分子間相互作用を制御した超分子色素増感太陽電池

Title 分子間相互作用を制御した超分子色素増感太陽電池( 本文_{(Fulltext) )} Author(s) 藤本, 准子 Report No.(Doctoral Degree) 博士(工学) 工博甲第548号 Issue Date 2019-03-25 Type 博士論文 Version ETD URL http://hdl.handle.net/20.500.12099/77935 ※この資料の著作権は、各資料の著者・学協会・出版社等に帰属します。

༤

༤ ኈ ㄽ ᩥ

ศᏊ㛫┦஫స⏝ࢆไᚚࡋࡓ㉸ศᏊⰍ⣲ቑឤኴ㝧㟁ụ

Supramolecular dye-sensitized solar cells controlled by intermolecular interactions

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30 ᖺᗘ

ᒱ㜧኱Ꮫ኱Ꮫ㝔ᕤᏛ◊✲⛉

≀㉁ᕤᏛᑓᨷ

┠ḟ 1 ❶ ᗎㄽ ______________________________________________________________________ 1 1-1. Ⰽ⣲ቑឤኴ㝧㟁ụ࡜᭱㏆ࡢືྥ ______________________________________________ 1 1-2. Ⰽ⣲ቑឤኴ㝧㟁ụࡢືసཎ⌮࡜᭱㏆ࡢືྥ ____________________________________ 3 1-3. 」ᩘࡢⰍ⣲࡟ࡼࡿⰍ⣲ቑឤኴ㝧㟁ụ __________________________________________ 6 1-4. ㉸ศᏊ࡟ࡼࡿⰍ⣲ቑឤኴ㝧㟁ụ ______________________________________________ 7 1-5. ᮏ◊✲ࡢᴫせ _____________________________________________________________ 11 2 ❶ ගྜᡂගᤕ㞟࢔ࣥࢸࢼ㘒యࡢS-ࢫࢱࢵࢡᵓ㐀ࢆᶍೌࡋࡓ ࣏ࣝࣇ࢕ࣜࣥⰍ⣲ቑឤኴ㝧㟁ụ ______________________________________________ 12 2-1. ᗎㄽ _____________________________________________________________________ 12 2-1.1. ⫼ᬒ _________________________________________________________________ 12 2-1.2. ┠ⓗ _________________________________________________________________ 17 2-2. ᐇ㦂㡯 ___________________________________________________________________ 18 2-2.1. ౑⏝ᶵჾ _____________________________________________________________ 18 2-2.2. ౑⏝ヨ⸆ _____________________________________________________________ 19 2-2.3. ྜᡂ᪉ἲ _____________________________________________________________ 20 2-2.4. Ⰽ⣲ቑឤኴ㝧㟁ụస〇᪉ἲ _____________________________________________ 24 2-3. ⤖ᯝ࡜⪃ᐹ _______________________________________________________________ 28 2-3.1. ࣏ࣝࣇ࢕ࣜࣥ 1ࠊ2ࠊ3 ࡢྜᡂ ___________________________________________ 28 2-3.2. ⁐ᾮ୰࡛ࡢ UV-VIS ࢫ࣌ࢡࢺࣝ __________________________________________ 29

2-3.3. 㓟໬ࢳࢱࣥୖ࡛ࡢᅛయ UV-VIS ࢫ࣌ࢡࢺࣝ ________________________________ 31 2-3.4. Ⰽ⣲ቑឤኴ㝧㟁ụ _____________________________________________________ 32 2-4. ⤖ㄽ _____________________________________________________________________ 35 3 ❶ ගྜᡂ཯ᛂ୰ᚰ࡜ගᤕ㞟࢔ࣥࢸࢼᶵ⬟ࢆᶍೌࡋࡓ ࢩ࣮ࣝࢻᆺ㉸ศᏊ࣏ࣝࣇ࢕ࣜࣥⰍ⣲ቑឤኴ㝧㟁ụ _______________________________ 36 3-1. ᗎㄽ _____________________________________________________________________ 36 3-1.1. ⫼ᬒ _________________________________________________________________ 36 3-1.2. ┠ⓗ _________________________________________________________________ 40 3-2. ᐇ㦂㡯 ___________________________________________________________________ 41 3-2.1 ౑⏝ᶵჾ _____________________________________________________________ 41 3-2.2 ౑⏝ヨ⸆ _____________________________________________________________ 42 3-3. ⤖ᯝ࡜⪃ᐹ _______________________________________________________________ 46 3-3.1 ᐇ㦂᪉ἲ _____________________________________________________________ 46 3-3.2 Ⰽ⣲ቑឤኴ㝧㟁ụࡢᛶ⬟ホ౯ ___________________________________________ 47 3-3.3 ⁐ᾮ୰࡛ࡢศගᏛⓗ ᐃ _______________________________________________ 49 3-3.4 ᅛయ࡛ࡢศගගᏛⓗ ᐃ _______________________________________________ 52 3-3.5. ᵓ㐀᭱㐺໬ ___________________________________________________________ 54 3-4 ⤖ㄽ _____________________________________________________________________ 55 4 ❶ ࣄࢻࣟ࢟ࢩ࢟ࣀࣜࣥ⨨᥮ศᩓᆺ࣏ࣝࣇ࢕ࣜࣥ࡟ࡼࡿ ගྜᡂගᤕ㞟࢔ࣥࢸࢼ㘒యࢆᶍೌࡋࡓⰍ⣲ቑឤኴ㝧㟁ụ ________________________________ 56 4-1. ᗎㄽ _____________________________________________________________________ 56

4-1.1. ⫼ᬒ _________________________________________________________________ 56 4-1.2. ┠ⓗ _________________________________________________________________ 59 4-2 ᐇ㦂㡯 ___________________________________________________________________ 60 4-2.1. ౑⏝ᶵჾ _____________________________________________________________ 60 4-2.2. ౑⏝ヨ⸆ _____________________________________________________________ 61 4-2.3. ྜᡂ᪉ἲ _____________________________________________________________ 62 4-2.4. ⁐ᾮ୰࡛ࡢ㘒ᙧᡂᐇ㦂 _________________________________________________ 64 4-2.5. 㓟໬ࢳࢱࣥ㟁ᴟୖ࡛ࡢ㘒ᙧᡂᐇ㦂 _______________________________________ 64 4-3. ⤖ᯝ࡜⪃ᐹ _______________________________________________________________ 65 4-3.1. ྜᡂ᪉ἲ _____________________________________________________________ 65 4-3.2. ⁐ᾮ୰ࡢศගගᏛⓗゎᯒ _______________________________________________ 66 4-3.3. ᡂ⭷ἲ㸯 㓟໬ࢳࢱࣥୖ࡛ᒙ≧࡟⮬ᕫ⤌⧊໬ࡉࡏࡿ ________________________ 68 Ⰽ⣲ቑឤኴ㝧㟁ụࡢᛶ⬟ホ౯ _____________________________________ 71 4-3.4. ᡂ⭷ἲϩ  ࢹࣥࢻ࣐࣮ࣜ≧ศᏊࢆసࡗࡓᚋ྾╔ࡉࡏࡿ ____________________ 73 4-3.5. ศᏊᵓ㐀ィ⟬ _________________________________________________________ 77 4-4. ⤖ㄽ _____________________________________________________________________ 79 ➨㸳❶ ࢔ࢽ࢜ࣥㄆ㆑࡟ࡼࡿⰍ┦ኚ໬ࢆ฼⏝ࡋࡓⰍ⣲ቑឤኴ㝧㟁ụ___________________ 80 5-1. ᗎㄽ _____________________________________________________________________ 80 5-1.1. ⫼ᬒ _________________________________________________________________ 80 5-1.2. ┠ⓗ _________________________________________________________________ 81 5.2 ᐇ㦂㡯 ___________________________________________________________________ 82 5-2.1 ౑⏝ᶵჾ _____________________________________________________________ 82

5-2.2 ౑⏝ヨ⸆ _____________________________________________________________ 83 5-2.3 Ⰽ⣲ቑឤኴ㝧㟁ụస〇᪉ἲ _____________________________________________ 83 5-3. ⤖ᯝ࡜⪃ᐹ _______________________________________________________________ 86 5-3.1. ྜᡂ᪉ἲ _____________________________________________________________ 86 5-3.2. 1H NMR ࡟ࡼࡿゎᯒ ____________________________________________________ 87 5-3.3. ⁐ᾮ୰࡛ࡢ྾཰ࢫ࣌ࢡࢺࣝ _____________________________________________ 90 5-3.4. Ⰽ⣲ቑឤኴ㝧㟁ụ _____________________________________________________ 92 5-3.5. ศᏊ㌶㐨ィ⟬ _________________________________________________________ 93 ⥲ᣓ___________________________________________________________________________ 95 ཧ⪃ᩥ⊩_______________________________________________________________________ 96 ௜㘓__________________________________________________________________________ 102 ᴗ⦼୍ぴ______________________________________________________________________ 107 ㅰ㎡__________________________________________________________________________ 112

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1❶ ᗎ

ᗎㄽ

1-1. Ⰽ⣲ቑឤኴ㝧㟁ụ࡜᭱㏆ࡢືྥ  ㏆ᖺࠊ㉳ࡇࡾ࠺ࡿ࢚ࢿࣝࢠ࣮ၥ㢟ࢆゎỴࡍࡿᡭẁ࡜ࡋ࡚ኴ㝧ග࢚ࢿࣝࢠ࣮ࡢ฼⏝ࡀ ὀ┠ࡉࢀ࡚࠸ࡿ 1ࠋࡑࡢ୰࡛ࡶග࢚ࢿࣝࢠ࣮ࢆ㟁Ẽ࢚ࢿࣝࢠ࣮࡟ኚ᥮࡛ࡁࡿኴ㝧㟁ụ ࡣࠊࡇࢀࡲ࡛࡟⢭ຊⓗ࡟◊✲ࡉࢀ࡚࠾ࡾࠊp ᆺ n ᆺࡢ༙ᑟయࢆ᥋ྜࡋࡓᵓ㐀ࢆᣢࡘ⤖ ᬗࢩࣜࢥࣥᆺኴ㝧㟁ụࡣᗈࡃᬑཬࡋ࡚࠸ࡿࠋࡲࡓࠊ◊✲ศ㔝࡟┠ࢆྥࡅࡿ࡜ࠊᐇ⏝໬ ࡟ྥࡅࡓᵝࠎ࡞ᙧែࡢኴ㝧㟁ụࡀᥦ᱌ࡉࢀ࡚ࡁࡓ2ࠋ

 Ⰽ⣲ቑឤኴ㝧㟁ụࡣO’Regan and Grätzel ࡽ࡟ࡼࡗ࡚ 1991 ᖺ࡟Ⓨ⾲ࡉࢀࠊࡑࢀ௨㝆 ㏆ᖺ࡟࠿ࡅ࡚┒ࢇ࡟◊✲ࡉࢀ࡚ࡁࡓ3, 4ࠋ฼Ⅼ࡜ࡋ࡚ࡣ⏕⏘ࢥࢫࢺࡀᏳࡃࠊ〇㐀ࡶᐜ᫆ ࡛࠶ࡾࠊ⌧Ꮡࡢࢩࣜࢥࣥᆺኴ㝧㟁ụ࡟ẚ࡭ࠊࢥࢫࢺࡣ 1/3 ࠿ࡽ 1/5 ࡟࡞ࡿ࡜ண᝿ࡉࢀ ࡚࠸ࡿⅬ࡛࠶ࡿ (⾲ 1)ࠋࡲࡓࠊⰍᙬ࣭㏱᫂ᛶࢆㄪ⠇࡛ࡁࠊࣇࣞ࢟ࢩࣈ࡛ࣝ࠶ࡾ㍍㔞࡛ ࠶ࡿࡇ࡜ࠊ≉࡟ྍどග࡛Ⓨ㟁࡛ࡁࡿࡓࡵࠊኴ㝧ග࠿ࡽࡢ࢚ࢿࣝࢠ࣮ኚ᥮ࡢࡳ࡞ࡽࡎࠊ ᒇෆእ࡛ࡢᵝࠎ࡞⏝㏵ࡀᮇᚅࡉࢀ࡚࠸ࡿࠋࡋ࠿ࡋࠊ⪏ೃᛶࠊ⪏ගᛶࠊ⪏⇕ᛶ࡞࡝ࡢ⪏ ஂᛶࡀၥ㢟࡜ࡋ࡚ᣲࡆࡽࢀ࡚࠸ࡿ௚ࠊ⌧ᅾࡢ༢୍Ⰽ⣲࡛ࡢ◊✲ᐊࣞ࣋ࣝࡢ5 mm ゅ⛬ ᗘࡢ࢞ࣛࢫᇶᯈ࡛ࡢ᭱㧗ኚ᥮ຠ⋡ࡣ13㸣࡟࡜࡝ࡲࡗ࡚࠾ࡾࠊ୍⯡ⓗ࡞ᐇ⏝໬࡟ྥࡅࡓ ࡉࡽ࡞ࡿ◊✲ࡀ⢭ຊⓗ࡟⾜ࢃࢀ࡚࠸ࡿ5ࠋ

2 ⾲ 1 ࢢࣞࢵࢶ࢙࣭ࣝࢭࣝࡢ≉ᚩ (ኚ᭦ࡋ࡚ᘬ⏝)6 䐟㻌㧗䛔ኚ᥮ຠ⋡ ࣭ࢩࣜࢥࣥኴ㝧㟁ụ࣭࣭࣭༢⤖ᬗ࡛28 %, ࢔ࣔࣝࣇ࢓ࢫ࡛22 %࡜ሗ࿌ (2017ᖺ⌧ᅾ) ⌮ㄽ㝈⏺ኴ㝧࢚ࢿࣝࢠ࣮ኚ᥮ຠ⋡:29%, 㛤ᨺ㟁ᅽ:᭱኱0.77V ࣭Ⰽ⣲ቑឤኴ㝧㟁ụ࣭࣭࣭⌧ᅾ᭱㧗13 %࡜ሗ࿌ࡉࢀ࡚࠸ࡿ (2017ᖺ⌧ᅾ) ⌮ㄽ㝈⏺ኴ㝧࢚ࢿࣝࢠ࣮ኚ᥮ຠ⋡:33 %,㛤ᨺ㟁ᅽ:1.0 V௨ୖ ղᏳ࠸〇㐀ࢥࢫࢺ ࣭࢔ࣔࣝࣇ࢓ࢫ Si ኴ㝧㟁ụ:100 ෇/Wpࠉ(2010ᖺ) ࣭Ⰽ⣲ቑឤኴ㝧㟁ụ:74෇/Wp (100MWp/ᖺ, η:7:11 %࡛,▼ཎ⏘ᴗヨ⟬) ࣭༢⤖ᬗSi ኴ㝧㟁ụ:360 㹼1000 ෇/Wp ࣭Ⰽ⣲ቑឤኴ㝧㟁ụ:60 㹼100 ෇/Wp (10 MWp/ᖺ, 7:11 %࡛⡿ᅜNRELࡢ Gregg ࡽヨ⟬) Ⓨ㟁ࢥࢫࢺ ࠉ⡿ᅜヨ⟬:ᑗ᮶ࠊⓎ㟁ࢥࢫࢺࡀ10෇๓ᚋ/kWh⛬ᗘࡀྍ⬟࡜ࡉࢀࡿ (ᖺ㛫5 MW 㹼10 MWࡢ⏕⏘つᶍ࡛) ࠉ᪥ᮏ࡛ࡣpn᥋ྜᆺኴ㝧㟁ụ(ࢩࣜࢥࣥኴ㝧㟁ụ)ࡀ2010ᖺࡇࢁ(ᖺ㛫50୓kW ࡢ⏕⏘つᶍ)࡟25෇/kWh⛬ᗘ࡟࡞ࡿ࡜ࡉࢀ࡚࠸ࡿ ճཎᮦᩱࡢ㈨※ⓗไ⣙ࡀᑡ࡞࠸ ࢭࣝࢆᵓᡂࡍࡿࢳࢱࢽ࢔,Ⰽ⣲ࠊࣚ࢘⣲࡞࡝ࡢ㟁ゎ㉁࡞࡝ࡢཎᮦᩱࡣ,ࢩࣜࢥࣥኴ㝧㟁ụ࡟ẚ࡭㈨※ⓗ࡞ไ⣙ࡀᑡ࡞ࡃ, 〇㐀ࣉࣟࢭࢫࡀ㠀ᖖ࡟⡆༢࡛┬࢚ࢿࣝࢠ࣮ⓗ࡛࠶ࡿ㧗┿✵,㧗 ࢆ౑⏝ࡍࡿᚲせࡀ࡞ࡃ,↓ᐖ࡛⎔ቃ࡟ඃࡋ࠸〇㐀ࣉࣟࢭࢫ࡛࠶ࡿ մከ✀ከᵝ࡞Ⰽ⣲ቑឤኴ㝧㟁ụࡢ〇సࡀྍ⬟ ከᵝ࡞᭷ᶵ⣔ቑឤⰍ⣲ࡸ㓟໬≀༙ᑟయ⭷ࡢ⤌ࡳྜࢃࡏࡀྍ⬟ յࣜࢧ࢖ࢡࣝᆺኴ㝧㟁ụ pn᥋ྜᆺࡢኴ㝧㟁ụ࡜ẚ࡭,㓟໬≀ࢆ౑⏝ࡋ࡚࠸ࡿࡇ࡜,ᐜ᫆࡟⇞↝࡛ࡁࡿ᭷ᶵ≀ࢆⰍ⣲࡟⏝࠸࡚࠸ ࡿࡇ࡜࠿ࡽ, ࣜࢧ࢖ࢡࣝ〇㐀ࡀᐜ࡛᫆࠶ࡾ⎔ቃởᰁ≀㉁ࡢ᤼ฟࡶᑡ࡞࠸

3 1-2. Ⰽ⣲ቑឤኴ㝧㟁ụࡢືసཎ⌮࡜᭱㏆ࡢືྥ ᅗ 1 Ⰽ⣲ቑឤኴ㝧㟁ụࡢືసཎ⌮  Ⰽ⣲ቑឤኴ㝧㟁ụෆࡢ㟁Ꮚ⛣ື㐣⛬ࢆᅗ 1 ࡟♧ࡋࡓࠋṇ཯ᛂࡢ㟁Ꮚ⛣ື㐣⛬ࡣࠊ ձ  㓟໬≀༙ᑟయୖ (㓟໬ࢳࢱࣥࡸ㓟໬ள㖄➼)࡟᥋㏆ࡋ࡚࠸ࡿⰍ⣲ࡀගࢆ྾཰ ࡋບ㉳≧ែ࡟࡞ࡿ ղ  ບ㉳Ⰽ⣲ࡢ LUMO ࠿ࡽ㓟໬≀༙ᑟయ࡬࡜㟁Ꮚࡀ⛣ືࡋࠊⰍ⣲ࡀ㓟໬య࡟࡞ ࡿ ճ  㓟໬≀༙ᑟయ࠿ࡽࠊ࢞ࣛࢫᇶᯈୖࡢࣇࢵ⣲ࢻ࣮ࣉ㓟໬ࢫࢬ (FTO)ࠊࢫࢬࢻ࣮ ࣉ㓟໬࢖ࣥࢪ࣒࢘ (ITO)ࡸ࢔ࣥࢳࣔࣥࢻ࣮ࣉ㓟໬࢖ࣥࢪ࣒࢘(ATO)➼ࡢ㏱᫂ᑟ 㟁⭷࡬㟁Ꮚࡀ⛣ືࡍࡿ մ ᅇ㊰ࢆ㏻ࡗ࡚ࠊᑐᴟࡢ㏱᫂ᑟ㟁⭷ୖࡢⓑ㔠 (Ⅳ⣲)ᑐᴟ࠿ࡽ㟁ゎ㉁࢖࢜ࣥࢆ௓ ࡋⰍ⣲ࡢ㓟໬యࡀ㑏ඖࡉࢀࡿ

4 յ Ⰽ⣲ࡀ㑏ඖࡉࢀࡓ஦࡟ࡼࡿ࣮࣍ࣝ࡬ࡢ㟁Ꮚࡢ⛣ືࡍࡿ ࡢࢧ࢖ࢡ࡛ࣝ⾜ࢃࢀࡿࠋ㏫཯ᛂ㐣⛬ࡣ Ⰽ⣲ୖ࠾ࡅࡿ㟁Ꮚບ㉳≧ែࡢ⦆࿴ࡸኻά 㓟໬༙ᑟయ࠿ࡽࡢⰍ⣲㓟໬య࡬ࡢ㟁Ꮚࡢ෌⤖ྜ 㓟໬༙ᑟయ࡜㟁ゎ㉁࢖࢜ࣥ㛫࡜ࡢ㟁Ꮚࡢ෌⤖ྜ 㓟໬ࢫࢬ㟁ᴟୖ࠿ࡽࡢ㟁ゎ㉁࡬ࡢ㟁Ꮚࡢ෌⤖ྜ ࡀᣲࡆࡽࢀࡿ (ኚ᭦ࡋ࡚ᘬ⏝6)ࠋ ࡇࡢṇ཯ᛂࢆஹ㐍ࡋࠊ㏫཯ᛂ㐣⛬ࢆᢚไࡍࡿࡇ࡜࡟ࡼࡗ࡚ࠊⰍ⣲ቑឤኴ㝧㟁ụࡢᛶ⬟ ࡣྥୖࡍࡿࠋ Ⰽ⣲ቑឤኴ㝧㟁ụࡢ◊✲࡟࠾ࡅࡿⰍ⣲㛤Ⓨ࡜ࡋ࡚ࡣࠊኴ㝧ගࡢ↷ᑕἼ㛗 (≉࡟ྍど ගࡸ㉥እᇦ)ࢆᗈࡃ྾཰࡛ࡁࠊࡼࡾᙉࡃගࢆ྾཰࡛ࡁࡿ (྾ගಀᩘȜࡀ㧗࠸)Ⰽ⣲ࡀồ ࡵࡽࢀࡿࡢࡣࡶࡕࢁࢇࠊ๓㏙ࡢ㏫཯ᛂࢆ㉳ࡇࡾ࡟ࡃ࠸Ⰽ⣲ࢆぢฟࡍࡇ࡜ࡀ┠ⓗ࡜ࡉࢀ ࡿࠋⰍ⣲ቑឤኴ㝧㟁ụ࡟⏝࠸ࡿⰍ⣲࡟ࡣ኱ࡁࡃ㠀㔠ᒓ⣔ 7࡜㔠ᒓ⣔ 8ࡢⰍ⣲ࡢ㸰ࡘ࡟ ศࡅࡽࢀࠊ᭦࡟ࡑࡢ୰࡛ࠊᵝࠎ࡞୺㦵᱁࡛ሗ࿌ࡉࢀ࡚ࡁࡓࠋ2018 ᖺࡲ࡛ࡢ㧗ຠ⋡࡞Ⰽ ⣲࡟ࡘ࠸࡚ࡣࠊ㠀㔠ᒓ⣔࡛ࡣࢳ࢔ࢰ࣮ࣝ⣔Ⰽ⣲࡛ኚ᥮ຠ⋡12.6 % (19.4 mA/cm2)9ࡸⰍ ⣲࡜᭷ᶵࢩࣜࢥࣥࢆඹ྾╔ࡍࡿࡇ࡜࡛14.3 % (18.27 mA/cm2)10ࡀሗ࿌ࡉࢀ࡚࠸ࡿࠋࡲ ࡓࠊ㔠ᒓࢆྵࡴ⣔࡟࠾࠸࡚ࡣ྾ගಀᩘࡢ㧗࠸࣏ࣝࣇ࢕ࣜࣥ⣔Ⰽ⣲࡛ࢻࢼ࣮-ȧ-࢔ࢡࢭ ࣉࢱ࣮ (௨ୗ D-ȧ-A)ࢆᵓ⠏ࡋࠊ13 %ࢆグ㘓ࡋࡓࡇ࡜ࡀሗ࿌ࡉࢀ࡚࠸ࡿ5ࠋ࠸ࡎࢀࡢⰍ ⣲ࡶࠊ㟁ὶ್࡟㏫཯ᛂࡢ㉳ࡇࡾ࡟ࡃࡉ࡟ࡶ↔Ⅼࢆᙜ࡚タィࡉࢀ࡚࠸ࡿࠋ

5 ᅗ 2 㧗ຠ⋡࡞Ⰽ⣲ቑឤኴ㝧㟁ụ⏝ࡢⰍ⣲5,9 ౛࠼ࡤࠊࠕⰍ⣲ୖ࡟࠾ࡅࡿບ㉳㟁Ꮚࡢ⦆࿴ࡸኻάࠖ࡟࠾࠸࡚ࠊ⪃࠼ࡽࢀࡿゎỴ⟇࡜ ࡋ࡚ࠊⰍ⣲ྠኈࡢจ㞟ࢆᢚไࡍࡿࡇ࡜࡞࡝ࡀᣲࡆࡽࢀࡿࠋᚑ᮶ࡢⰍ⣲ࡣ఍ྜᢚไࡍࡿ ࡓࡵ࡟ࠊࢹ࢜࢟ࢩࢥ࣮ࣝ㓟 (௨ୗ DCA)࡞࡝ࡀ⏝࠸ࡽࢀ࠾ࡾࠊⰍ⣲࡜ඹ྾╔ࡉࡏࡿࡇ ࡜࡛จ㞟ࢆᢚไࡋࠊⰍ⣲㛫࡛ࡢບ㉳Ꮚྠኈࡢኻάࢆᢚไࡍࡿࠋࡇࡢ DCA ࡢῧຍࡣ㓟 ໬ࢳࢱࣥ⾲㠃ࢆそ࠺஦࡛ࠕ㓟໬≀༙ᑟయ࡜㟁ゎ㉁࢖࢜ࣥ㛫࡜ࡢ㟁Ꮚࡢ෌⤖ྜࠖࢆᢚไ ࡍࡿࡇ࡜ࡶ࡛ࡁࡿࠋࡇࡢ㟁Ꮚࡢ₃ࢀࢆᢚไࡍࡿࡇ࡜࡛ TiO2 ୰ࡢ㟁Ꮚᣑᩓಀᩘ࡜㟁Ꮚ ᑑ࿨ࡀ኱ࡁࡃ࡞ࡾࠊ㛤ᨺ㟁ᅽ (Voc)ࡀྥୖࡍࡿ࡜⪃࠼ࡽࢀ࡚࠸ࡿ 11ࠋ㏆ᖺ࡟࠾ࡅࡿⰍ ⣲㛤Ⓨ࡟࠾࠸࡚ࠊࡇࡢ DCA ࡜ྠ➼ࡢാࡁࢆᢸࡗ࡚࠸ࡿࡢࡀࠊ㛗㙐Ⅳ⣲㙐࡛࠶ࡿࠋࡲ ࡓࠊ྾ගಀᩘࡢ㧗࠸Ⰽ⣲ࡣࠊບ㉳≧ែ࠿ࡽࡢኻάࡀ᪩࠸ࡇ࡜ࡶ▱ࡽࢀ࡚࠾ࡾࠊບ㉳ࡋ ࡓⰍ⣲ࡀኻάࡋ࡞࠸ࡼ࠺࡞㓟໬≀༙ᑟయ࡬ࡢ㟁Ꮚࡢὀධࡸࠊ㓟໬≀༙ᑟయ୰ࡢ㟁Ꮚࡢ ᣑᩓࡀ㉳ࡇࡍࡓࡵࡢ㥑ືຊࡀᚲせ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋࡇࡢ㥑ືຊ࡜ࡋ࡚ࡣ๓㏙ࡢ D-ȧ-A ⣔ࡀᣲࡆࡽࢀࠊ㟁Ꮚࢻࢼ࣮࡜ࡋ࡚ࢪ࢔ࣜࣝ࢔࣑ࣀᇶ➼ࡢⰾ㤶᪘࢔࣑ࣀᇶ࡛ȧ ඹᙺ⣔࡬㟁Ꮚࢆ୚࠼ࠊ࢝ࣝ࣎࢟ࢩᇶࡸࢩ࢔ࣀ࢔ࢡࣜࣝ㓟➼ࡀ⨨᥮ࡉࢀ࡚࠸ࡿ࣋ࣥࢰࢳ ࢔ࢰ࣮ࣝ⎔ࡀ࣏ࣝࣇ࢕ࣜࣥ⎔࡞࡝࠿ࡽ࢔ࢡࢭࣉࢱ࣮࡜ࡋ࡚㟁Ꮚࢆᙉࡃ྾ᘬࡍࡿ஦࡟ ࡼࡾࠊ㓟໬≀༙ᑟయ࡬㟁Ꮚࢆὀධࡋࡸࡍࡃࡋ࡚࠸ࡿ(ᅗ 2)ࠋ

6 1-3. 」ᩘࡢⰍ⣲࡟ࡼࡿⰍ⣲ቑឤኴ㝧㟁ụ   ୍᪉࡛ࠊග྾཰㡿ᇦࡢᣑ኱ࠊ㟁Ꮚࡢᩚὶࢆ┠ⓗ࡜ࡋࡓ」ᩘࡢⰍ⣲ࢆΰྜࡋࡓ⣔ࡀ, ሗ ࿌ࡉࢀ࡚࠸ࡿ (ᅗ 3)ࠋ㏆ᖺ࡛」ᩘࡢⰍ⣲ࢆΰྜࡋࡓሗ࿌౛ࡣࠊ࣏ࣝࣇ࢕ࣜࣥ⣔Ⰽ⣲ (Ȣmax=448, 581, 645 nm)࡜࣏ࣝࣇ࢕ࣜࣥࡢ྾཰ᖏࡀ࡞࠸㡿ᇦ (525 nm)ࢆ྾཰ࡍࡿⰍ⣲ ࢆ⤌ࡳྜࢃࡏኚ᥮ຠ⋡12.3% (17.66 mA/cm2)12ࠊࡲࡓࠊኴ㝧ගୗ࡛ࡢኚ᥮ຠ⋡ࡀ6%⛬ ᗘࡢⰍ⣲ 13,14,15 ࢆ⤌ࡳྜࢃࡏࠊ1000 ࣝࢡࢫࡢ⎔ቃගୗ࡛ኚ᥮ຠ⋡ 28.9 % (138ȣA/ cm2)16࡞࡝ࡢ㧗ኚ᥮ຠ⋡࡞Ⰽ⣲ቑឤኴ㝧㟁ụࡀሗ࿌ࡉࢀ࡚࠸ࡿࠋࡇࢀࡽࡢⰍ⣲ࡢඹ྾ ╔࡟ࡼࡿሗ࿌ࡣࠊ୍᪉ࡢⰍ⣲ࡀ௚᪉ࡢⰍ⣲࡟࡞࠸྾཰ᇦ࡟྾཰ࢆᣢࡘ஦ࡀ≉ᚩ࡛࠶ࡾࠊ ┦ᑐⓗ࡟ྍどᇦ࡟ᗈ࠸྾཰ᇦࢆᣢࡘࡇ࡜ࡀ࡛ࡁࡿࠋ ᅗ 3 ␗✀ࡢ୺㦵᱁ࡢ⤌ࡳྜࢃࡏࡢ౛16,12

7 1-4. ㉸ศᏊ࡟ࡼࡿⰍ⣲ቑឤኴ㝧㟁ụ ᮏ◊✲ࡢ୺║࡛࠶ࡿ␗✀ࡢࡲࡓࡣྠ✀ࡢⰍ⣲ࡢ఍ྜ≧ែࢆไᚚࡋࡓࠊ࠸ࢃࡺࡿ㉸ศ ᏊⰍ⣲࡛ࡢⰍ⣲ቑឤኴ㝧㟁ụ࡬ࡢᛂ⏝ࡶ᳨ウࡉࢀ࡚ࡁࡓࠋ ࡇࢀࡲ࡛ࠊ⮬ᕫ⤌⧊໬࡟ࡼࡿ㉸ศᏊ໬ࡣ㛗ᖺ࡟Ώࡗ࡚◊✲ࡉࢀ࡚ࡁࡓ17,18ࠋⰍ⣲㛤 Ⓨ࡟࠾࠸࡚ࠊ㉸ศᏊࢆ⏝࠸ࡿࡇ࡜࡟㛵ࡍࡿ࣓ࣜࢵࢺ࡜ࡋ࡚ࡣࠊྜᡂ࡛ᑟධ࡞࡝ࡀᅔ㞴 ࡞ࣇ࣮ࣛࣞࣥ࡞࡝ࢆ⣔࡟ᑟධࡍࡿࡇ࡜ࡀྍ⬟࡟࡞ࡿⅬࠊ㍈㓄఩Ꮚࡢ฼⏝࡟ࡼࡿྜᡂࢫ ࢸࢵࣉࡢ▷⦰໬࡞࡝〇㐀ࢥࢫࢺࡢ๐ῶࡀᮇᚅࡉࢀࡿࠋࡲࡓࠊࣂ࢖࣑࣓࢜ࢸ࢕ࢡࢫࡢほ Ⅼ࠿ࡽࠊ᳜≀࡞࡝࡟ぢࡽࢀࡿࡼ࠺࡞ගྜᡂ19–23ࢆேᕤⓗ࡟෌⌧ࡍࡿ࡞࡝ࠊᏛ⾡ⓗ࡞ព ⩏ࡶ⛎ࡵ࡚࠸ࡿࠋ ㉸ศᏊⰍ⣲࡟ࡼࡿⰍ⣲ቑឤኴ㝧㟁ụࡢ୺࡞╔║Ⅼ࡜ࡋ࡚ࡣࠊ㟁Ⲵศ㞳≧ែࡢ㛗ᑑ࿨ ໬࡟ࡼࡿᛶ⬟ࡢྥୖࠊ࣮࣍ࣝࢺࣛࢵࣆࣥࢢࠊ㍺㏦࡟ࡼࡾ㟁ゎ㉁࠿ࡽ㟁Ꮚࡢᤵཷࡢᐜ᫆ ໬ࠊ྾཰ᇦࡢ␗࡞ࡿⰍ⣲ࢆ࢔ࣥࢸࢼศᏊ࡜ࡋࡓ྾཰ᇦࡢᣑᙇ࡜㟁Ꮚࡢᩚὶ࡞࡝ࡀ࠶ࡆ ࡽࢀࡿࠋ ࡲࡎࠊ㟁Ⲵศ㞳≧ែࡢ㛗ᑑ࿨໬࡟ࡘ࠸࡚㏙࡭ࡿࠋᅗ 4 ࡣ࣏ࣝࣇ࢕ࣜࣥ࡜ࣇ࣮ࣛࣞࣥ ࡢȧ┦஫స⏝࡟ࡼࡿ㉸ศᏊ໬࡛Ⰽ⣲ቑឤኴ㝧㟁ụ࡟୚࠼ࡿᙳ㡪࡟ࡘ࠸࡚ሗ࿌ࡉࢀࡓ ࡶࡢ࡛࠶ࡿ 24,25ࠋⴭ⪅ࡽࡣࣇ࣮ࣛࣞࣥࢆ⏝࠸ࡓ⌮⏤࡜ࡋ࡚ࡣࠊ࣏ࣝࣇ࢕ࣜࣥ࡜ࡢ㟁Ꮚ ⛣ືࡢ෌㓄ิ࢚ࢿࣝࢠ࣮ࡢᕪࡀᑠࡉࡃࠊ㟁Ⲵศ㞳≧ែࡀ㛗ᑑ࿨໬ࡍࡿࡓࡵࠊⰍ⣲ୖ࡟ ࠾ࡅࡿບ㉳㟁Ꮚࡢ⦆࿴ࡸኻάࡀ㉳ࡇࡽ࡞࠸ࡇ࡜ࢆ≺࠸࡜ࡋ࡚࠸ࡿࠋᅗ 4 ᕥᅗ࡛ࡣ༢⊂ ࡢ࣏ࣝࣇ࢕ࣜࣥⰍ⣲࡟ࣇ࣮ࣛࣞࣥࢆຍ࠼ࡓ࡜ࡇࢁࠊIsc ࡀ 0.035 mA/cm2 ࠿ࡽ 0.11 mA/cm2ࡲ࡛ⴭࡋࡃྥୖࡋࡓ࡜ሗ࿌ࡉࢀ࡚࠸ࡿࠋ

8 ᅗ 4 ࣇ࣮ࣛࣞࣥ࡜࣏ࣝࣇ࢕ࣜࣥ࡟ࡼࡿⰍ⣲ቑឤኴ㝧㟁ụ24,25 ࡲࡓࠊ࣮࣍ࣝࢺࣛࢵࣆࣥࢢ࡟ࡘ࠸࡚ࡣ௨ୗࡢࡼ࠺࡞◊✲ࡀሗ࿌ࡉࢀ࡚࠸ࡿࠋ ᅗ 5࡟♧ࡍⰍ⣲ቑឤኴ㝧㟁ụࡣࠊSpacer 㒊࡟ࢪࣇ࢙ࢽࣝ࢔࣑ࢻᇶࢆ Donor 㒊࡟࣏ࣝ ࣇ࢕ࣜࣥ࡜ࣇ࢙ࣟࢭࣥࢆᑟධࡋ࡚࠸ࡿࠋ᭦࡟㓟໬ࢳࢱࣥ࡬ࡢ࢔࣮ࣥ࢝㒊࡜ࡋ࡚ࠊ࣏ࣝ ࣇ࢕ࣜࣥள㖄㘒య࡬ࡢ㍈㓄఩Ꮚ࡜ࡋ࡚࢖࣑ࢲࢰ࣮ࣝࢆ⏝࠸ࡓ⣔࡛࠶ࡿࠋ㍈㓄఩Ꮚࡢ࢖ ࣑ࢲࢰ࣮ࣝࡸ࢔࣮ࣥ࢝㒊ࢆ┤᥋࣏ࣝࣇ࢕ࣜࣥ࡟ᑟධࡋ࡞࠸ࡇ࡜࡟ࡼࡾࠊྜᡂࡀ㠀ᖖ࡟ ᐜ᫆࡟࡞ࡿࠋࡇࡢ⣔ࡢ୺║ࡣDonor 㒊࡟ࣇ࢙ࣟࢭࣥࢆᑟධࡋࡓࡇ࡜࡛࠶ࡿࠋࣇ࢙ࣟࢭ ࣥࡀ㟁ゎ㉁ࡢDonor 㒊࡟ධࡿ஦࡟ࡼࡾࠊ㓟໬ࡉࢀࡸࡍࡃ࡞ࡾࠊ࣏ࣝࣇ࢕ࣜࣥ࠿ࡽࣇ࢙ ࣟࢭࣥ࡬ࡢ࣮࣍ࣝ⛣ືࡀ㉳ࡇࡾࡸࡍࡃ࡞ࡿ⤖ᯝࠊ㟁ゎ㉁࠿ࡽ㟁Ꮚࢆཷࡅྲྀࡾࡸࡍࡃ࡞ ࡿ࡜⪃࠼ࡽࢀࡿࠋ ᅗ 5 ࣇ࢙ࣟࢭࣥᑟධ࡟ࡼࡿⰍ⣲ቑឤኴ㝧㟁ụ26

9 ࢔ࢽ࢜ࣥㄆ㆑ࢆ฼⏝ࡋࡓ⣔ࡶሗ࿌ࡉࢀ࡚࠸ࡿ27,28ࠋᅗ 5 ࡢ⣔࡛ࡣᅗ 6 ࡜ྠᵝ࡟࢔ࣥ ࣮࢝㒊࡜ࡋ࡚࢝ࣝ࣎ࣥ㓟ࢆࠊள㖄࣏ࣝࣇ࢕ࣜࣥ࡬ࡢ㍈㓄఩Ꮚ࡜ࡋ࡚࢖࣑ࢲࢰ࣮ࣝࢆ⏝ ࠸ࠊ࢔ࢽ࢜ࣥࢆㄆ㆑ࡍࡿDonor 㒊ࢆᣢࡗࡓᵓ㐀࡛࠶ࡿࠋࡇࡢ Donor 㒊ࡀ࢔ࢽ࢜ࣥࢆㄆ ㆑ࡍࡿࡇ࡜࡟ࡼࡾࠊ㟁Ꮚ≧ែࡀኚ໬ࡋࠊ㓟໬㟁఩ࡀ࢝ࢯ࣮ࢻࢩࣇࢺࡍࡿࡇ࡜࡛ࠊ㓟໬ ࡉࢀࡸࡍࡃ࡞ࡿ⤖ᯝࠊ࣮࣍ࣝ⛣ືࡀ㉳ࡇࡾࡸࡍࡃ࡞ࡾࠊ㟁ゎ㉁࠿ࡽ㟁Ꮚࢆཷࡅྲྀࡾࡸ ࡍࡃ࡞ࡿ࡜ⴭ⪅ࡽࡣ㏙࡭࡚࠸ࡿࠋ ᅗ 6 ࣮࣍ࣝ⛣ືࢆ฼⏝ࡋࡓⰍ⣲ቑឤኴ㝧㟁ụ27

10 ᭱ᚋ࡟྾཰ᇦࡢ␗࡞ࡿⰍ⣲ྠኈࢆ఍ྜไᚚࡋࡓ㉸ศᏊ࢔ࣥࢸࢼຠᯝ࡟ࡘ࠸࡚㏙࡭ ࡿ(ᅗ 7ࠊᅗ 8ࠊᅗ 9)ࠋ๓㏙ࡢⰍ⣲ΰྜ⣔࡜␗࡞ࡿⅬࡣࠊἼ㛗㡿ᇦࡢᗈᇦ໬ࡢࡳ࡞ࡽ ࡎࠊHOMO-LUMO ࡢ࢚ࢿࣝࢠ࣮ᕪ࠿ࡽࠊ㟁Ꮚ࡜࢚ࢿࣝࢠ࣮ࡢᩚὶࢆ┠ⓗ࡜ࡋ࡚࠸ࡿ Ⅼ࡛࠶ࡿ30,31,32ࠋ ᅗ 7 BODIPY ࢆ࢔ࣥࢸࢼⰍ⣲ศᏊ࡜ࡍࡿ㉸ศᏊⰍ⣲ቑឤኴ㝧㟁ụ30 ᅗ 8 ࣏ࣝࣇ࢕ࣜࣥࢆ࢔ࣥࢸࢼศᏊ࡜ࡍࡿⰍ⣲ቑឤኴ㝧㟁ụ31 ᅗ 9 ࣝࢸࢽ࣒࢘㘒య࡜࣏ࣝࣇ࢕ࣜࣥࡢⰍ⣲ቑឤኴ㝧㟁ụ32

11 1-5. ᮏ◊✲ࡢᴫせ ㉸ศᏊⰍ⣲࡟ࡼࡿⰍ⣲ቑឤኴ㝧㟁ụ࡟ࡘ࠸࡚㏙࡭࡚ࡁࡓࡀࠊࡑࡢṤ࡝࡛ศᏊ㛫┦஫స ⏝ࡑࡢࡶࡢࡀⰍ⣲ቑឤኴ㝧㟁ụ࡟୚࠼ࡿᙳ㡪࡟ࡘ࠸᳨࡚ウࡣࡉࢀ࡚࠸࡞࠸ࠋᮏ◊✲࡛ ࡣࠊࣂ࢖࣑࣓࢜ࢸ࢕ࢡࢫ (⏕ែᶍೌ)ࡢほⅬ࠿ࡽࠊ⏕≀ࡢගྜᡂගᤕ㞟ࢩࢫࢸ࣒࡟╔┠ ࡋࠊศᏊ㛫┦஫స⏝ࢆไᚚࡋࡓ㉸ศᏊࡢⰍ⣲ቑឤኴ㝧㟁ụ࡬ࡢᛂ⏝ࢆ┠ⓗ࡜ࡍࡿࠋ  ➨1 ❶࡛ࡣ඲యࡢᗎㄽࢆ㏙࡭ࡓࠋ ➨2 ❶ࡣගྜᡂගᤕ㞟࢔ࣥࢸࢼ㘒య (LH2, B850)ࡢ π ࢫࢱࢵࢡᵓ㐀ࢆᶍೌࡋࠊ࢖࣑ ࢲࢰ࣮ࣝ࡜࣐ࢢࢿࢩ࣒࢘࡜ࡢ㓄఩࡟ࡼࡾ㉸ศᏊࢆᙧᡂࡍࡿ࣏ࣝࣇ࢕ࣜࣥࢆ⏝࠸࡚Ⰽ ⣲ቑឤኴ㝧㟁ụࢆస〇ࡋࡓࠋ ➨3 ❶ࡣගྜᡂ࢔ࣥࢸࢼ㘒య(LH1-RC)࡛ぢࡽࢀࡿࡼ࠺࡞ࢩ࣮ࣝࢻ(ᅖ࠸)ᆺ࢔ࣥࢸࢼ ᵓ㐀ࢆᶍೌࡋࠊ࢔ࣥࢸࢼศᏊ࡜ࡋ࡚ள㖄࣏ࣝࣇ࢕ࣜࣥ (ZnTPP)ࢆ⏝࠸ࠊ཯ᛂ୰ᚰศᏊ ࡜ࡋ࡚㓟໬ள㖄࡬ࡢ࢔࣮ࣥ࢝㒊࡜ࡋ࡚࢝ࣝ࣎࢟ࢩᇶࢆ㸯ࡘࠊZnTPP ࡬ࡢ㓄఩Ꮚ࡜ࡋ࡚ ࣔࣀ࢝ࣝ࣎࢟ࢩࣇ࢙ࢽࣝࢺࣜࣆࣜࢪ࣏ࣝࣝࣇ࢕ࣜࣥ (FbPyP)ࢆ⏝࠸ࠊZnTPP ࠿ࡽ FbPyP ࡬ࡢ࢚ࢿࣝࢠ࣮⛣ື࡛ᛶ⬟ࡀྥୖࡍࡿⰍ⣲ቑឤኴ㝧㟁ụࡢస〇ࢆ┠ⓗ࡜ࡋࡓࠋ ➨4 ❶࡛ࡣ㐺ษ࡞㊥㞳ࢆಖࡗ࡚ศᩓࡋ࡚࠸ࡿ᳜≀ࡢ࢔ࣥࢸࢼࢡࣟࣟࣇ࢕ࣝࢆᶍೌࡋࠊ ᑐ㠃ࡍࡿ meso ఩࡟ 8-ࣄࢻࣟ࢟ࢩ࢟ࣀࣜࣥ(8-HQ)ࢆ⨨᥮ࡋࡓ࣏ࣝࣇ࢕ࣜࣥࢆ⏝࠸ࠊ㔠 ᒓ㘒໬࡟ࡼࡾ࣏ࣝࣇ࢕ࣜࣥࡀ୍ᐃ㊥㞳࡛ศᩓࡍࡿ㉸ศᏊ࣏ࣝࣇ࢕ࣜࣥࢹࣥࢻ࣐࣮ࣜ ࡟ࡼࡿⰍ⣲ቑឤኴ㝧㟁ụࡢస〇ࢆ┠ⓗ࡜ࡋࡓࠋ  ➨ 5 ❶࡛ࡣ࢔ࢽ࢜ࣥㄆ㆑࡟ࡼࡿ྾཰Ἴ㛗ࡢ㛗Ἴ㛗໬(Ⰽ┦ኚ໬)ࢆ฼⏝ࡋࡓⰍ⣲ቑឤ ኴ㝧㟁ụࡢᛶ⬟ࡢྥୖࢆヨࡳࡓࠋ

12

2❶  ග

ගྜ

ྜᡂ

ᡂග

ගᤕ

ᤕ㞟

㞟࢔

࢔ࣥ

ࣥࢸ

ࢸࢼ

ࢼ㘒

㘒య

యࡢ

ࡢS-ࢫࢱࢵࢡᵓ㐀ࢆᶍೌࡋࡓ

࣏ࣝࣇ࢕ࣜࣥⰍ⣲ቑឤኴ㝧㟁ụ

2-1. ᗎㄽ 2-1.1. ⫼ᬒ  Ⰽ⣲ቑឤኴ㝧㟁ụࡢⰍ⣲࡜ࡋ࡚ࠊ࣏ࣝࣜࣇ࢕ࣥࡣ⣸እ࣭ྍどᇦࡢ྾ගಀᩘࡀ኱ࡁ࠸ ࡇ࡜ࠊᵝࠎ࡞⨨᥮ᇶࡢᑟධࡀᐜ࡛᫆࠶ࡿࡇ࡜࠿ࡽ┒ࢇ࡟ሗ࿌ࡉࢀ࡚࠸ࡿࠋࡇࢀࡲ࡛࣏ ࣝࣇ࢕ࣜࣥࢆ⏝࠸࡚ࠊ࣏ࣝࣇ࢕ࣜࣥྠኈࢆ⤖ྜࡉࡏࠊⰍ⣲ቑឤኴ㝧㟁ụࡢගᤕ㞟ࡸ㟁 Ꮚὀධຠ⋡ࢆྥୖࡉࡏࡿ◊✲ࡀሗ࿌ࡉࢀ࡚ࡁࡓ33–39ࠋࡋ࠿ࡋࠊ࣏ࣝࣇ࢕ࣜࣥྠኈࡢ⤖ ྜ࡟ࡣඹ᭷⤖ྜࡀ⏝࠸ࡽࢀ࡚࠾ࡾࠊࢺ࣮ࢱ࡛ࣝࡢ཰⋡ࡣపࡃࠊ࣏ࣝࣇ࢕ࣜࣥከ㔞యࢆ ඹ᭷⤖ྜ࡛ྜᡂࡍࡿࡇ࡜ࡀᅔ㞴࡛࠶ࡿࠋ  ᅗ 10 ࡣ⣚Ⰽගྜᡂ⣽⳦ Rhodopseudomonas acidophila ࡢගᤕ㞟࢔ࣥࢸࢼ⣔ࡢ⤖ᬗᵓ 㐀࡛࠶ࡿࠋගྜᡂ࡟࠾࠸࡚ࠊࡲࡎࡇࢀࡽࡢ࢔ࣥࢸࢼ⣔(LH2)࡛ගᤕ㞟ࡀ⾜ࢃࢀࠊග࡟ ࡼࡿບ㉳࢚ࢿࣝࢠ࣮ࡀ཯ᛂ୰ᚰ(Reaction Center/RC)࡬㏦ࡽࢀࡿࡇ࡜࠿ࡽጞࡲࡿࠋࡇࡢ LH2 ࡛ࡣࣂࢡࢸࣜ࢜ࢡࣟࣟࣇ࢕ࣝ a ࡀࣜࣥࢢ≧㓄ิࡋ࡚Ꮡᅾࡋ࡚࠸ࡿࠋLH2 ࢆᙧᡂ ࡍࡿࣂࢡࢸࣜ࢜ࢡࣟࣟࣇ࢕ࣝࡢࣜࣥࢢࡣ B850 ࡜ B800 ࡟ศ࠿ࢀ࡚࠸ࡿࠋB800 ࡛ࡣ 9 ศᏊࡢࣂࢡࢸࣜ࢜ࢡࣟࣟࣇ࢕ࣝ a ࡀศᏊ㠃ࢆࡑࢁ࠼࡚ྠ୍ᖹ㠃ୖ࡟ᏑᅾࡋࠊB850 ࡛ ࡣ 18 ศᏊࡢࣂࢡࢸࣜ࢜ࢡࣟࣟࣇ࢕ࣝ a ࡀศᏊ㠃ࢆᑡࡋࡎࡽࡋ࡚ࢫࢱࢵࢡࡋ࡚Ꮡᅾࡋ ࡚࠸ࡿࠋࡇࢀࡽࡢࣜࣥࢢ≧ࡢ࣏ࣝࣇ࢕ࣜࣥୖࢆບ㉳࢚ࢿࣝࢠ࣮ࡀ㧗㏿࡛⛣ືࡍࡿ (B800 ࠿ࡽ B800: ~500 fsࠊB850 ࣜࣥࢢୖ: 100㹼200 fsࠊB800 ࠿ࡽ B850: 1.2 psࠊLH2 ࠿ࡽLH1: 3.5 psࠊLH1 ࠿ࡽ RC: 35 ps)ࠋB850 ࡛ࡣ㓄ิࡋࡓࣂࢡࢸࣜ࢜ࢡࣟࣟࣇ࢕ࣝ a ࡣ㑄⛣཮ᴟᏊ࣮࣓ࣔࣥࢺࡢ┦஫స⏝ࢆ㉳ࡇࡋࠊ෇࿘ࡢ᥋⥺࡟ྥࡃࡼ࠺࡟㓄ิࡋ࡚࠸ࡿ (ᅗ 10)ࠋࡇࡢࡇ࡜ࡀせᅉ࡜࡞ࡾࠊ」ᩘࡢศᏊ࡛ບ㉳Ꮚ≧ែࢆ⥔ᣢࡋࠊኻάࢆ㜵࠸࡛࠸ ࡿ࡜⪃࠼ࡽࢀࡿࠋࡇࡢࡼ࠺࡟ග࡟ࡼࡗ࡚ບ㉳ࡉࢀࡓ࢚ࢿࣝࢠ࣮ࡣLH2ࠊLH1ࠊ཯ᛂ୰

13

ᚰࡢ㡰࡟᪉ྥࢆಖࡗ࡚⛣ືࡍࡿࠋࡑࡋ࡚ࠊᅗ 11 ࡢ LH1-RC ࡢ཯ᛂ୰ᚰ࡟ὶࡉࢀࡿࠋ

ᅗ 10 ගྜᡂ⣽⳦ࡢගᤕ㞟࢔ࣥࢸࢼ㘒య40,41,42

14 ࣂ࢖࣑࣓࢜ࢸ࢕ࢡࢫࡢほⅬ࠿ࡽࠊᵝࠎ࡞࣏ࣝࣇ࢕ࣜࣥࡸࣇࢱࣟࢩ࢔ࢽࣥ࡞࡝ࡢⰍ⣲ ࡢ⮬ᕫ⤌⧊໬ࡀሗ࿌ࡉࢀ࡚ࡁࡓ43ࠋ୍᪉ࠊᡃࠎࡣN-࣓ࢳࣝ࢖࣑ࢲࢰ࣮ࣝࢆ⨨᥮ࡋࡓ࣏ ࣝࣇ࢕ࣜࣥࢆྜᡂࡋࠊගྜᡂࡢࢫ࣌ࢩࣕࣝ࣌࢔ࡸ࢔ࣥࢸࢼ㘒యࢆᶍೌࡋࡓ㉸ศᏊ࣏ࣝ ࣇ࢕ࣜࣥ࡬ࡢ⮬ᕫ⤌⧊໬ࢆሗ࿌ࡋ࡚ࡁࡓ44,45ࠋࡇࢀࡽࡢศᏊࡣN-࣓ࢳࣝ࢖࣑ࢲࢰ࣮ࣝ ࠿ࡽ㔠ᒓ࡬ࡢ༠ྠⓗ࡞㓄఩࡟ࡼࡾࠊ᭷ᶵ⁐፹୰࡛୰ᚰࢆࡎࡽࡋ࡚ȧࢫࢱࢵ࢟ࣥࢢࡋࡓ ஧㔞యࡸከ㔞య㸦J ఍ྜ㸧࡬⮬ᕫ⤌⧊໬ࡍࡿࠋᅗ 12

ࡣ᭷ᶵ⁐፹୰࡛࢖࣑ࢲࢰ࣮ࣝ

࠿ࡽ୰ᚰ㔠ᒓ࡬ࡢ㓄఩࡛ከ㔞య࡬⮬ᕫ⤌⧊໬ࡍࡿ࣏ࣝࣇ࢕࡛ࣜࣥ࠶ࡿࠋࢫ࣌ࢩ

ࣕࣝ࣌࢔ࣔࢹ࡛ࣝ࠶ࡿ஧㔞యࡣࠊ྾཰ࢫ࣌ࢡࢺࣝࡼࡾ

10

-9

M ࡢప⃰ᗘ࡛ࡶᏳᐃ

࡟Ꮡᅾࡍࡿࡇ࡜ࡀ☜ㄆࡉࢀ࡚࠸ࡿࠋ࣏ࣝࣇ࢕ࣜࣥࡢ⮬ᕫ⤌⧊໬ࡣࠊ࣏ࣝࣇ࢕ࣜ

ࣥࡢ

meso ఩࡟㔠ᒓ࡬㓄఩࡛ࡁࡿ⨨᥮ᇶࢆᑟධࡋࠊ㓄఩Ꮚࢆཷࡅධࢀࡿࡇ࡜ࡢ

࡛ࡁࡿ㔠ᒓࢆ୰ᚰ㔠ᒓ࡜ࡋ࡚ᑟධࡍࡿࡇ࡜࡟ࡼࡾ⮬ᕫ⤌⧊໬ࡉࡏࡿࠋ࣏ࣝࣇ࢕

ࣜࣥࡢ୰ᚰ㔠ᒓ࡟ࡣள㖄ࡸ࣐ࢢࢿࢩ࣒࢘ࡢ௚࡟ࡶࣝࢸࢽ࣒࢘ࡸࢥࣂࣝࢺࠊ࢜ࢫ

ࢽ࣒࢘࡞࡝ࡀ࠶ࡆࡽࢀࡿࠋࡇࡢ୰࡛ࡶ㸳㓄఩ࢆ࡜ࡿள㖄ࡣ㓄఩Ꮚ࡜ᙉࡃ⤖ྜࡍ

ࡿࡓࡵ࡟ࡼࡃ⏝࠸ࡽࢀࡿࠋࡲࡓࠊ࣐ࢢࢿࢩ࣒࢘ࡣ

6 㓄఩ࢆ࡜ࡿࡇ࡜ࡀ▱ࡽࢀ࡚

࠸ࡿࠋᑟධࡍࡿ⨨᥮ᇶ࡟ࡣ࢖࣑ࢲࢰ࣮ࣝࡸࣆࣜࢪࣥ࡞࡝Ꮩ❧㟁Ꮚᑐࢆᣢࡘࡶࡢ

ࢆ฼⏝ࡍࡿ

46

ࠋ

ᅗ 12 ࢖࣑ࢲࢰ࣮ࣝ⨨᥮࣏ࣝࣇ࢕ࣜࣥࢆ⏝࠸ࡓ⮬ᕫ⤌⧊໬44,45

15

ගྜᡂ⣽⳦ࡢ࢔ࣥࢸࢼ㘒య

_{(B850)ࢆᶍೌࡋࡓࣜࣥࢢ≧࡟⮬ᕫ⤌⧊໬ࡍࡿ࣏}

ࣝࣇ࢕ࣜࣥࡶሗ࿌ࡉࢀ࡚࠸ࡿ

(

ᅗ 13

)

47

ࠋࡇࡢ࣏ࣝࣇ࢕ࣜࣥࡣ᭷ᶵ⁐፹୰࡛ከ㔞

໬ࡍࡿ࣏ࣝࣇ࢕࡛ࣜࣥ࠶ࡿࠋᕼ㔘⁐፹୰࡛ࡣ

_{n=0, 1, 2 ࡲ࡛ࡢᵓ㐀࡛Ꮡᅾࡍࡿࡀࠊ}

⁐፹ࢆ⃰⦰ࡍࡿ࡜

n=5, 6 ࡢ᫬࡟ࣜࣥࢢ≧࡟࡞ࡿ࣏ࣝࣇ࢕࡛ࣜࣥ࠶ࡿࠋࡇࡢࣔࢹ

ࣝࡣኳ↛ࡢ࢔ࣥࢸࢼ㘒య

_{(B850)ࡀ஧㔞యࢆᇶᮏ༢఩࡜ࡋࠊࣜࣥࢢ≧࡟㓄ิࡋ࡚}

࠸ࡿⅬ࡟╔┠ࡋࠊᵓ⠏ࡉࢀࡓࡶࡢ࡛࠶ࡿࠋ

ᅗ 13 ⎔≧࣏ࣝࣇ࢕ࣜࣥࡢᵓ㐀47

16 ࡲࡓࠊ᭱㏆࡛ࡣࠊN-࣓ࢳࣝ࢖࣑ࢲࢰ࣮ࣝࢆ㸯ࡘࠊᏳᜥ㤶㓟ࢆ㸱ࡘ⨨᥮ࡋࡓ࣏ࣝࣇ࢕ ࣜࣥࢆྜᡂࡋࠊỈ୰࡟࠾࠸࡚ࡶ஧㔞య࡬⮬ᕫ⤌⧊໬ࡍࡿࡇ࡜ࢆሗ࿌ࡋ࡚ࡁࡓ (ᅗ 14)48ࠋࡋ࠿ࡋࠊࡇࢀࡽࡢ࣏ࣝࣇ࢕ࣜࣥࡣࠊ⁐ᾮ୰ࡢ⮬ᕫ⤌⧊໬࡛࠶ࡾࠊⰍ⣲ቑឤኴ㝧 㟁ụ࡜ࡋ࡚฼⏝ࡍࡿ࡟ࡣ㓟໬ࢳࢱࣥ㟁ᴟୖ࡛ࡢ⮬ᕫ⤌⧊໬ࡀᚲせ࡜࡞ࡿࠋ ᅗ 14 Ỉ୰࡛஧㔞໬ࡍࡿ࣏ࣝࣇ࢕ࣜࣥ48 㓟໬ࢳࢱࣥ㟁ᴟୖ࡛࣏ࣝࣇ࢕ࣜࣥࡢ⮬ᕫ⤌⧊໬࡟ࡼࡿ㓄ྥไᚚ࡜఍ྜไᚚࡀྍ⬟ ࡟࡞ࢀࡤࠊ㑄⛣཮ᴟᏊ┦஫స⏝࡜ȧ㌶㐨ࡢ㔜࡞ࡾࢆ฼⏝ࡋࡓຠ⋡ࡢࡼ࠸Ⰽ⣲ቑឤኴ㝧 㟁ụࡢ㛤Ⓨࡀᮇᚅ࡛ࡁࡿࠋ

17 2-1.2. ┠ⓗ  ࡑࡇ࡛ࠊᮏ◊✲࡛ࡣ N-࣓ࢳࣝ࢖࣑ࢲࢰ࣮ࣝࢆ㸰ࡘࠊᏳᜥ㤶㓟ࢆ㸰ࡘ⨨᥮ࡋࡓ࣏ࣝ ࣇ࢕ࣜࣥࡢMg 㘒యࢆྜᡂࡋࠊᏳᜥ㤶㓟ࡢ࢝ࣝ࣎ࣥ㓟ࢆ࢔࣮ࣥ࢝㒊࡜ࡋ࡚⏝࠸ࡿࡇ࡜ ࡛㓟໬ࢳࢱࣥ㟁ᴟୖ࡟ගྜᡂࡢගᤕ㞟࢔ࣥࢸࢼ㘒యB85040,41,49ࡢࡼ࠺࡞⮬ᕫ⤌⧊໬࡟ ࡼࡾ୰ᚰࢆࡎࡽࡋ࡚ȧࢫࢱࢵ࢟ࣥࢢࡋࡓᵓ㐀ࢆᣢࡘ࣏ࣝࣇ࢕ࣜࣥከ㔞య㸦J ఍ྜ㸧ࢆ ྾╔ࡉࡏࠊࡑࡢⰍ⣲ቑឤኴ㝧㟁ụࢆస〇ࡋ࡚ᛶ⬟ࢆホ౯ࡋࡓࡢ࡛ሗ࿌ࡍࡿࠋ ᅗ 15 ᮏ◊✲ࡢᴫᛕᅗ

18 2-2. ᐇ㦂㡯 2-2.1. ౑⏝ᶵჾ ᮏ◊✲࡛ࡣ⾲ 2 ࡟♧ࡋࡓᶵჾ࡛ ᐃࢆ⾜ࡗࡓࠋ ⾲ 2 ౑⏝ࡋࡓᶵჾ 㡯┠ ౑⏝ᶵჾ 1_{H NMR  ECS-400 (᪥ᮏ㟁Ꮚ)} ㉁㔞ศᯒ MStation JMS-700 ㉁㔞ศᯒ⿦⨨

ᅛయUV-VIS ࢫ࣌ࢡࢺࣝ HITACHI U-4000 ᾮయUV-VIS ࢫ࣌ࢡࢺࣝ UV-1700 ᓥὠ〇సᡤ

ⓑ㔠ࡢ┿✵⵨╔ IB- ION COATER

ࢯ࣮࣮ࣛࢩ࣑࣮ࣗࣞࢱ࣮ YSS-150A ᒣୗ㟁⿦ᰴᘧ఍♫ UV ࢜ࢰࣥࢡ࣮ࣜࢼ࣮ Filgen ࢔ࢡࢩࣙࣥࢫ࣌ࢡࢺࣝ ศගィჾ CEP-2000 ⺯ගࢫ࣌ࢡࢺࣝ RF-5300PC ᓥὠ〇సᡤ

19 2-2.2. ౑⏝ヨ⸆ ᮏ◊✲࡛ࡣ⾲ 3 ࡟♧ࡋࡓヨ⸆ࢆ㉎ධࡋࠊࣆ࣮ࣟࣝࡣ⵨␃ࡋࠊࡑࡢ௚ࡣࡑࡢࡲ ࡲ౑⏝ࡋࡓࠋ ⾲ 3 ౑⏝ࡋࡓヨ⸆ ヨ⸆ྡ ㉎ධඛ ୕ࡩࡗ໬࡯࠺⣲ࢪ࢚ࢳ࢚࣮ࣝࢸࣝ㘒య ࿴ග⣧⸆ᕤᴗ(ᰴ) 2,3-ࢪࢡࣟࣟ-5,6-ࢪࢩ࢔ࣀ-1,4-࣋ࣥࢰ࢟ࣀࣥ ᮾி໬ᡂᕤᴗᰴᘧ఍♫ ࢪࢡ࣓ࣟࣟࢱࣥ ࿴ග⣧⸆ᕤᴗᰴ ࣉࣟࣆ࢜ࣥ㓟 ࿴ග⣧⸆ᕤᴗ(ᰴ) 1-࣓ࢳࣝ-2-࣑࣍ࣝࣝ࢖࣑ࢲࢰ࣮ࣝ (ᰴ)࣡ࢥ࣮ࢣ࣑࢝ࣝ 4-࣑࣍ࣝࣝᏳᜥ㤶㓟࣓ࢳࣝ ALDRICH 㐣ሷ⣲㓟࣐ࢢࢿࢩ࣒࢘ ࿴ග⣧⸆ᕤᴗ(ᰴ) ⮯໬࣐ࢢࢿࢩ࣒࢘-ࢪ࢚ࢳ࢚࣮ࣝࢸࣝ㘒య ALDRICH ࣆ࣮ࣟࣝ ᮾி໬ᡂᕤᴗᰴᘧ఍♫ ࢺࣜࣇࣝ࢜ࣟ㓑㓟 ࿴ග⣧⸆ᕤᴗ(ᰴ) 㓑㓟ள㖄 ࿴ග⣧⸆ᕤᴗ(ᰴ)

20 2-2.3. ྜᡂ᪉ἲ ᅗ 16 5,10,15-ࢺࣜࢫ(4-࢝ࣝ࣎࢟ࢩࣇ࢙ࢽࣝ)-20-(1-࣓ࢳࣝ࢖࣑ࢲࢰ࣮ࣝ-2-࢖ࣝ)࣏ࣝࣇ࢕ ࣜࣥMg 㘒య (2)  5,10,15-ࢺࣜࢫ(4-࣓ࢺ࢟ࢩ࢝ࣝ࣎ࢽࣝࣇ࢙ࢽࣝ)-20-(1-࣓ࢳࣝ࢖࣑ࢲࢰ࣮ࣝ-2-࢖ࣝ)࣏ࣝࣇ࢕ࣜࣥࡢྜᡂ  30 mL ࡢ 2 ࡘཱྀࣇࣛࢫࢥ࡟ 4-࣑࣍ࣝࣝᏳᜥ㤶㓟࣓ࢳࣝ (246 mg, 1.50 mmol)ࠊ 1-࣓ࢳࣝ-2-࣑࣍ࣝࣝ࢖࣑ࢲࢰ࣮ࣝ (84.0 mg, 1.50 mmol)ࠊࣉࣟࣆ࢜ࣥ㓟 (10 ml)ࠊ ↓Ỉ㓑㓟 (0.6 ml)ࢆᖖ ୗ࡛ 10 ศᨩᢾࡋࡓࠋ⁐ゎࢆ☜ㄆࡋࠊࣇࣛࢫࢥࢆ࢔࣑ࣝ ࣍࢖࡛ࣝそࡗ࡚ࢩࣜࣥࢪ࡛ࣆ࣮ࣟࣝ (0.168 ml, 2.00 mmol)ࢆࡺࡗࡃࡾ⁲ୗࡋࡓࠋ 140Υ࡛ 3 ᫬㛫㑏ὶࡉࡏࠊᖖ ࡲ࡛෭ࡲࡋࠊ࢚ࣂ࣏࣮ࣞࢱ࡛⃰⦰ࡋࡓࠋ㐣๫㔞ࡢ ࢔ࣥࣔࢽ࢔࡛୰࿴ࠊℐ㐣ࢆ⾜࠺஦࡟ࡼࡾ㯮Ⰽᅛయࢆᚓࡓࠋࡇࢀࢆ࢔࣑ࣝࢼ࢝ࣛ ࣒ࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮ (ActivityϪ, ᒎ㛤⁐፹;ࢪࢡ࣓ࣟࣟࢱࣥ:㓑㓟࢚ࢳࣝ=15:1) ࡛⢭〇ࡋࠊ┠ⓗ໬ྜ≀ࢆ⣸Ⰽᅛయ (89.0 mg, 0.112 mmol, 22%)࡜ࡋ࡚ᚓࡓࠋ 1_{H NMR (600 MHz, CDCl} 3) G -2.81 (s, 2H, NH), 3.45 (s, 3H, imidazole-CH3), 4.10 (s,

9H, benzoate-CH3), 7.47 (d, 1H, imidazole), 7.66 (d, 1H, imidazole), 8.25-8.30 (m, 6H,

benzen), 8.44 (d, 6H, benzen), 8.83-8.84 (m, 8H, pyrrole); UV-VIS Ȣmax (CH2Cl2)=

420, 517, 554, 590, 643 nm; FluorescenceȢmax (CH2Cl2,Ȣex =420) 650, 712; FAB-MS

21 5,10,15-ࢺࣜࢫ(4-࢝ࣝ࣎࢟ࢩࣇ࢙ࢽࣝ)-20-(1-࣓ࢳࣝ࢖࣑ࢲࢰ࣮ࣝ-2-࢖ࣝ)࣏ࣝ ࣇ࢕ࣜࣥࡢྜᡂ  30 mL ࡢࣇࣛࢫࢥ࡟ 5,10,15-ࢺࣜࢫ(4-࣓ࢺ࢟ࢩ࢝ࣝ࣎ࢽࣝࣇ࢙ࢽࣝ)-20-(1-࣓ ࢳࣝ࢖࣑ࢲࢰ࣮ࣝ-2-࢖ࣝ)࣏ࣝࣇ࢕ࣜࣥࢆධࢀࠊࢸࢺࣛࣄࢻࣟࣇࣛࣥ (10 mL)࡟ ⁐ゎࡉࡏࡓࠋ1 M NaOH Ỉ⁐ᾮ (10 mL)ࢆຍ࠼ࠊ24 ᫬㛫᧠ᢾࡋࡓࠋ᭷ᶵᒙࢆ㝖ࡁࠊ Ỉᒙࢆࢡ࣒ࣟࣟ࣍ࣝ10 mL ࡛ 3 ᅇὙίࡋࡓࠋỈᒙࢆ 1 M ሷ㓟࡛୰࿴ࡋࠊ┠ⓗ⏕ ᡂ≀ࢆ⣸Ⰽᅛయ࡛ᚓࡓࠋ(50 mg, 40%) 5,10,15-ࢺࣜࢫ(4-࢝ࣝ࣎࢟ࢩࣇ࢙ࢽࣝ)-20-(1-࣓ࢳࣝ࢖࣑ࢲࢰ࣮ࣝ-2-࢖ࣝ)࣏ࣝࣇ ࢕ࣜࣥMg 㘒య (2)ࡢྜᡂ  30 mL ࣇࣛࢫࢥ࡟ࠊ5, 10, 15-ࢺࣜࢫ(4-࢝ࣝ࣎࢟ࢩࣇ࢙ࢽࣝ)-20-(1-࣓ࢳࣝ࢖࣑ ࢲࢰ࣮ࣝ-2-࢖ࣝ)࣏ࣝࣇ࢕ࣜࣥ (50 mg, 0.016 mmol)࡜㐣㓟໬࣐ࢢࢿࢩ࣒࢘ (90 mg, 16 mmol)ࢆຍ࠼ࠊࣆࣜࢪࣥ (10 mL)࡟⁐ゎࡋࠊ❅⣲ୗ࡛ 24 ᫬㛫㑏ὶࡋࡓࠋ ᐊ ࡲ࡛෭ࡲࡋࡓᚋࠊ⁐፹ࢆῶᅽ⃰⦰ࡋࡓࠋṧࡗࡓᅛయࢆ࣎ࣟࣥ㓟⦆⾪ᾮ(pH=5)ࠊ

Ỉ࡛Ὑίࡋ࡚┠ⓗ⏕ᡂ≀ࢆᚓࡓ (20 mg, 0.026 mmol, 61%)ࠋUV-VIS λmax (phosphate buffer pH7.4) 428, 567, 613 nm.

22 ᅗ 17 5,10,15-ࢺࣜࢫ(4-࢝ࣝ࣎࢟ࢩࣇ࢙ࢽࣝ)-20-(1-࣓ࢳࣝ࢖࣑ࢲࢰ࣮ࣝ-2-࢖ࣝ)࣏ࣝࣇ࢕ ࣜࣥMg 㘒య (3)ࡢྜᡂ⤒㊰ 5,15-ࣅࢫ(4-࣓ࢺ࢟ࢩ࢝ࣝ࣎ࢽࣝࣇ࢙ࢽࣝ)-10,20-ࣅࢫ(1-࣓ࢳࣝ࢖࣑ࢲࢰ࣮ࣝ-2-࢖ࣝ)࣏ࣝࣇ࢕ࣜࣥࡢྜᡂ 50 mLࣇࣛࢫࢥ࡟4-࣓ࢺ࢟ࢩ࢝ࣝ࣎ࢽࣝࣇ࢙ࢽࣝࢪࣆ࣓ࣟࢱࣥ (280 mg, 1.0 mmol), 1-࣓ࢳࣝ-2-࢖࣑ࢲࢰ࣮ࣝ࢝ࣝࣂࣝࢹࣄࢻ (110 mg, 1.0 mmol)ࢆࣉࣟࣆ࢜ ࣥ㓟 (10 mL)࡜↓Ỉ㓑㓟(0.5 mL)࡟⁐࠿ࡋࠊ9᫬㛫㑏ὶࡋࡓࠋ⁐፹ࢆῶᅽ⃰⦰ࡋࠊ ṧࡗࡓ㯮ⰍࡢᅛయࢆⅣ㓟Ỉ⣲ࢼࢺ࣒ࣜ࢘Ỉ⁐ᾮ࡛Ὑίࡋࡓࠋ࣒࢝ࣛࢡ࣐ࣟࢺࢢ ࣛࣇ࢕࣮ࢆ⾜࠸ (Al2O3, activity Ϫ, ethyl acetate: hexane=1: 1 to 1:0)ࠊ┠ⓗ⏕ᡂ≀

ࢆ⣸Ⰽᅛయ࡜ࡋ࡚ᚓࡓ(120 mg, 0.16 mmol, 16 %)ࠋ1H NMR (600 MHz, CDCl3) δ -2.85 (s, 2H), 3.43-3.49 (s, 6H, N-CH3), 4.14 (s, 6H, methoxy), 7.49 (d, 2H, imidazole), 7.68 (d, 2H, imidazole), 8.30 (d, 4H, phenyl), 8.48 (d, 4H, phenyl), 8.87 (m, 8H,

pyrrolic-șH); UV-vis λmax (CH2Cl2) 431, 541, 548, 588, 643 nm; FAB-MS m/z = 738.2703.

23 5,15-ࣅࢫ(4-࢝ࣝ࣎࢟ࢩࣇ࢙ࢽࣝ)-10,20-ࣅࢫ(1-࣓ࢳࣝ࢖࣑ࢲࢰ࣮ࣝ-2-࢖ࣝ)࣏ࣝ ࣇ࢕ࣜࣥࡢྜᡂ  10 mL ࣇࣛࢫࢥ࡟ 5, 15-ࣅࢫ(4-࣓ࢺ࢟ࢩ࢝ࣝ࣎ࢽࣝࣇ࢙ࢽࣝ)-10, 20-ࣅࢫ(1-࣓ ࢳࣝ࢖࣑ࢲࢰ࣮ࣝ-2-࢖ࣝ)࣏ࣝࣇ࢕ࣜࣥ࡜ THF (10 mL)ࢆධࢀ⁐ゎࡋࡓࠋ1M Ỉ㓟 ໬ࢼࢺ࣒ࣜ࢘Ỉ⁐ᾮࢆ10 mL ຍ࠼ࠊ21 ᫬㛫᧠ᢾࡋࡓࠋ᭷ᶵᒙࢆ㝖ࡁࠊỈᒙࢆࢡ ࣒ࣟࣟ࣍ࣝ10 mL ࡛ 3 ᅇὙίࡋࡓࠋỈᒙࢆ 1 M ሷ㓟࡛୰࿴ࡋࠊ┠ⓗ⏕ᡂ≀ࢆ⣸ Ⰽᅛయ࡛ᚓࡓࠋ(12 mg, 50%) 5,15-ࣅࢫ(4-࢝ࣝ࣎࢟ࢩࣇ࢙ࢽࣝ)-10,20-ࣅࢫ(1-࣓ࢳࣝ࢖࣑ࢲࢰ࣮ࣝ-2-࢖ࣝ)࣏ࣝ ࣇ࢕࣐ࣜࣥࢢࢿࢩ࣒࢘㘒య (3)ࡢྜᡂ 30 mLࣇࣛࢫࢥ࡟ࠊ5, 15-ࣅࢫ(4-࢝ࣝ࣎࢟ࢩࣇ࢙ࢽࣝ)-10, 20-ࣅࢫ(1-࣓ࢳࣝ࢖࣑ࢲ ࢰ࣮ࣝ-2-࢖ࣝ)࣏ࣝࣇ࢕ࣜࣥ (12 mg, 0.016 mmol)࡜㐣㓟໬࣐ࢢࢿࢩ࣒࢘ (50 mg, 22 mmol)ࢆຍ࠼ࠊࣆࣜࢪࣥ (2 mL)࡟⁐ゎࡋࠊ❅⣲ୗ࡛24᫬㛫㑏ὶࡋࡓࠋᐊ ࡲ ࡛෭ࡲࡋࡓᚋࠊ⁐፹ࢆῶᅽ⃰⦰ࡋࡓࠋṧࡗࡓᅛయࢆ࣎ࣟࣥ㓟⦆⾪ᾮ (pH=5)ࠊỈ

࡛Ὑίࡋ࡚┠ⓗ⏕ᡂ≀ࢆᚓࡓ (3.2 mg, 0.0043 mmol, 33 %). UV-vis λmax (phosphate buffer pH7.4) 380, 427, 449, 568, 594, 611 nm; Fluorescence λmax (λex = 449) 621, 673 nm.

24 2-2.4. Ⰽ⣲ቑឤኴ㝧㟁ụస〇᪉ἲ స⏝ᴟస〇  FTO ㏱᫂㟁ᴟࢆ⣧Ỉ࡜ VISTA ⁐ᾮࠊ⣧Ỉࠊ࢔ࢭࢺࣥࠊ2-ࣉࣟࣃࣀ࣮࡛ࣝࡑࢀ ࡒࢀ30 ศ㛫㉸㡢Ἴ࡟ࡼࡾὙίࡋࠊ40 mM ᅄሷ໬ࢳࢱࣥỈ⁐ᾮ୰࡛ 70Υࠊ30 ศ ࡛ Ỉฎ⌮ࡋࡓࠋ㓟໬ࢳࢱ࣮ࣥ࣌ࢫࢺ(PST-18NR, ⢏ᚄ 18 nm, ᪥ᮏゐ፹໬ᡂ)ࢆ 㟁ᴟ࡟ཌࡉ8ȣm ࡟࡞ࡿࡼ࠺࡟ሬᕸࡋࠊ125Υ࡛ࣉࣜ࢔ࢽ࣮ࣝࡋࡓࠋ500Υ࡛࢔ࢽ ࣮ࣝࡋࡓࠋ㟁ᴟࢆ෌ࡧ40 mM ᅄሷ໬ࢳࢱࣥỈ⁐ᾮ୰࡛ 70Υࠊ30 ศ࡛ Ỉฎ⌮ࡋ ࡓᚋࠊ500Υ࡛࢔ࢽ࣮ࣝࡋࡓࠋ࡛ࡁࡓ㟁ᴟࢆ 100ȣM ࡢⰍ⣲⁐ᾮ࡟ᐊ ࡛ 24 ᫬㛫 ࡑࢀࡒࢀࡢⰍ⣲ࢆᾐࡋࡓࠋ ᑐᴟస〇  ⓑ㔠ࢆFTO ㏱᫂㟁ᴟ࡟┿✵⵨╔ࡋࡓ (┿✵⵨╔⿦⨨/ᰴᘧ఍♫࢚࢖ࢥ࣮)ࠋ 㟁ゎ㉁  ࢸࢺࣛࣉࣟࣆࣝ࢔ࣥࣔࢽ࣒࣮࢘ࣚࢪࢻ 1 Mࠊࣚ࢘⣲ 0.1 M ࢔ࢭࢺࢽࢺࣜ ࣝ㸸࢚ࢳ࣮ࣞࣥ࢝࣎ࢿ࣮ࢺ㸻㸲㸸㸯

25 㟁ᴟࡢ㈞ࡾྜࢃࡏ

 స⏝ᒁࡢ㓟໬ࢳࢱࣥ㠃✚ࡣ0.3 cm2࡟࡞ࡿࡼ࠺࡟ࡋࠊᑐᴟ࡜స⏝ᴟࢆ᥋╔ᛶࡢ ࣇ࢖࣒ࣝ(HIMILAN, Mitsui-Dupont Polychemical, 35 μm of thickness)࡛㈞ࡾྜࢃࡏࡓ (ᅗ

18 స〇ࡋࡓⰍ⣲ቑឤኴ㝧㟁ụࡢᶍᘧᅗ50ᅗ 18)ࠋ

26 㟁ụ≉ᛶホ౯ ࢯ࣮࣮ࣛࢩ࣑࣮ࣗࣞࢱ(YSS-150Aࠊᒣୗ㟁⿦)࡜࣏ࢸࣥࢩࣙࣥࢫࢱࢵࢺ (VersaSTAT㸲/ᮾ㝧ࢸࢡࢽ࢝)ࢆ⏝࠸࡚㟁ụࡢ≉ᛶホ౯ࢆ⾜ࡗࡓࠋ࢔ࢡࢩࣙࣥࢫ࣌ ࢡࢺࣝࡢ ᐃ࡟ࡣCEP-2000 ᆺศගឤᗘ ᐃ⿦⨨ࢆ౑⏝ࡋࠊ ᐃ࣮ࣔࢻ㸸DCࠊ ࣇ࢛ࢺࣥᩘ㸸0.5™1016/(s࣭cm2)࡛⾜ࡗࡓࠋࡲࡓࠊගᙉᗘࡣ 100mW/cm2ࠊAM1.5 ࡢ᮲௳࡛ࠊ㐽ග࣐ࢫࢡࢆ⏝࠸࡚ග㟁ᴟ㠃✚ࢆ0.2 cm2࡟ࡋࡓࠋ ᢬ᢠ್ࡀࢮࣟࡢ᫬Isc(▷⤡ග㟁ὶ)ࠊ᢬ᢠ್ࡀ↓㝈኱ࡢ᫬ Voc (㛤ᨺ㟁ᅽ)ࡀᚓࡽࢀࠊ ࢭࣝࡢฟຊP ࡣᘧ(1)ࡢࡼ࠺࡟࡞ࡿࠋ P = IV ᘧ 1 㟁ụ≉ᛶࢆホ౯ࡍࡿࣃ࣓࣮ࣛࢱ࡜ࡋ࡚ࣇ࢕ࣝࣇ࢓ࢡࢱ࣮(fill factor:F. F.)ࡀ࠶ࡾࠊ ᘧ(2)ࡢࡼ࠺࡟ᐃ⩏ࡉࢀࡿࠋ F.F=Pmax/(Voc࣭Isc)    ᘧ 2 Pmax㸸ࢭࣝࡢ᭱኱ฟຊ[W] Voc㸸㛤ᨺ㟁ᅽ[V] Isc㸸▷⤡ග㟁ὶ[A] ࢭࣝࡢ᭱⤊ⓗ࡞ホ౯ࡣࠊග࢚ࢿࣝࢠ࣮ࡢኚ᥮ຠ⋡Ȟ࡛࠶ࡾࠊȞࡣᘧ(3)ࡢࡼ࠺࡟ ᐃ⩏ࡉࢀ࡚࠸ࡿࠋ

27

Ȟ=ኴ㝧㟁ụࡢฟຊ/ࢭࣝ࡬ࡢධᑕ࢚ࢿࣝࢠ࣮  ™100  ᘧ 3

እ㒊㔞Ꮚຠ⋡(IPCE) ᐃ

ᘧ(4)࡛⾲ࡉࢀࡿ IPCE ࡣࠊCEP-2000 ᆺศගឤᗘ ᐃ⿦⨨ࢆ⏝࠸ࠊ࢟ࢭࣀࣥࣛࣥ

ࣉࢆග※࡜ࡋࠊගᙉᗘ100 mW/cm2 (AM1.5)ࠊDC ࣮ࣔࢻ࡛ ᐃࡋࡓࠋ

IPCE (%)= 1240 iphoto (A/cm2)/Ȣ(nm)/Iinc (W/cm2) ™100   ᘧ 4

iphoto㸸༢Ⰽග࡟࠾ࡅࡿග㟁ὶ[A/cm2], Ȣ:ධᑕගࡢἼ㛗[nm]

28 2-3. ⤖ᯝ࡜⪃ᐹ 2-3.1. ࣏ࣝࣇ࢕ࣜࣥ 1ࠊ2ࠊ3 ࡢྜᡂ  3 ࡢྜᡂࡣࠊ࣏ࣝࣇ࢕ࣜࣥࡢᑐ㠃ࡍࡿ࣓ࢯ఩࡟㸰ࡘࡢ N-࣓ࢳࣝ࢖࣑ࢲࢰ࣮ࣝࠊ ௚᪉ࡢ㸰ࡘ࡟Ᏻᜥ㤶㓟ࢆᑟධࡍࡿࡓࡵ࡟ࠊࡲࡎࠊᏳᜥ㤶㓟࣓ࢳࣝࢆ⨨᥮ࡋࡓࢪ ࣆ࣓ࣟࢱࣥࢆྜᡂࡋࡓࠋḟ࡟ࠊࡇࡢࢪࣆ࣓ࣟࢱࣥࢆ N-࣓ࢳࣝ࢖࣑ࢲࢰ࣮ࣝ࢝ࣝ ࣂࣝࢹࣄࢻ࡜ࣉࣟࣆ࢜ࣥ㓟୰࡛㑏ὶࡍࡿࡇ࡜࡛ࠊ┠ⓗࡢࣇ࣮࣮ࣜ࣋ࢫ࣏ࣝࣇ࢕ ࣜࣥࢆྜᡂࡋࠊ࣒࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮࡛༢㞳ࡋࡓ(y=5%)ࠋࡑࡢᚋࠊỈ㓟໬ ࢼࢺ࣒ࣜ࢘Ỉ⁐ᾮ࡟ࡼࡗ࡚࢚ࢫࢸࣝຍỈศゎࢆ⾜ࡗࡓࠋࡉࡽ࡟ࠊ㐣㓟໬࣐ࢢࢿ ࢩ࣒࢘࡜ࣆࣜࢪࣥ୰࡛㑏ὶࡉࡏࡿࡇ࡜࡟ࡼࡗ࡚ࠊ࣐ࢢࢿࢩ࣒࢘㘒య (3)ࢆᚓࡓࠋ ࡲࡓࠊࢥࣥࢺ࣮ࣟࣝ࡜ࡋ࡚ࠊN-࣓ࢳࣝ࢖࣑ࢲࢰ࣮ࣝࢆ㸯ࡘࠊᏳᜥ㤶㓟ࢆ 3 ࡘ⨨ ᥮ࡋࡓ࣏ࣝࣇ࢕ࣜࣥ48ࡢMg 㘒య 2 ࡜ TCPP ࡢ Mg 㘒య 1 ࡶྠᵝ࡟ྜᡂࡋࡓࠋ ᅗ 19 ᮏ◊✲࡛⏝࠸ࡓ࣏ࣝࣇ࢕ࣜࣥ

29 2-3.2. ⁐ᾮ୰࡛ࡢ UV-VIS ࢫ࣌ࢡࢺࣝ  1ࠊ2ࠊ3 ࡣ࢝ࣝ࣎ࣥ㓟ྠኈࡢỈ⣲⤖ྜࡢࡓࡵࠊࢪࢡ࣓ࣟࣟࢱࣥࡸ࢔ࢭࢺࢽࢺࣜ ࣝ࡞࡝ࡢ᭷ᶵ⁐፹࡬ࡢ⁐ゎᗘࡀప࠸ࡀࠊpH=7.4 ࣜࣥ㓟⦆⾪ᾮࢆ⏝࠸ࡿ࡜࢝ࣝ࣎ ࢟ࢩ࣮ࣛࢺ࢖࢜ࣥࡢ≧ែ࡛⁐ゎࡋࡓࠋUV-VIS ࢫ࣌ࢡࢺࣝ࠿ࡽࠊࡲࡎࠊSoret ᖏ࡟ ╔┠ࡋࡓ (⾲ 4, ᅗ 20)ࠋ1 ࡣ 421 nm ࡟㗦࠸ࣆ࣮ࢡࢆ♧ࡋࡓࡇ࡜࠿ࡽ༢㔞య࡛࠶ ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡲࡓࠊ2 ࡛ࡣ 428 nm ࢆ㡬Ⅼ࡜ࡋࣈ࣮ࣟࢻ࡞ࣆ࣮ࢡࢆ♧ࡍࡇ ࡜ࡀࢃ࠿ࡗࡓࠋࡇࢀࡣ┤஺ࡍࡿ㑄⛣཮ᴟᏊࡢ࠺ࡕࠊ͆face-to-face͇ࡢᡂศࡀ┦஫ స⏝ࡋ࠶ࡗ࡚▷Ἴ㛗࡟ࢩࣇࢺࡋࠊࡲࡓࠊ͆head-to-tail͇ࡢ㑄⛣཮ᴟᏊࡢ┦஫స⏝ ࡛ࠊ㛗Ἴ㛗ࢩࣇࢺࡋࡓࡓࡵ࡜⪃࠼ࡽࢀࡿ51ࠋࣆ࣮ࢡࡀศ⿣ࡋ࡞࠿ࡗࡓࡢࡣࠊ⁐፹ ࡛࠶ࡿỈࡀMg ࡜┦஫స⏝ࡋࡓࡓࡵ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋ3 ࡛ࡣ 380 nm ࡜ 449 nm ࡟ศ⿣ࡍࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡇࢀࡣ 2 ࡜ྠᵝ࡟࣏ࣝࣇ࢕ࣜࣥࡀ఍ྜࡋࡓࡇ࡜࡟ ࡼࡾ㉳ࡇࡿ㑄⛣཮ᴟᏊ┦஫స⏝࡟ࡼࡿࡶࡢ࡜⪃࠼ࡽࢀࡿࠋ2ࠊ3 ࢆẚ㍑ࡍࡿ࡜ࠊ2 ࡣ⣙30 nm (1610 cm-1)ࠊ3 ࡣ 69 nm (4040 cm-1)ศ⿣ࡋ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡇ ࡢศ⿣Ἴ㛗ࡢᕪ࠿ࡽ2 ࡣ஧㔞య㸦22㸧ࢆᙧᡂࡋ࡚࠾ࡾࠊࡲࡓ3 ࡣከ㔞య (3n)ࢆᙧ ᡂࡋ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡿ*1ࠋḟ࡟ࠊQ-band ࡟╔┠ࡍࡿ࡜ࠊ஧㔞య (22)࠿ࡽከ㔞య (3n)࡟࡞ࡿ࡟ࡘࢀ࡚ࠊȜȘ/Ȝșࡀ0.71 ࠿ࡽ 0.50 ࡬࡜ῶᑡࡍࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋ᭦ ࡟3 ࡛ࡣࠊ594 nm ࡟᪂ࡓ࡞ࣆ࣮ࢡࡀฟ⌧ࡍࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡇࡢࣆ࣮ࢡࡣ࣏ ࣝࣇ࢕ࣜࣥ࡟⨨᥮ࡉࢀࡓMg ࡀ 6 㓄఩ᛶࢆ࡜ࡗࡓ᫬࡟ぢࡽࢀࡿࣆ࣮ࢡ࡛࠶ࡿ52ࠋ ࡇࢀࡽࡢࡇ࡜࠿ࡽࠊྜᡂࡋࡓ࣏ࣝࣇ࢕ࣜࣥMg 㘒యࡣࣜࣥ㓟⦆⾪ᾮ୰࡛㓄఩࡟ࡼ ࡾ୰ᚰࢆࡎࡽࡋ࡚ȧࢫࢱࢵ࢟ࣥࢢࡋࡓከ㔞య (J ఍ྜయ)࡟࡞ࡗ࡚࠸ࡿ࡜⪃࠼ࡽ ࢀࡿࠋࡲࡓࠊ⺯ගࢫ࣌ࢡࢺ࡛ࣝࡶࠊ1 ࡀ 613 nm ࢆ♧ࡋࠊ3 ࡀ 621 nm ࡢࣆ࣮ࢡࢆ ♧ࡋࠊࣆ࣮ࢡࡀ8 nm 㛗Ἴ㛗࡬ࢩࣇࢺࡋࡓࡇ࡜࠿ࡽࠊȧࢫࢱࢵ࢟ࣥࢢ࡟ࡼࡿከ㔞 య㸦J ఍ྜ㸧ࡢᙧᡂ࡛ࠊHOMO-LUMO 㛫ࡢ࢚ࢿࣝࢠ࣮ࢠࣕࢵࣉࡀᑠࡉࡃ࡞ࡗ࡚ ࠸ࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋ

30 ᅗ 20 ࣏ࣝࣇ࢕ࣜࣥ 1, 2, 3 ࡢ྾཰ࢫ࣌ࢡࢺࣝ (ࣜࣥ㓟⦆⾪ᾮ pH=7.4) ⾲ 4 ࣏ࣝࣇ࢕ࣜࣥ 1, 2, 3 ࡢ྾཰ࢫ࣌ࢡࢺࣝ (ࣜࣥ㓟⦆⾪ᾮ pH=7.4)࡜ 㓟໬ࢳࢱࣥୖ࡛ࡢ྾཰ࢫ࣌ࢡࢺࣝ 㸨㸯_Ỉࡢ Mg ࡬ࡢ㓄఩࡟ࡼࡾ༢㔞య࡜ࡢᖹ⾮ࡶぢࡽࢀࡿࡢ࡛ࠊỈ୰࡛ࡣ༢㔞య࣭ ஧㔞య࣭୕㔞య࣭ᅄ㔞య͐ከ㔞య (3n)࡜ࡢᖹ⾮ΰྜ≀࡛Ꮡᅾࡋ࡚࠸ࡿ࡜⪃࠼ࡽ ࢀࡿࠋN-࣓ࢳࣝ࢖࣑ࢲࢰ࣮ࣝ࡜࢔ࣝ࢟ࣝ㙐ࢆ⨨᥮ࡋࡓ࣏ࣝࣇ࢕ࣜࣥ Co 㘒యࡣ᭷ ᶵ⁐፹୰࡛404 nmࠊ474 nm ࡢศ⿣ࣆ࣮ࢡ (3650 cm-1)ࢆ♧ࡋࠊ90㹼500 㔞యࡢከ 㔞యࢆᙧᡂࡍࡿࡇ࡜࠿ࡽࠊᡃࠎࡢ㉸ศᏊ࣏ࣝࣇ࢕ࣜࣥ (3n)ࡶ 380 nmࠊ449 nm ࡢ ศ⿣ࣆ࣮ࢡ(4040 cm-1)࡜ࡑࡢࣈ࣮ࣟࢻ໬ࢆ⪃៖ࡍࡿ࡜ࠊྠ⛬ᗘ࠿ࡑࢀ௨ୖࡢከ㔞 యࢆᙧᡂࡋ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡿࠋỈ୰࡛ከ㔞యࢆᙧᡂࡍࡿࡢࡣࠊ(N-࣓ࢳࣝ࢖࣑ ࢲࢰ࣮ࣝࡢ༠ྠⓗ࡞㓄఩࡟ຍ࠼ࠊ)␯Ỉᛶ┦஫స⏝࡜ȧࢫࢱࢵ࢟ࣥࢢࡀ㉳ࡇࡗ࡚ ࠸ࡿࡓࡵ࡜⪃࠼ࡽࢀࡿࠋ

31 2-3.3. 㓟໬ࢳࢱࣥୖ࡛ࡢᅛయ UV-VIS ࢫ࣌ࢡࢺࣝ  ୍᪉ࠊ㓟໬ࢳࢱࣥ㟁ᴟୖ࡛ࡶ⮬ᕫ⤌⧊໬ࡀ㉳ࡇࡿ࠿࡝࠺࠿ࢆ᳨ウࡍࡿࡓࡵࠊ1ࠊ 2ࠊ3 ࢆ࣓ࢱࣀ࣮ࣝ࡟⁐ゎࡋࠊ㓟໬ࢳࢱࣥ㟁ᴟࢆᾐࡍࡇ࡜࡟ࡼࡾࠊⰍ⣲ࢆ྾╔ࡉ ࡏࡓ㸨2_{ࠋᅗ 21 ࡣ 1ࠊ2ࠊ3 ࡢ㓟໬ࢳࢱࣥୖ࡛ࡢ UV-VIS ࢫ࣌ࢡࢺ࡛ࣝ࠶ࡿࠋQ-band} ࡟╔┠ࡍࡿ࡜ࠊ⁐ᾮ≧ែ࡜ྠᵝ࡟ࠊȜȘ/Ȝșࡀከ㔞໬ࡍࡿ࡟㐃ࢀ࡚0.66 ࠿ࡽ 0.30 ࡬࡜ᑠࡉࡃ࡞ࡗ࡚࠸ࡃࡇ࡜ࡀࢃ࠿ࡗࡓࠋ᭦࡟3 ࡛ࡣࠊ6 㓄఩ᛶࢆ࡜ࡗࡓ㝿࡟ぢࡽ ࢀࡿ᪂ࡓ࡞ࣆ࣮ࢡࡀ593 nm ࡟ฟ⌧ࡋࡓࠋࡇࢀࡽࡢࡇ࡜࠿ࡽࠊྜᡂࡋࡓ࣏ࣝࣇ࢕ ࣜࣥMg 㘒యࡣ㓟໬ࢳࢱࣥ㟁ᴟୖࠊᅛయ≧ែ࡛ࡶ Mg ࡬ࡢ㓄఩࡟ࡼࡿከ㔞య㸦J ఍ྜ㸧ࢆᙧᡂࡍࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡲࡓࠊUV-VIS ࢫ࣌ࢡࢺࣝ࡟ࡼࡿ Q-band ࡢ 608 nm ࠿ࡽ 611 nm ࡬ࡢ㛗Ἴ㛗ࢩࣇࢺ࠿ࡽࠊከ㔞య (J ఍ྜ)ࡢᙧᡂ࡟క࠺ศᏊ㛫 ┦஫స⏝࡟ࡼࡿLUMO (S1)ࡢศ⿣ࡶ♧၀ࡉࢀࡓࠋ *2_{ 1ࠊ2ࠊ3 ࡣ࢝ࣝ࣎ࣥ㓟ྠኈࡢỈ⣲⤖ྜ࡟ࡼࡾࠊ᭷ᶵ⁐፹࡟ࡣ⁐ࡅ࡟ࡃ࠸ࡀࠊ} ࣓ࢱࣀ࣮ࣝࡢࡼ࠺࡞Ỉ⣲⤖ྜࢆษࡿ⁐፹࡟ࡣྍ⁐࡛࠶ࡿࠋࡓࡔࡋࠊ⁐ᾮ୰࡛ࡣ ୺࡟༢㔞య≧ែ࡛Ꮡᅾࡍࡿࠋ ᅗ 21 ࣏ࣝࣇ࢕ࣜࣥ 1, 2, 3 ࡢ㓟໬ࢳࢱࣥୖ࡛ࡢ྾཰ࢫ࣌ࢡࢺࣝ

32 2-3.4. Ⰽ⣲ቑឤኴ㝧㟁ụ  ࡇࡢ㓟໬ࢳࢱࣥ㟁ᴟୖ࡛⮬ᕫ⤌⧊໬ࡉࡏࡓ࣏ࣝࣇ࢕ࣜࣥࢆⰍ⣲ቑឤኴ㝧㟁ụ ࡜ࡋ࡚ᛶ⬟ࢆホ౯ࡋࡓ㸦⾲ 5㸧ࠋ ⾲ 5 ࣏ࣝࣇ࢕ࣜࣥ 1, 2, 3 ࡢኴ㝧㟁ụᛶ⬟ ( ᐃ᮲௳㸸ගᙉᗘ 100 mW/cm2, AM:1.5, ᭷ຠ㠃✚ 0.2 cm2) ᅗ 22 ࣏ࣝࣇ࢕ࣜࣥ 1, 2, 3 ࡟ࡼࡿⰍ⣲ቑឤ㟁ụࡢ IPCE ( ᐃ᮲௳㸸DC ࣮ࣔࢻ, ࣇ࢛ࢺࣥᩘ 0.5™1016, ᭷ຠ㠃✚ 0.2 cm2)           Wavelength (nm) IP C E (%)

33 ࡲࡎࠊ㟁ὶ್࡟╔┠ࡍࡿ࡜ࠊ1 ࡜ 2 ࢆẚ㍑ࡍࡿ࡜ࠊ஧㔞య (22)ࡣ 1.7 ಸ࡟㟁ὶ ್ࡀୖ᪼ࡋࠊ༢㔞య࠿ࡽከ㔞య (3n)࡟࡞ࡿ࡜ 1.81 ಸ࡟㟁ὶ್ࡀୖ᪼ࡍࡿࡇ࡜ࡀ ࢃ࠿ࡗࡓࠋ୍᪉ࠊࢥࣥࢺ࣮ࣟࣝᐇ㦂࡜ࡋ࡚ࠊ1ࠊ2ࠊ3 ࡀ㓄఩⤖ྜࢆࡋ࡞࠸ (Mg ࢆᑟධࡋ࡚࠸࡞࠸)ࣇ࣮࣮ࣜ࣋ࢫ࣏ࣝࣇ࢕ࣜࣥࡢኴ㝧㟁ụᛶ⬟ࢆ ᐃࡋࡓ (ࢧ࣏ ࣮㊰ࢹ࣮ࢱཧ↷)ࠋࡇࡢࢥࣥࢺ࣮ࣟࣝᐇ㦂࠿ࡽࠊ࣏ࣝࣇ࢕ࣜࣥ࡟࠾࠸࡚ࠊN-࣓ࢳ ࣝ࢖࣑ࢲࢰ࣮ࣝࡢ⨨᥮ᩘࡀከࡃ࡞ࡿ࡟ࡘࢀ࡚ࠊJsc ࡀῶᑡࡋ࡚㟁Ꮚὀධࡀ㉳ࡇࡾ ࡟ࡃࡃ࡞ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡇࢀࡽࡢ⤖ᯝࢆ⪃៖ࡍࡿ࡜ࠊከ㔞య࡟࡞ࡿ࡟㐃ࢀ ࡚㉳ࡇࡿ㟁ὶ್ࡢୖ᪼ࡣ N-࣓ࢳࣝ࢖࣑ࢲࢰ࣮ࣝࡢᙳ㡪࡛ࡣ࡞ࡃࠊ࣏ࣝࣇ࢕ࣜࣥ ࡀȧࢫࢱࢵ࢟ࣥࢢᵓ㐀㸦J ఍ྜ㸧ࢆᙧᡂࡍࡿࡇ࡜࡟ࡼࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋከ㔞 య㸦J ఍ྜ㸧ࡀ஧㔞య࡜࠶ࡲࡾᕪࡀ࡞࠸ࡢࡣࠊN-࣓ࢳࣝ࢖࣑ࢲࢰ࣮ࣝࡢ⨨᥮ᩘࡢ ቑຍࡢࡓࡵࠊᛶ⬟ࡀከ㔞య (J ఍ྜ)࠿ࡽᚓࡽࢀࡿᮏ᮶ࡢ್ࡼࡾࡶᑠࡉࡃ࡞ࡗࡓ࡜ ⪃࠼ࡽࢀࡿࠋ ḟ࡟ࠊ㟁ᅽ࡟╔┠ࡍࡿ࡜ࠊ1 ࡜ 2 ࢆẚ㍑ࡍࡿ࡜஧㔞య (22)ࡣ 1.87 ಸࠊከ㔞య ஧㔞య (3n)1.7 ಸ࡟ྥୖࡍࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡇࢀࡣࠊ༢㔞యࡣࣛࣥࢲ࣒࡞྾╔ (ࡲࡓࡣࠊ1 ࡢࣛࣥࢲ࣒࡞఍ྜయ࡛྾╔)࡛࠶ࡿࡀࠊ஧㔞యࠊከ㔞య㸦J ఍ྜ㸧ࡣ つ๎ⓗ࡞㓄ྥไᚚ࡟ࡼࡿከ㔞య࡛ࠊ㓟໬ࢳࢱࣥ㟁ᴟୖ࡟྾╔ࡉࢀࡿࡓࡵࠊ㓟໬ ࢳࢱࣥ㟁ᴟ࠿ࡽ㟁ゎᾮ୰ࡢ I3- ࡬ࡢ㟁Ꮚࡢ෌⤖ྜࡀᢚไࡉࢀࡓࡶࡢ࡜⪃࠼ࡽࢀ ࡿࠋ ࡇࢀࡽࡢ⤖ᯝ࠿ࡽࠊኚ᥮ຠ⋡ࡣ༢㔞య0.18%࠿ࡽ஧㔞యࠊከ㔞య 0.60㸣࡬࡜⣙ 3 ಸୖ᪼ࡋࡓࠋ

IPCE ࡟╔┠ࡍࡿ࡜ (ᅗ 22)ࠊ1 ࡜ 2ࠊ3 ࢆẚ㍑ࡍࡿ࡜ࠊSoret ᖏ࡛ࡣࠊIPCE ࡣ༢

㔞య1 ࠿ࡽ஧㔞య(22)࡛ 1.16 ಸࠊከ㔞య (3n)࡛ 1.03 ಸୖ᪼ࡋࠊ༢㔞య࡟ࡃࡽ࡭

ࣈ࣮ࣟࢻ໬ࣆ࣮ࢡࡀᚓࡽࢀࡓࠋSoret ᖏ࡛ࡣ ͆face-to-face͇࡜͆head-to-tail͇ࡢ

34 ྾཰ᖏࡀᗈࡀࡗࡓࡓࡵIPCE ࡀࣈ࣮ࣟࢻ໬ࡋࡓ࡜⪃࠼ࡽࢀࡿࠋࡲࡓࠊQ-band ࡛ࡣ IPCE ࡀ஧㔞య (22)࡛ 1.25 ಸࠊከ㔞య (3n)࡛ 2 ಸୖ᪼ࡋࡓࠋIPCE ࡀྥୖࡋࡓࡢ ࡣࠊ㑄⛣཮ᴟᏊ┦஫స⏝࡟ࡼࡿIPCE ࡢࣈ࣮ࣟࢻ໬࡟ຍ࠼ࠊ㐃⥆ࡋࡓȧࢫࢱࢵ࢟ ࣥࢢᵓ㐀(ȧ㌶㐨ࡢ㔜࡞ࡾ)࡟ࡼࡗ࡚ගບ㉳࡟ࡼࡾⓎ⏕ࡋࡓ࣮࣍ࣝࡀȧ㟁Ꮚ࡟ࡼ ࡾࢺࣛࢵࣆࣥࢢ(i.e.࣮࣍ࣝ⛣ື)ࡉࢀ㓟໬ࢳࢱࣥ࠿ࡽࡢ㏫㟁Ꮚ⛣ືࡀᢚไࡉࢀࡿ

ࡓࡵ53,54ࠊ㟁Ꮚὀධຠ⋡ (quantum yield of electron injection)ࡀྥୖࡋࡓࡢ࡛ࡣ࡞ ࠸࠿࡜⪃࠼ࡽࢀࡿ*4ࠋ *3_{ LHE(ග྾཰ຠ⋡)=(1-10}-Abs._{)™100 ࡜⾲ࡉࢀࡿࠋ} *4_{ IPCE(Ȣ)=LHE(Ȣ)࣭ȭ} inj࣭Ȟe (ȭinj㸸㟁Ꮚὀධࡢ㔞Ꮚ཰⋡, Ȟe: 㟁Ꮚ཰㞟ຠ⋡㸸ὀධࡉࢀࡓ㟁Ꮚࡀእ㒊ᅇ㊰࡟ὶ ࢀࡿຠ⋡)

35 2-4. ⤖ㄽ  ᡃࠎࡣ N-࣓ࢳࣝ࢖࣑ࢲࢰ࣮ࣝ 2 ࡘ࡜Ᏻᜥ㤶㓟 2 ࡘࢆ⨨᥮ࡋࡓ࣏ࣝࣇ࢕ࣜࣥ Mg 㘒యࢆྜᡂࡋࠊ㓟໬ࢳࢱࣥ㟁ᴟୖ࡛ࡢ㑄⛣཮ᴟᏊ┦஫స⏝࡜ȧࢫࢱࢵ࢟ࣥࢢ ࢆ᭷ࡍࡿከ㔞య㸦J ఍ྜ㸧࡬ࡢ⮬ᕫ⤌⧊໬࡟ᡂຌࡋࡓࠋࡲࡓࠊࡇࡢ࣏ࣝࣇ࢕ࣜࣥ ㉸ศᏊࢆ⏝࠸ࡓⰍ⣲ቑឤኴ㝧㟁ụࡣࠊከ㔞య㸦J ఍ྜ㸧ࡢᙧᡂ࡟ࡼࡾࠊIPCE ࡢ ࣈ࣮ࣟࢻ໬࡜ቑຍࢆᘬࡁ㉳ࡇࡋࠊኚ᥮ຠ⋡ࡀྥୖࡍࡿࡇ࡜ࢆぢฟࡋࡓࠋ௒ᚋࠊ Ⰽ⣲ቑឤኴ㝧㟁ụࡢ㛤Ⓨ࡟࠾࠸࡚Ⰽ⣲ࡢ㑄⛣཮ᴟᏊ┦஫స⏝ࡸࠊȧࢫࢱࢵ࢟ࣥ ࢢࢆ⮬ᕫ⤌⧊໬࡛ไᚚࡍࡿࡇ࡜࡛ࠊ᭦࡞ࡿኚ᥮ຠ⋡ࡢྥୖࡀᮇᚅࡉࢀࡿࠋ

36

3❶  ග

ගྜ

ྜᡂ

ᡂ཯

཯ᛂ

ᛂ୰

୰ᚰ

ᚰ࡜

࡜ග

ගᤕ

ᤕ㞟

㞟࢔

࢔ࣥ

ࣥࢸ

ࢸࢼ

ࢼᶵ

ᶵ⬟

⬟ࢆ

ࢆᶍ

ᶍೌ

ೌࡋ

ࡋࡓ

ࡓ

ࢩ࣮ࣝࢻᆺ㉸ศᏊ࣏ࣝࣇ࢕ࣜࣥⰍ⣲ቑឤኴ㝧㟁ụ

3-1. ᗎㄽ 3-1.1. ⫼ᬒ  ࡇࢀࡲ࡛࡟➨㸯❶࡛㏙࡭ࡓ௚࡟ࡶᵝࠎ࡞࢔ࣥࢸࢼᶵ⬟ࢆᮇᚅࡋࡓ࣏ࣝࣇ࢕ࣜ ࣥࡀྜᡂࡉࢀ࡚ࡁࡓ55ࠋ  ᅗ 23 ࡣ࢚ࢿࣝࢠ࣮⛣ືࡸ㟁Ꮚࡢᩚὶࢆ┠ⓗ࡟ࡋࡓ࣏ࣝࣇ࢕࡛ࣜࣥ࠶ࡿࠋ࣏ࣝ ࣇ࢕ࣜࣥࣇ࣮࣮ࣜ࣋ࢫࡢLUMO ࡢ࢚ࢿࣝࢠ࣮‽఩ࡣ࣏ࣝࣇ࢕ࣜࣥள㖄㘒యࡼࡾ ࡶప࠸ࡇ࡜ࡀ▱ࡽࢀ࡚࠾ࡾ 56ࠊp-i-n ࡢࡼ࠺࡞ᵓ㐀ࢆྲྀࡿࡇ࡜࡛ࠊள㖄࣏ࣝࣇ࢕ ࣜࣥ࠿ࡽࣇ࣮࣮ࣜ࣋ࢫ࣏ࣝࣇ࢕ࣜࣥ࡬࡜࢚ࢿࣝࢠ࣮⛣ືࡀ㉳ࡇࡿࡇ࡜ࡀሗ࿌ࡉ ࢀ࡚࠸ࡿࠋ ᅗ 23 ࣏ࣝࣇ࢕ࣜࣥள㖄㘒య࡜࣏ࣝࣇ࢕ࣜࣥࣇ࣮࣮ࣜ࣋ࢫࢆ ⤌ࡳྜࡉࡏࡓⰍ⣲ቑឤኴ㝧㟁ụ56 

37  ᅗ 24 ࡣ㠀㔠ᒓ᭷ᶵศᏊ࡛࠶ࡿ JH1 ࡢࣆࣜࢪࣥ࡜ள㖄ࡢ㓄఩࡟ࡼࡾࠊᇶᯈୖ࡛ ⮬ᕫ⤌⧊໬ࡍࡿ㉸ศᏊ࡛࠶ࡿࠋⴭ⪅ࡽࡣ JH1 ࡢኚ᥮ຠ⋡ࡀ 2.46㸣ࡋ࠿࡞࠿ࡗࡓ ࡢ࡟ᑐࡋࠊࢩࣜࣝᇶࢆ࣏ࣝࣇ࢕ࣜࣥ࡟⨨᥮ࡋࡓP2 ࢆ㓄఩ࡉࡏࡿ࡜ࠊ4.39% (9.39 mA/cm2)ࡲ࡛ᛶ⬟ࡀྥୖࡍࡿࡇ࡜ࢆぢฟࡋ࡚࠸ࡿࠋࡑࡋ࡚ࠊࡇࡢ࢔ࣥࢸࢼࢩࢫࢸ ࣒ࢆ⏝࠸ࡿࡇ࡜࡟ࡼࡾࠊ㓟໬ࢳࢱࣥ⾲㠃ࢆⰍ⣲ࢆจ㞟ࡉࡏࡿࡇ࡜࡞ࡃそ࠺ࡇ࡜ ࡀ࡛ࡁࠊࡑࡢ⤖ᯝࠊ㟁Ⲵࡢ෌⤖ྜࡀ㉳ࡇࡽ࡞ࡃ࡞ࡗࡓࡇ࡜࡟ࡼࡿ㛤ᨺ㟁ᅽVocࡢ ྥୖࡀ93 mV ぢࡽࢀࡓࠋ ᅗ ᅗ 24  ㍈㓄఩Ꮚ࡜࢔࣮ࣥ࢝㒊఩ࢆ฼⏝ࡋࡓⰍ⣲ቑឤኴ㝧㟁ụ57

38  ᅗ 25 ࡣࢪࣇ࢙ࢽࣝ࢔ࣛࢽࣥ⨨᥮࣏ࣝࣇ࢕ࣜࣥள㖄㘒య (FF-ZnP)࡜ࢪࣇ࢙ࢽ ࣝ࢔ࣛࢽࣥ⨨᥮࣏ࣝࣇ࢕ࣜࣥࣇ࣮࣮ࣜ࣋ࢫ (FF-H2P-COOH)ࢆ⤌ࡳྜࢃࡏࠊ㓟໬ ࢳࢱࣥୖ࡛Ỉ⣲⤖ྜ࡟ࡼࡿ⮬ᕫ⤌⧊໬࡟ࡼࡾ⌫≧ᵓ㐀ࢆᙧᡂࡍࡿⰍ⣲࡛࠶ࡿࠋ ࡇࡢ㉸ศᏊᵓ㐀࡟ࡼࡾࠊIPCE ࡛ Soret ᖏ࡟㢧ⴭ࡞ᛶ⬟ࡢྥୖࡀぢࡽࢀࡓ࡜➹⪅ ࡽࡣሗ࿌ࡋ࡚࠸ࡿࠋࡇࡢࡼ࠺࡞Ỉ⣲⤖ྜ࡟ࡼࡾ⮬ᕫ⤌⧊໬ࡍࡿ㉸ศᏊࡢⰍ⣲ቑ ឤኴ㝧㟁ụࡢᛂ⏝ࡣ௚࡟ࡶሗ࿌ࡉࢀ࡚࠸ࡿ58ࠋ ᅗ ᅗ 25 Ỉ⣲⤖ྜ࡟ࡼࡾ⌫≧࡟⮬ᕫ⤌⧊໬ࡍࡿ࣏ࣝࣇ࢕ࣜࣥ࡟ࡼࡿⰍ⣲ቑឤኴ㝧㟁ụ59

39 ᮏ◊✲࡛ࡣගྜᡂ⣽⳦ࡢ LH1-RC ࡟╔┠ࡋࡓࠋගྜᡂ⣽⳦ࡸ᳜≀ࡣᙅ࠸ගࢆ ຠ⋡ࡼࡃ⿵㊊࡛ࡁࡿගᤕ㞟࢔ࣥࢸࢼ」ྜయࢆ᭷ࡋ࡚࠸ࡿ40,49,60ࠋࡇࡢࡼ࠺࡞⏕≀ Ꮫⓗࢩࢫࢸ࣒࡟╔┠ࡋࠊගྜᡂ࡟⏝࠸ࡽࢀࡿ࢔ࣥࢸࢼ㘒యࢆᶍೌࡋࡓ⣔ࡀሗ࿌ ࡉࢀ࡚ࡁࡓ61–63ࠋ ගྜᡂ࡟࠾ࡅࡿගᤕ㞟࢔ࣥࢸࢼຠᯝࡣࠊ➨㸰❶࡛㏙࡭ࡓࡼ࠺ ࡞B850 ࡢගᤕ㞟࢔ࣥࢸࢼຠᯝࡣග࢚ࢿࣝࢠ࣮ࡢຠ⋡ⓗ࡞྾཰ࡔࡅ࡛ࡣ࡞ࡃࠊ㟁 Ꮚఏ㐩⣔࡬࡜ࡘ࡞ࡀࡿ཯ᛂ୰ᚰ࡬ࡢ࢚ࢿࣝࢠ࣮⛣ືࡢᶵ⬟ࡶᢸࡗ࡚࠸ࡿࠋ ග ྜᡂ⣽⳦ࡢLH-RC ࠿ࡽࢡࣟࣟࣇ࢕ࣝࡢࡳࢆᢤࡁฟࡋࡓࡢࡀᅗ 26 ࡛࠶ࡿࠋᵓ㐀 ࡢ≉ᚩ࡜ࡋ࡚ࡣRC ࢆࣜࣥࢢ≧࡟㐃࡞ࡗࡓ LH1 ࡀྲྀࡾᅖࢇ࡛࠸ࡿࠋLH1ࠊRC ࡑ ࢀࡒࢀࡀ࢔ࣥࢸࢼศᏊ࡜ࡋ࡚ࠊ㟁Ⲵศ㞳୰ᚰ࡜ࡋ࡚ᶵ⬟ࡋ࡚࠸ࡿࠋࡇࡢࡼ࠺࡟ࠊ ບ㉳Ꮚ࡛ᅖ࠸㎸ࡴࡇ࡜࡟ࡼࡗ࡚ࠊRC ࡛ࡢບ㉳ᏊࡢᏑᅾ☜⋡ࡀ㧗ࡃ࡞ࡿ࡜⪃࠼ࡽ ࢀ࡚࠸ࡿࠋ ᅗ ᅗ 26 LH1-RC ࡢ࣏ࣝࣇ࢕ࣜࣥ⤖ᬗᵓ㐀64  ࡇࡢᵝ࡞RC ࢆ㓟໬≀༙ᑟయ࡟྾╔࡛ࡁࢀࡤࠊ㟁ᴟഃ࡬ບ㉳㟁ᏊࡢᏑᅾ☜⋡ศ ᕸࢆㄏᑟ࡛ࡁࡿ࡜⪃࠼ࡽࢀࡿࠋ

40 3-1.2. ┠┠ⓗ ᅗ 27 ᮏ◊✲ࡢᴫᛕᅗ  ᮏ◊✲࡛ࡣࠊගྜᡂ཯ᛂ୰ᚰ࡜࢔ࣥࢸࢼ㘒యࡢᶍೌࢆ┠ⓗ࡜ࡋࠊࣔࣀ࢝ࣝ࣎ ࢟ࢩࣇ࢙ࢽࣝࢺࣜࣆࣜࢪ࣏ࣝࣝࣇ࢕ࣜࣥࢆ཯ᛂ୰ᚰࠊࢸࢺࣛࣇ࢙ࢽ࣏ࣝࣝࣇ࢕ ࣜࣥள㖄㘒యࢆ࢔ࣥࢸࢼศᏊ࡜ࡋ࡚⏝࠸ࠊ㓟໬ள㖄ୖ࡟ᴫᛕᅗࡢࡼ࠺࡞㉸ศᏊ ࢆᵓ⠏ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓࠋ

41 3-2. ᐇ㦂㡯 3-2.1 ౑⏝ᶵჾ ᮏ◊✲࡛ࡣ⾲ 6 ࡟♧ࡋࡓᶵჾ࡛ ᐃࢆ⾜ࡗࡓࠋ ⾲ 6 ౑⏝ࡋࡓᶵჾ 㡯┠ ౑⏝ᶵჾ 1_{H NMR  ECS-400 (᪥ᮏ㟁Ꮚ)} ㉁㔞ศᯒ AXIMA Resonance ᓥὠ〇సᡤ

ᅛయUV-VIS ࢫ࣌ࢡࢺࣝ HITACHI U-4000 ᾮయUV-VIS ࢫ࣌ࢡࢺࣝ UV-1700 ᓥὠ〇సᡤ

ⓑ㔠ࡢ┿✵⵨╔ IB- ION COATER

ࢯ࣮࣮ࣛࢩ࣑࣮ࣗࣞࢱ࣮ YSS-150A ᒣୗ㟁⿦ᰴᘧ఍♫ UV ࢜ࢰࣥࢡ࣮ࣜࢼ࣮ Filgen ࢔ࢡࢩࣙࣥࢫ࣌ࢡࢺࣝ ศගィჾ CEP-2000 ᅛయ⺯ගࢫ࣌ࢡࢺࣝ Fluorolog-3 HORIBA ⺯ගᑑ࿨ Quantaurus-Tau ὾ᯇ࣍ࢺࢽࢡࢫ ᾮయ⺯ගࢫ࣌ࢡࢺࣝ RF-5300PC ᓥὠ〇సᡤ

42 3-2.2 ౑౑⏝ヨ⸆ ᮏ◊✲࡛ࡣ⾲⾲ 7 ࡟♧ࡋࡓヨ⸆ࢆ㉎ධࡋࠊࣆ࣮ࣟࣝࡣ⵨␃ࡋࠊࡑࡢ௚ࡣࡑࡢࡲ ࡲ౑⏝ࡋࡓࠋ ⾲ 7 ౑⏝ࡋࡓヨ⸆ ヨ⸆ྡ ㉎ධඛ ୕ࡩࡗ໬࡯࠺⣲ࢪ࢚ࢳ࢚࣮ࣝࢸࣝ㘒య ࿴ග⣧⸆ᕤᴗ(ᰴ) 2,3-ࢪࢡࣟࣟ-5,6-ࢪࢩ࢔ࣀ-1,4-࣋ࣥࢰ࢟ࣀࣥ ᮾி໬ᡂᕤᴗᰴᘧ఍♫ ࢪࢡ࣓ࣟࣟࢱࣥ ࿴ග⣧⸆ᕤᴗᰴ 4-ࣆࣜࢪࣝ࢔ࣝࢹࣄࢻ ᮾி໬ᡂᕤᴗᰴᘧ఍♫ 4-࣑࣍ࣝࣝᏳᜥ㤶㓟࣓ࢳࣝ ALDRICH

5,10,15,20-tetraphenylporphyrin zinc complex ALDRICH

ࣆ࣮ࣟࣝ ᮾி໬ᡂᕤᴗᰴᘧ఍♫

ࢺࣜࣇࣝ࢜ࣟ㓑㓟 ࿴ග⣧⸆ᕤᴗ(ᰴ)

43 Ⰽ⣲ቑឤኴ㝧㟁ụస〇᪉ἲ 㓟໬ள㖄㟁ᴟࡢస〇 ࣮࣌ࢫࢺㄪ〇 ศᩓ๣࡜ࡋ࡚࢔ࢭࢳࣝ࢔ࢭࢺࣥࢆྵࡴ᭷ᶵ⁐๣࡟ 50㹼70 㸣࡜࡞ࡿࡼ࠺㓟໬ள 㖄⢊ᮎZnO-410 ࢆΰྜࡋࡓࠋ FTO ᇶᯈࡢὙί ᇶᯈ࡜ࡋ࡚⏝࠸ࡿ FTO ࢞ࣛࢫࡣࠊUV ࢜ࢰࣥࢡ࣮ࣜࢼ࣮ࢆ⏝࠸㓟⣲㞺ᅖẼୗ࡛ UV ࢆ 1 ᫬㛫↷ᑕࡍࡿࡇ࡜࡛᭷ᶵ≀ࡢ㝖ཤࢆ⾜ࡗࡓࠋ 㓟໬ள㖄ⷧ⭷ࡢస〇 ࢫࢡ࣮ࣜࣥ༳ๅ࡟ࡼࡗ࡚FTO ࢞ࣛࢫୖ࡟㓟໬ள㖄࣮࣌ࢫࢺࢆሬᕸࡋࡓࠋ༳ๅ᮲ ௳ࡣ㓟໬ள㖄ከᏍ㉁ⷧ⭷ࡀ⭷ཌ10ȣmࠊ┤ᚄ 6 mm ࡢ෇ᰕ≧࡜࡞ࡿࡼ࠺࡟タᐃࡋ ࡓࠋ ᚋฎ⌮ ༳ๅࡋࡓᇶᯈࢆ80Υ࡛ 30 ศ஝⇱ࡋࠊUV ࢜ࢰࣥࢡ࣮ࣜࢼ࣮ࢆ⏝࠸㓟⣲㞺ᅖẼୗ ࡛UV ࢆ 1 ᫬㛫↷ᑕࡍࡿࡇ࡜࡛᭷ᶵ≀ࡢ㝖ཤࢆ⾜ࡗࡓࠋ  Ỉฎ⌮ 〇⭷ࡋࡓ㓟໬ள㖄ከᏍ㉁㟁ᴟࢆ 50Υ࡟ಖࡗࡓ㓟໬ள㖄㣬࿴Ỉ⁐ᾮ࡟ 10 ศ㛫ᾐ ₕࡉࡏࡿࡇ࡜࡟ࡼࡾ Ỉฎ⌮ࢆ⾜ࡗࡓࠋฎ⌮ᚋࠊ㓟໬ள㖄㣬࿴Ỉ⁐ᾮ࠿ࡽྲྀࡾ ฟࡋࡓస⏝ᴟࢆ100 Υ

44 ࡢᜏ ᶵෆ࡛30 ศ㛫஝⇱ࡉࡏࡓࠋ Ⰽ⣲྾╔ 4a ࡢ࣏ࣝࣇ࢕࣓ࣜࣥࢱࣀ࣮ࣝ⁐ᾮࢆస〇ࡋࠊసࡗࡓ㓟໬ள㖄㟁ᴟࢆᐊ ࡛ 12 ᫬ 㛫ᾐࡋࡓࠋ ᑐᴟస〇  ⓑ㔠ࢆFTO ㏱᫂㟁ᴟ࡟┿✵⵨╔ࡋࡓ (┿✵⵨╔⿦⨨/ᰴᘧ఍♫࢚࢖ࢥ࣮)ࠋ 㟁ゎ㉁  ࢸࢺࣛࣉࣟࣆࣝ࢔ࣥࣔࢽ࣒࣮࢘ࣚࢪࢻ 1 Mࠊࣚ࢘⣲ 0.1 M ࢔ࢭࢺࢽࢺࣜ ࣝ㸸࢚ࢳ࣮ࣞࣥ࢝࣎ࢿ࣮ࢺ㸻4㸸1 ࢭࣝࡢస〇 Ⰽ⣲ࢆ྾╔ࡉࡏࡓ㓟໬ள㖄ከᏍ㉁㟁ᴟࡣ⇕⁐⼥᥋╔ࢩ࣮ࢺ(ࣁ࢖࣑ࣛࣥࠊཌࡉ 50 ȣm) ࢆࢫ࣮࣌ࢧ࣮࡜ࡋ࡚ᑐᴟ࡜㈞ࡾྜࢃࡏࠊ㟁ゎᾮࡣᑐᴟ࡟࠶ࡅࡓ✰࠿ࡽ┿✵ ᘬࡁ࡟ࡼࡾὀධࡋࠊᑐᴟࡢ✰ࡢୖ࡟ࣁ࢖࣑ࣛࣥࠊ࢝ࣂ࣮࢞ࣛࢫࢆ஌ࡏࠊຍ⇕ࡋ ࡚ᑒṆࡋࡓࠋࡲࡓࠊ ᐃ᫬࡟࠾ࡅࡿ᥋ゐ᢬ᢠࢆῶᑡࡉࡏࡿࡓࡵ࡟In/Ga ࢆሬࡾ㖡 ࢸ࣮ࣉࢆ㈞ࡗࡓࠋ ᅗ 28 ࡟ᑒṆᆺࢭࣝࡢస〇᪉ἲ࡜ᑍἲࢆ♧ࡍࠋ Ⰽ⣲ὀධ ᑐᴟഃࡢ✰࠿ࡽࠊ10ȣL ࢩࣜࣥࢪ࡛Ⰽ⣲ 5 ⁐ᾮ (㹼3eq.)ࢆὀධࡋἜᅇ┿✵࣏ࣥࣉ ࡛ᘬࡗᙇࡗࡓࠋ㟁ゎᾮࢆὀධᚋࠊࢸ࣮ࣉ࡛ᑒṆࡋࡓࠋ

45

ᅗ

46

3-3. ⤖⤖ᯝ࡜⪃ᐹ 3-3.1 ᐇ㦂᪉ἲ

 FbPyP (4aࠊ4bࠊ4c)ࡢᩥ⊩ࢆཧ⪃࡟ྜᡂࡋ66ࠊZnTPP (5)ࡣ SigmaAldrich ♫࠿ࡽ ㉎ධࡋࡓࠋࡲࡎFbPyP ࢆసᡂࡋࡓ ZnO 㟁ᴟୖ࡟྾╔ࡉࡏࠊⰍ⣲ቑឤኴ㝧㟁ụࢆ

⤌ࡳ❧࡚ࡓ65ࠋࡑࡇ࡟࣓ࢱࣀ࣮ࣝ࡟⁐ゎࡋࡓ ZnTPP ࢆⰍ⣲ቑឤኴ㝧㟁ụࡢⓑ㔠 ᑐᴟഃ࡟㛤ࡅࡓ✰࠿ࡽὀධࡋࡓࠋ(ᐇ㦂㡯ཧ↷)

ᅗ 29 ᮏ◊✲࡛౑⏝ࡋࡓࣇ࣮࣮ࣜ࣋ࢫ࣏ࣝࣇ࢕ࣜࣥ (FbPyP:4aࠊ4bࠊ4c)࡜

47 3-3.2 Ⰽ⣲ቑឤኴ㝧㟁ụࡢᛶ⬟ホ౯  Ⰽ⣲ቑឤኴ㝧㟁ụࡢᛶ⬟ࢆ⾲࡟♧ࡋࡓ (⾲ 8)ࠋFbPyP (4a)ࢆ྾╔ࡋࡓୖ࡟ ZnTPP (5)ࢆ 10 ᙜ㔞ຍ࠼ࡓሙྜࡢ㟁ὶ್࡜ኚ᥮ຠ⋡ࡀ᭱ࡶ㧗ࡃࠊ▷⤡㟁ὶᐦᗘࡀ 0.442 mA/cm2࠿ࡽ1.937 mA/cm2ࡲ࡛ⴭࡋࡃྥୖࡋࡓࠋᑐ↷ᐇ㦂࡜ࡋ࡚⾜ࡗࡓࠊ 㓟໬ࢳࢱࣥࡢࡳࡢ≧ែ࡟⁐፹ࡢ࣓ࢱࣀ࣮ࣝࡢࡳࢆὀධࡋࡓሙྜࠊ࡯࡜ࢇ࡝ᛶ⬟ ࡟ኚ໬ࡣ࡞࠿ࡗࡓ(ࢧ࣏࣮ࢺࢹ࣮ࢱཧ↷)ࠋࡇࢀࡽࡢ⤖ᯝ࠿ࡽ࢔ࣥࢸࢼຠᯝࠊ༶ࡕ LUMO ࡢ࢚ࢿࣝࢠ࣮‽఩ࡀ㧗࠸ ZnTPP (5)࠿ࡽప࠸ࣇ࣮࣮ࣜ࣋ࢫ࡬࡜࢚ࢿࣝࢠ࣮ ࡀ⛣ືࡋࡓ࡜⪃࠼ࡽࢀࡿࠋࡲࡓࠊZnTPP (5)ࢆ኱㐣๫ࡢ 20 ᙜ㔞ࡍࡿ࡜ࠊ▷⤡㟁ὶ ᐦᗘࡀⴭࡋࡃపୗࡋࡓࠋࡇࢀࡣࠊFbPyP (4a)࡟㓄఩ࡍࡿࡇ࡜ࡀ࡛ࡁ࡞࠸ ZnTPP (5) ࡀධᑕගࢆ㐽ࡗ࡚ࡋࡲࡗࡓࡓࡵ࡜⪃࠼ࡽࢀࡿࠋࡇࡢࡇ࡜࠿ࡽࠊ࢚ࢿࣝࢠ࣮⛣ື ࡣࠊ㓄఩⤖ྜࡋࡓZnTPP (5)࠿ࡽ FbPyP (4a)㛫ࡢࡳ࡛㉳ࡇࡿ࡜⪃࠼ࡽࢀࡿࠋ ⾲ ⾲ 8 స〇ࡋࡓⰍ⣲ቑឤኴ㝧㟁ụࡢᛶ⬟ ( ᐃ᮲௳㸸ගᙉᗘ 100 mW/cm2, AM:1.5, ᭷ຠ㠃✚ 0.2 cm2) Jsc Voc η (mA/cm2) (mV) (%) 4a 0.44 404 0.66 0.12 4a + 5 (1 equiv.) 0.49 404 0.67 0.13 4a + 5 (3 equiv.) 1.61 496 0.61 0.49 4a + 5 (10 equiv.) 1.94 498 0.59 0.57 5 (10 equiv.) 0.12 424 0.61 0.03 4c 1.60 520 0.67 0.56 4c + 5 (10 equiv.) 1.69 500 0.66 0.56 F. F.

48 ᅗ ᅗ 30 స〇ࡋࡓⰍ⣲ቑឤኴ㝧㟁ụࡢ IPCE ( ᐃ᮲௳㸸DC ࣮ࣔࢻ, ࣇ࢛ࢺࣥᩘ 0.5™1016, ᭷ຠ㠃✚ 0.2 cm2)  ᭦࡟ࠊIPCE ࡟ࡘ࠸࡚ࡶ᳨ウࡋࡓ (ᅗ 30)ࠋ࣏ࣝࣇ࢕ࣜࣥࡢ≉ᚩⓗ࡞ࣆ࣮ࢡ࡛ ࠶ࡿQ-ࣂࣥࢻ (560 nm)࡟╔┠ࡋࡓࠋFbPyP (4a)࡜ ZnTPP (5)ࡢ྾཰ᇦࡀ㔜」ࡍࡿ ࡓࡵࠊࡑࡢẚ⋡᳨࡛ウࡋࡓࠋIPCE ࡣ FbPyP (4a)ࡀ 510 nm ࡛ 2.0 % (FbPyP ࡢࡳ)

࠿ࡽ10.5% (FbPyP (4a)㸩ZnTPP (5) 10 equiv.)࡬ྥୖࡋࠊ560 nm (ZnTPP 5)࡟ᑐࡍࡿ 510 nm (FbPyP 4a) ࡢ IPCE ẚ⋡ࡣ 0.83 ࠿ࡽ 0.92 ࡬ቑຍࡋࡓࠋᑐ↷ᐇ㦂࡜ࡋ࡚ࠊ

ఱࡶ྾╔ࡋ࡚࠸࡞࠸ZnO 㟁ᴟ࡟ ZnTPP (5)ࢆὀධࡋࡓࡀࠊ㟁ụᛶ⬟࡟኱ࡁ࡞ኚ໬ ࡣぢࡽࢀ࡞࠿ࡗࡓ(ࢧ࣏࣮ࢺࢹ࣮ࢱཧ↷)ࠋ᭦࡟ࠊZnO 㟁ᴟ࡟ࣆࣜࢪࣥࢆᣢࡓ࡞࠸

ࢺࣜࢫࣇ࢙ࢽࣝࣔࣀ࢝ࣝ࣎࢟ࢩࣇ࢙ࢽ࣏ࣝࣝࣇ࢕ࣜࣥ(4c)ࢆ྾╔ࡉࡏࠊZnTPP (5) ࢆὀධࡍࡿ࡜ࠊࡇࡢሙྜࡶྠᵝ࡟㟁ụᛶ⬟࡟኱ࡁ࡞ኚ໬ࡣ࡞࠿ࡗࡓ(ࢧ࣏࣮ࢺࢹ

࣮ࢱཧ↷)ࠋFbPyP (4a)ࡣ ZnTPP (5)࠿ࡽບ㉳࢚ࢿࣝࢠ࣮ࢆຠ⋡ⓗ࡟ཷࡅྲྀࡾࠊ FbPyP (4a)࠿ࡽ ZnO 㟁ᴟ࡬ࡢຠ⋡ⓗ࡞㟁Ꮚὀධࡀ㉳ࡇࡗࡓ࡜⪃࠼ࡽࢀࡿࠋ

49 3-3.3 ⁐ᾮ୰࡛ࡢศගᏛⓗ ᐃ  ZnTPP (5)࠿ࡽ FbPyP (4a)࡬ࡢ࢚ࢿࣝࢠ࣮⛣ືࢆㄪ࡭ࡿࡓࡵ࡟ࠊศග≉ᛶࢆ࢔ ࢭࢺࢽࢺࣜࣝ⁐፹୰࡛ ᐃࡋࡓࠋࡇࡢ ᐃ࡟࠾࠸࡚ࡣࠊFbPyP (4a)ࡢ௦ࢃࡾ࡟࢚ ࢫࢸࣝ໬ྜ≀࡛࠶ࡿ4b ࢆ⏝࠸࡚ࠊ⁐ᾮ୰࡛࢝ࣝ࣎ࣥ㓟஧㔞యࢆᙧᡂࡋ࡞࠸ࡼ࠺ ࡟ࡋࡓ (⾲ 9)ࠋ ZnTPP (5)ࡢ⺯ගἼ㛗࡜ࠊ4b ࡢ྾཰Ἴ㛗ࡀ㔜」ࡍࡿࡇ࡜ࡀࢃ࠿

ࡗࡓࠋࡇࡢ㔜」࡟ࡼࡾZnTPP (5)࡜ 4b 㛫࡛ Fluorescence Resonance Energy Transfer (FRET)67ࡀZnTPP(5)࡜ 4b ࡢ㛫࡛㉳ࡇࡗࡓ࡜⪃࠼ࡽࢀࡿࠋࡇࡢ FRET ࡀ㉳ࡇࡿࡇ ࡜࠿ࡽࠊZnTPP (5)࡜ 4b ࡀ᥋㏆ࡍࡿࡇ࡜ࡀ♧၀ࡉࢀࡓ68–70ࠋ ࡋࡓࡀࡗ࡚ࠊ4b ࡣ ZnTPP (5)࠿ࡽཷࡅྲྀࡗࡓ࢚ࢿࣝࢠ࣮ࡢࡓࡵ 710nm ࡛⺯ගࢆⓎࡋࡓ࡜⪃࠼ࡽࢀࡿࠋ ࡇࡢⅬࢆ᫂☜࡟ࡍࡿࡓࡵ࡟ࠊບ㉳ࢫ࣌ࢡࢺࣝࢆ710 nm ࡛ ᐃࡋࡓ (ᅗ 31)ࠋ 4b ࡢࢫ࣌ࢡࢺࣝࡣ࣏ࣝࣇ࢕ࣜࣥࡢ4 ࡘࡢ Q ࣂࣥࢻࢆ♧ࡋࡓࠋ 4b ࡟ ZnTPP (5)ࢆ 100 ᙜ㔞⁲ୗࡍࡿ࡜ZnTPP (5)࠿ࡽㄏᑟࡉࢀࡓບ㉳✀࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿ 570 nm ࡜ 590 nm ࠾ࡼࡧ 620 nm ࡟᪂ࡋ࠸ࣆ࣮ࢡࡀ⌧ࢀࡓࠋ᪂ࡋ࠸ࣆ࣮ࢡࡣࠊ4b ࡢࣆࣜࢪ ࣝᇶࡢZn ࡬ࡢ㓄఩࡟㉳ᅉࡍࡿ CT 㑄⛣ࡀ㉳ࡇࡾࠊἼ㛗ࡢ㛗Ἴ㛗໬ࡀ㉳ࡇࡗࡓ࡜ ⪃࠼ࡽࢀࡿ (3-3.5 ࢆཧ↷)ࠋᑐ↷ᐇ㦂࡜ࡋ࡚ࠊ710 nm ࡛ ZnTPP (5)ࡢບ㉳ࢫ࣌ࢡ ࢺࣝࢆ ᐃࡋࡓࡀࠊບ㉳ࡣぢࡽࢀ࡞࠿ࡗࡓ (ࢧ࣏࣮ࢺࢹ࣮ࢱཧ↷)ࠋࡇࢀࡽࡢ⤖ ᯝ࠿ࡽࠊ⁐ᾮ୰࡛ZnTPP (5)࠿ࡽ 4b ࡬࢚ࢿࣝࢠ࣮⛣ືࡀ㉳ࡇࡿࡇ࡜ࡀ♧၀ࡉࢀ ࡓࠋ

50 ⾲ ⾲ 9 ⁐ᾮ୰࡛࣏ࣝࣇ࢕ࣜࣥ 4b, 5 ࡢ྾཰ࢫ࣌ࢡࢺࣝ࡜⺯ගࢫ࣌ࢡࢺࣝ (1.85 ȣM in MeCN) ᅗ 31 ⁐ᾮ୰ࡢ 710 nm ࡛ࡢ࣏ࣝࣇ࢕ࣜࣥ 4b ࡢບ㉳ࢫ࣌ࢡࢺࣝ (1.85 ȣM in MeCN) 6RUHW EDQG QP E        =Q733      4EDQG QP $EVRUSWLRQ QP )OXRUHVFHQFH

51  ⁐ᾮ୰ࡢFRET ࡜⺯ගᑑ࿨ࡢᅉᯝ㛵ಀ࡟ࡘ࠸᳨࡚ウࡋࡓ (⾲ 10)ࠋ4b ࡟ ZnTPP (5)ࢆຍ࠼࡚࠸ࡃ࡜ࠊZnTPP (5)ࡢⓎගἼ㛗࡛࠶ࡿ 710 nm ࡢ⺯ගᑑ࿨ࡣ 10.36 ns 㸦0equiv㸧࠿ࡽ 9.19 ns (20equiv.)ࡲ࡛▷ࡃ࡞ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋ᭦࡟ࠊ⁐ᾮ୰ࡢ ࣏ࣝࣇ࢕ࣜࣥࡢ⮬ᕫ⤌⧊໬ࢆ⪃៖ࡍࡿ࡜ࠊᚓࡽࢀࡓῶ⾶᭤⥺࠿ࡽồࡵࡽࢀࡿ⺯ ගᑑ࿨ࢆ⾲ࡍȫࡣ㸰ᡂศ࡟ศࡅࡿࡇ࡜ࡀ࡛ࡁࠊȫ_㸯ࡣ1.3 ns ࠿ࡽ 2.1 ns ࡲ࡛ఙࡧ ࡿ஦ࡀࢃ࠿ࡗࡓࠋࡲࡓࠊᑐ↷ᐇ㦂࡜ࡋ࡚ࠊ㓄఩ࡋ࡞࠸4c̓̓࡟ZnTPP (5)ࢆ⁲ୗࡋ ⺯ගᑑ࿨ࢆほᐹࡍࡿ࡜ࠊ10.09 ns ࠿ࡽ 8.89 ns ࡲ࡛▷ࡃ࡞ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡲ ࡓ⁐ᾮ୰ࡢ࣏ࣝࣇ࢕ࣜࣥࡢ≧ែ࡜ῶ⾶᭤⥺࠿ࡽ⪃៖ࡍࡿ࡜ศゎ࡛ࡁ࡞࠸༢୍ᡂ ศ⣔࡜⪃࠼ࡽࢀࠊȫࢆ」ᩘ࡟ศゎࡍࡿࡇ࡜ࡀ࡛ࡁ࡞࠿ࡗࡓࠋࡇࡢࡇ࡜࠿ࡽࠊ4b ࡟ZnTPP (5)ࢆຍ࠼ࡓ㝿࡟ぢࡽࢀࡿ Fb ࣏ࣝࣇ࢕ࣜࣥࡢ⺯ගᑑ࿨ࡢ㛗ᑑ࿨໬ࡣ㘒 యᙧᡂ࡟ࡼࡿࡶࡢ࡜⪃࠼ࡽࢀࡿࠋࡇࡢ㘒యᙧᡂࡋࡓᡂศ࡟ࡼࡿ⺯ගᑑ࿨ࡢ㛗ᑑ ࿨໬࠿ࡽࡶ⁐ᾮ୰ࡢບ㉳ࢫ࣌ࢡࢺ࡛ࣝぢࡽࢀࡓFRET ࡀ㉳ࡇࡗࡓࡇ࡜ࡀ♧၀ࡉ ࢀࠊኴ㝧㟁ụᛶ⬟ࡢྥୖ࡟㈉⊩ࡋࡓ࡜⪃࠼ࡽࢀࡿࠋ ⾲ 10 ࣏ࣝࣇ࢕ࣜࣥ 4b ࡟ ZnTPP (5)ࢆ⁲ୗࡋࡓ㝿ࡢ⺯ගᑑ࿨ࡢኚ໬ (0.1ȣM in toluene, Ȣex=405 nm, Ȣem=710 nm)

0 equiv. 3 equiv. 6 equiv. 10 equiv. 20 equiv.

4b

W (ns) 10.36

10.20

9.88

9.72

9.19

W

_

(ns)

-

1.34

1.64

2.00

2.09

W

_

(ns)

-

10.24

10.10

10.04

9.96

4c' (X=CH, X=Me)

W (ns) 10.09

9.94

9.59

9.46

8.89

52 3-3.4 ᅛయ࡛ࡢศගගᏛⓗ ᐃ

ࡉࡽ࡟ࠊZnO ୖ࡛ FbPyP (4a)ࠊZnTPP (5)ࠊ࠾ࡼࡧ FbPyP (4a)+ZnTPP (5)ࡢ྾཰ ࢫ࣌ࢡࢺࣝࠊ⺯ගࢫ࣌ࢡࢺࣝཬࡧບ㉳ࢫ࣌ࢡࢺࣝࢆ ᐃࡋࡓ (⾲ 11ࠊᅗ 32)ࠋ ࡲࡎࠊ྾཰ࢫ࣌ࢡࢺࣝ࡟࠾࠸࡚ࠊFbPyP (4a)࡜ ZnTPP (5)ࡢΰྜయࡢ Q ࣂࣥࢻ╔ ┠ࡍࡿ࡜ࠊZnTPP (5)༢⊂ࡢἼ㛗ࡼࡾⱝᖸ㛗Ἴ㛗ࢩࣇࢺࡋ࡚࠸ࡿࡇ࡜࠿ࡽࣆࣜࢪ ࣝᇶࡢZ㹬࣏ࣝࣇ࢕ࣜࣥ࡬ࡢ㓄఩ࡀ㉳ࡇࡾࠊFbPyP (4a)࡟⤌⧊໬ࡋࡓ ZnTPP ࡢ྾ ཰ࢫ࣌ࢡࢺࣝࢆ㊊ࡋྜࢃࡏࡓἼ㛗࡜ᙉᗘ࡟࡞ࡗ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡲࡓࠊ ⺯ගࢫ࣌ࢡࢺ࡛ࣝࡣࠊFbPyP (4a)ࡣ࢝ࣝ࣎ࣥ㓟ྠኈࡢ஧㔞໬࡟ࡼࡿ⺯ගἼ㛗ࡢࣈ ࣮ࣟࢻ໬ࡀ675 nm ࠿ࡽ 750 nm ࡢ⠊ᅖ࡛㉳ࡇࡗࡓࡀࠊFbPyP (4a)࡜ ZnTPP (5)ࡢ ΰྜయ࡛ࡣࣈ࣮ࣟࢻ໬ࡀᾘኻࡍࡿࡇ࡜࠿ࡽࠊZnTPP ࡬ࡢ㓄఩࡟ࡼࡾࠊᅛయ໬ࡍ ࡿ㝿࡟஧㔞໬ࡀጉࡆࡽࢀࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡇࡢ࡜ࡁ࡟ZnTPP (5)ࡢ 621 nm ࡢ ⺯ගࡀᾘගࡍࡿࡇ࡜ࡶࢃ࠿ࡗࡓࠋ⺯ගࢫ࣌ࢡࢺࣝ࡜྾཰ࢫ࣌ࢡࢺࣝࡢ⤖ᯝ࠿ࡽࠊ ⁐ᾮ࡜ྠᵝ࡟ZnTPP ࡢ⺯ගࢫ࣌ࢡࢺࣝ࡜ FbPyP (4a)ࡢ྾཰ࢫ࣌ࢡࢺࣝࡀ㔜」ࡍ

ࡿࡇ࡜࠿ࡽࠊZnTPP (5)ࠊFbPyP (4a)㛫࡛ FRET ࡀ㉳ࡇࡗࡓࡇ࡜ࡀ♧၀ࡉࢀࡓࠋࡲ ࡓࠊFbPyP (4a)ࡢ⺯ග (740 nm)࡛ࡢບ㉳ࢫ࣌ࢡࢺࣝ࡟࠾࠸࡚ࠊFbPyP (4a)࡜ ZnTPP (5)ࡢΰྜయ࡛ࡑࢀࡒࢀࡢ༢୍Ⰽ⣲࡛ࡣぢࡽࢀ࡞࠿ࡗࡓࠊ625 nm ࡜ 675 nm ࡟᪂ ࡓ࡞ࣆ࣮ࢡࡀฟ⌧ࡍࡿࡇ࡜ࡀࢃ࠿ࡗࡓ*ࠋࡇࢀࡣFbPyP (4a)ࡢࣆࣜࢪࣥࡢ ZnTPP (5)ࡢள㖄࡬ࡢ㓄఩࡟㉳ᅉࡍࡿ CT 㑄⛣࡟ࡼࡾἼ㛗ࡢ㛗Ἴ㛗࠿ࡀ㉳ࡇࡗࡓࡇ࡜⪃ ࠼ࡽࢀࡿࠋ(ࡇࢀࡽࡢ⤖ᯝ࠿ࡽᅛయ≧ែ࡛ࡶ ZnTPP (5)࠿ࡽ FbPyP (4a)࡬࢚ࢿࣝࢠ ࣮⛣ືࡀ㉳ࡇࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋ) *_{▷Ἴ㛗ഃࡢQ ࣂࣥࢻࡢࣆ࣮ࢡࡀ྾཰ࢫ࣌ࢡࢺࣝ࡜ྜ⮴ࡋ࡞࠸ࡀࠊບ㉳ࢫ࣌ࢡ} ࢺ࡛ࣝࣂ࣮ࣞ࡟╔┠ࡍࡿ࡜ࠊ྾཰ࢫ࣌ࢡࢺࣝࡢࣆ࣮ࢡ࡜ྜ⮴ࡍࡿࡇ࡜࠿ࡽࠊෆ 㒊㐽ⶸࡀ㉳ࡇࡗࡓ࡜⪃࠼ࡽࢀࡿࠋ

53 ⾲ ⾲ 11 㓟໬ள㖄ୖࡢ 4a, 5 ࡢ྾཰ࢫ࣌ࢡࢺࣝ࡜⺯ගࢫ࣌ࢡࢺࣝ ᅗ 32 ᅛయ࡛ࡢ 800 nm ࡛ࡢ࣏ࣝࣇ࢕ࣜࣥ 4a, 4a+5, 5 ࡢບ㉳ࢫ࣌ࢡࢺࣝ 6RUHW EDQG QP )E3\3D        =Q733       QP QP $EVRUSWLRQ )OXRUHVFHQFH 4EDQG FbPyP (4a) FbPyP (4a) + ZnTPP (5) ZnTPP (5)

54 3-3.5. ᵓ㐀᭱㐺໬  」ྜయ࡟㛵ࡋ࡚ࠊᵓ㐀᭱㐺໬࡜HOMO-LUMO ࢆồࡵࡓࠋ」ྜయ (ᅗ 33)࡛ࣆ ࣜࢪࣥ࡜ள㖄ࡢ⤖ྜ㊥㞳ࡀ2.25ύࠊࡲࡓࠊ࣏ࣝࣇ࢕ࣜࣥࡢ୰ᚰࡢ N ࡜ள㖄࡜ࡢ ㊥㞳ࡣ5 ࡣ 1.90ύࡔࡗࡓࡢ࡟ᑐࡋࠊ㓄఩ࡀ㉳ࡇࡿ࡜ 2.1ύ࡜࡞ࡾࠊ㓄఩࡟ࡼࡾࣆ ࣜࢪࣥഃ࡬ᘬࡗᙇࡽࢀ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡲࡓࠊ㓄఩ࡢゅᗘࡣ┤ゅ࠿ࡽ10r ഴ࠸࡚㓄఩ࡋ࡚࠸ࡓࡇ࡜ࡀࢃ࠿ࡗࡓࠋ ᅗ ᅗ 33  DFT ィ⟬࡟ࡼࡿᵓ㐀᭱㐺໬ 4a+5 ࡢᵓ㐀᭱㐺໬

55

 ࡇࡢᵓ㐀ࢆඖ࡟㌶㐨࢚ࢿࣝࢠ࣮࠿ࡽ HOMO-LUMO ࡢ࢚ࢿࣝࢠ࣮ᕪࢆồࡵࡓ (ᅗ 34)࡜ࡇࢁࠊ4a ༢⊂࡛ࡣ 0.0685 a.u. (ᅗ 34a)࡟ᑐࡋࠊ4a㸩5 ࡛ࡣ 0.0374 a.u.

(ᅗ 34b)࡬ᑠࡉࡃ࡞ࡗࡓࠋࡇࡢ HOMO-LUMO ࢠࣕࢵࣉࡢῶᑡࡀ᪂ࡋ࠸ࣆ࣮ࢡࡢ ฟ⌧࡟㉳ᅉࡍࡿ࡜♧၀ࡉࢀࡓࠋ

ᅗ

ᅗ 34 a) 4a ࡢ HOMO-LUMO b)4a㸩5 ࡢ HOMO-LUMO

3-4 ⤖ㄽ

㟁Ꮚὀධ㒊఩࡜ࡋ࡚㓟໬ள㖄ୖ࡟྾╔ࡋࡓࣔࣀ࢝ࣝ࣎࢟ࢩࣇ࢙ࢽࣝࢺࣜࣆࣜ ࢪࣝࣇ࢙ࢽ࣏ࣝࣝࣇ࢕ࣜࣥ (4a)ࡣ ZnTPP (5)࡜㘒యࢆᙧᡂࡍࡿࡇ࡜࡟ࡼࡾࠊJsc

࡜IPCE ࡢ Q-band ࡀⴭࡋࡃྥୖࡋࡓࠋࡲࡓࠊศගᏛⓗ ᐃ࠿ࡽ ZnTPP ࠿ࡽ PyP (4a)࡬࡜ FRET ࡟ࡼࡿ࢚ࢿࣝࢠ࣮⛣ືࡀ㉳ࡇࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋ

 

56

4❶ ࣄ

ࣄࢻ

ࢻࣟ

ࣟ࢟

࢟ࢩ

ࢩ࢟

࢟ࣀ

ࣀࣜ

ࣜࣥ

ࣥ⨨

⨨᥮

᥮ศ

ศᩓ

ᩓᆺ

ᆺ࣏

࣏ࣝ

ࣝࣇ

ࣇ࢕

࢕ࣜ

ࣜࣥ

ࣥ࡟

࡟ࡼ

ࡼࡿ

ࡿ

ග

ගྜ

ྜᡂ

ᡂග

ගᤕ

ᤕ㞟

㞟࢔

࢔ࣥ

ࣥࢸ

ࢸࢼ

ࢼ㘒

㘒య

యࢆ

ࢆᶍ

ᶍೌ

ೌࡋ

ࡋࡓ

ࡓⰍ

Ⰽ⣲

⣲ቑ

ቑឤ

ឤኴ

ኴ㝧

㝧㟁

㟁ụ

ụ

4-1. ᗎㄽ 4-1.1. ⫼ᬒ  ᳜≀ࡢගྜᡂࡣ 7-16Å ࡢ㊥㞳ࢆಖࡕࠊศᩓࡋࡓࢡࣟࣟࣇ࢕ࣝศᏊ࡟ࡼࡾຠ⋡ ⓗ࡞ග㟁ኚ᥮ࢆ⾜࠺ࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋࡇࢀࡲ࡛ࠊࣂ࢖࣑࣓࢜ࢸ࢕ࢡࢫࡢศ 㔝࡟࠾࠸࡚ࠊࡇࡢศᩓᆺࡢ࣏ࣝࣇ࢕ࣜࣥ࢔ࣥࢸࢼ㘒యࡀሗ࿌ࡉࢀ࡚ࡁࡓࡀࠊⰍ ⣲ቑឤኴ㝧㟁ụ࡬ᛂ⏝ࡋࡓ౛ࡣᑡ࡞࠸ࠋⰍ⣲ቑឤኴ㝧㟁ụ࡬ࡢ࣓ࣜࢵࢺࡣࠊⰍ ⣲ྠኈࡢ㐺ษ࡞ศᩓ࡟ࡼࡗ࡚ບ㉳Ꮚࡢ㠀ᒁᅾ໬ࡀ㉳ࡇࡿࡇ࡜ࠊ㐺ษ࡞✵Ꮝࢆᣢ ࡕ㓟໬≀༙ᑟయୖࢆそ࠺ࡇ࡜࡟ࡼࡗ࡚ࠊ㓟໬≀༙ᑟయ࡜㟁ゎ㉁㛫ࡢ㟁Ⲵࡢ෌⤖ ྜࡀᢚไࡉࢀࡿࡇ࡜࡟ࡼࡾ㛤ᨺ㟁ᅽࡢྥୖࡀᮇᚅࡉࢀࡿ71–76ࠋ ᅗ 35 ᳜≀ࡢගᤕ㞟࢔ࣥࢸࢼ㘒య78

57  ࡇࢀࡲ࡛ࠊ୕ḟඖⓗ࡟ᗈࡀࡗ࡚⮬ᕫ⤌⧊໬ࡍࡿ࣏ࣝࣇ࢕ࣜࣥࢆ⏝࠸ࠊᵝࠎ࡞ ◊✲ࡀሗ࿌ࡉࢀ࡚ࡁࡓ77,79ࠋࣔࣀ8-ࣄࢻࣟ࢟ࢩ࢟ࣀࣜࣥ⨨᥮࣏ࣝࣇ࢕ࣜࣥࡣ⁐ᾮ ୰࡛࣒࢞ࣜ࢘ (Ga)࡟ࡼࡾ 3 㔞໬ࡍࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋࡇࡢ㘒యᵓ㐀ࡢ࣏ࣝ ࣇ࢕ࣜࣥࡣ୰ᚰ㛫࡛15-18ύࡢ㊥㞳ࢆಖࡗ࡚࠸ࡿࠋගྜᡂ࡛ࡢ࢔ࣥࢸࢼ㘒యࡣ᳜ ≀ࡢࢡࣟࣟࣇ࢕ࣝྠኈࡀ 7-16ύࡢ㊥㞳࡟࠶ࡿࡢ࡛ࠊFörster ᆺࡢ࢚ࢿࣝࢠ࣮⛣ື ᶵᵓ࡜ບ㉳཮ᴟᏊ┦஫స⏝࠿ࡽ⪃៖ࡍࡿ࡜᭱㐺࡞㊥㞳࡟Ꮡᅾࡍࡿ࡜⪃࠼ࡽࢀࡿࠋ ࡋࡓࡀࡗ࡚ᙧᡂࡉࢀࡓ㉸ศᏊ࡛ࡶྠᵝ࡟᭱㐺࡞㓄ྥ࡟ࡼࡿ࢚ࢿࣝࢠ࣮⛣ືࡀ㉳ ࡇࡿ࡜⪃࠼ࡽࢀࡿࠋࡲࡓࠊᑐ㠃࡟8-ࣄࢻࣟ࢟ࢩ࢟ࣀࣜࣥࢆ⨨᥮ࡍࡿࡇ࡜࡟ࡼࡾࠊ ࢹࣥࢻ࣐࣮ࣜ≧ࡢ࢔ࣥࢸࢼ㘒యࢆᙧᡂࡍࡿࡇ࡜ࢆሗ࿌ࡉࢀ࡚࠸ࡿࠋ ᅗ ᅗ 36 ⁐ᾮ୰࡛3 㔞యཬࡧከ㔞య࡜࡞ࡿ8-ࣄࢻࣟ࢟ࢩ࢟ࣀࣜࣥ⨨᥮࣏ࣝࣇ࢕ࣜࣥGa 㘒యࡢᶍᘧᅗ77  

58 ࡲࡓࠊⰍ⣲ቑឤኴ㝧㟁ụ࡟࠾࠸࡚ࠊⰍ⣲࠿ࡽ㓟໬≀༙ᑟయࡢ࢔࣮ࣥ࢝㒊࡜ࡋ ࡚ᵝࠎ࡞⨨᥮ᇶࡀᑟධࡉࢀ࡚ࡁࡓ80ࠋࡑࡢ୰࡛ࡶࠊ8-ࣄࢻࣟ࢟ࢩ࢟ࣀࣜࣥࢆ㸯ࡘ ⨨᥮ࡋࡓ࣏ࣝࣇ࢕ࣜࣥள㖄㘒యࡀሗ࿌ࡉࢀ࡚࠾ࡾࠊࡇࡢ࣏ࣝࣇ࢕ࣜࣥࡣ㓟໬ࢳ ࢱࣥୖ࡛࢝ࣝ࣎ࣥ㓟ࡼࡾࡶ㓟ᛶ᮲௳ୗ࡟ᙉ࠸ࡇ࡜ࡀሗ࿌ࡉࢀ࡚࠾ࡾ81ࠊኴ㝧㟁ụ ࡢᛶ⬟࡟㛵ࡋ࡚ࡣ࢝ࣝ࣎࢟ࢩᇶࢆ⨨᥮ࡋࡓ࣏ࣝࣇ࢕ࣜࣥ࡜࡯࡜ࢇ࡝ኚࢃࡽ࡞࠸ (TPPZn-COOH Jsc=5.40 mA/cm2, TPPZnOQ Jsc=5.29 mA/cm2, ఱࢀࡶจ㞟ᢚไ๣

ࡢDCA ࢆῧຍ)ࠋ

ᅗ

59 4-1.2. ┠┠ⓗ  ࡑࡇ࡛ᮏ◊✲࡛ࡣࠊ࣏ࣝࣇ࢕ࣜࣥࡢᑐ㠃ࡍࡿmeso ఩࡟ 8-ࣄࢻࣟ࢟ࢩ࢟ࣀࣜࣥ ࢆᑟධࡋࠊ㓟໬ࢳࢱࣥୖ࡛࢔࣑ࣝࢽ࣒࢘-࣏ࣝࣇ࢕ࣜࣥ࡟ࡼࡾࢹࣥࢻ࣐࣮ࣜ≧ࡢ ㉸ศᏊᵓ㐀ࢆ᭷ࡍࡿⰍ⣲ቑឤኴ㝧㟁ụࡢస〇ࢆ┠ᣦࡋࡓࠋ ᅗ 38 ᮏᐇ㦂ࡢ┠ⓗ࡛࠶ࡿ࢔࣑ࣝࢽ࣒࢘࡟ࡼࡾ ࢹࣥࢻ࣐࣮ࣜ≧࡟ከ㔞໬ࡍࡿ࣏ࣝࣇ࢕ࣜࣥ