子錯体を合成する方法であって、前記拡張ビオローゲンと前記ポルフィリンとを溶媒中で混合する工程を包含する、方法。
- 請求項4に記載の方法であって、前記溶媒がベンゾニトリルである、方法。
- 請求項1に記載の超分子錯体からなる人工光合成反応中心用材料。
- 請求項1に記載の超分子錯体と、白金触媒とを含む、水素発生光触媒。
- 水素を合成する方法であって、請求項1に記載の超分子錯体と白金触媒とを含む水素発生光触媒の存在下で、水に光を照射する工程を包含する、方法。
- 光を電流に変換するための素子であって、導電性基材上に積層された超分子錯体を有し、該超分子錯体が、請求項1に記載された超分子錯体である、素子。
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JP2004068247A JP4201339B2 (ja) | 2004-03-10 | 2004-03-10 | 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 |
EP05720405A EP1724261A4 (en) | 2004-03-10 | 2005-03-09 | PHOTOCHARGE SEPARATION USING SUPRAMOLECULAR COMPLEX VIOLOGICAL DERIVATIVE PI-ELECTRON AND PORPHYRIN |
US10/592,037 US8436242B2 (en) | 2004-03-10 | 2005-03-09 | Photocharge separation using supramolecular complex of π-electron type extended viologen derivative and porphyrin |
PCT/JP2005/004134 WO2005087741A1 (ja) | 2004-03-10 | 2005-03-09 | 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 |
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