ㄽᩥᑂᰝࡢせ᪨༤ኈࡢᑓᨷศ㔝ࡢྡ⛠༤ ኈ㸦 ⌮Ꮫ 㸧Ꮫ఩ᤵ୚ࡢせ௳Ꮫ఩つ๎➨ 4 ᮲➨ձ࣭2 㡯ヱᙜẶྡஂ㔝 ᑦஅㄽᩥ㢟┠
Studies on Molecular Recognition and Supramolecular Polymerization of Bisporphyrin
Cleft Molecules㸦 ࣅࢫ࣏ࣝࣇ࢕ࣜࣥࢡࣞࣇࢺศᏊࡢศᏊㄆ㆑ཬࡧ㉸ศᏊ㔜ྜ࡟㛵ࡍࡿ◊✲ 㸧ㄽᩥᑂᰝᢸᙜ⪅୺  ᰝ   ᩍ ᤵ  ⅊㔝 ᓅᬕᑂᰝጤဨ   ᩍ ᤵ  Ᏻಸ Ꮫ㸦Ꮫ⾡࣭♫఍㐃ᦠᐊ㸧        ᑂᰝጤဨ   ᩍ ᤵ  ྜྷ⏣ ᣑே                 ᑂᰝጤဨ   ෸ᩍᤵ  ᮌཎ ఙ୍ (ඛ㐍⌮ᕤ⣔⛉Ꮫ◊✲⛉໬ᏛᕤᏛࣉࣟࢢ࣒ࣛ ) ࠝㄽᩥᑂᰝࡢせ᪨ࠞ ᖹ㠃ᛶࡢⰾ㤶᪘ศᏊࢆ஧ࡘ⧅࠸ࡔࣆࣥࢭࢵࢺᆺࡢ࣍ࢫࢺศᏊࡣࠊ஧ࡘࡢⰾ㤶᪘㒊఩࡟ᣳࡲࢀࡓ✵Ꮝ㸦ࢡࣞࣇࢺ㸧ࢆࡶࡗ࡚࠾ࡾࠊ✀ࠎࡢᖹ㠃ศᏊࢆ✵Ꮝෆ࡟ໟ᥋ࡍࡿࠋ࣏ࣝࣇ࢕ࣜࣥࡣ㟁Ꮚ㇏ᐩ࡞ᗈ࠸ȧඹᙺᖹ㠃ࢆࡶࡕࠊ௚ศᏊ࡜ȧ㸫ȧࢫࢱࢵ࢟ࣥࢢࡸࢻࢼ࣮࢔ࢡࢭࣉࢱ࣮┦஫స⏝ࢆᙧᡂࡍࡿࡓࡵࠊࣆࣥࢭࢵࢺᆺࡢ࣍ࢫࢺศᏊࡢ㛤Ⓨ࡟ᗈࡃ฼⏝ࡉࢀ࡚ࡁࡓࠋᮏᏛ఩ㄽᩥ࡛ࡣࠊ஧ࡘࡢ࣏ࣝࣇ࢕ࣜࣥࢆ⧅࠸ࡔࣆࣥࢭࢵࢺᆺࣅࢫ࣏ࣝࣇ࢕ࣜࣥ࣍ࢫࢺศᏊࡢศᏊㄆ㆑࡜㉸ศᏊ㔜ྜ࡟㛵ࡍࡿ◊✲ࢆ⾜ࡗࡓࠋࣅࢫ࣏ࣝࣇ࢕ࣜࣥศᏊࡢ⮬ᕫ఍ྜཬࡧࢤࢫࢺໟ᥋㸸ࢡࣞࣇࢺᵓ㐀ࢆࡶࡘࣅࢫ࣏ࣝࣇ࢕ࣜࣥࡣࠊ⁐ᾮ୰࡛┦⿵ⓗ࡞⮬ᕫ఍ྜ஧㔞యࢆᙧᡂࡍࡿᖹ⾮ࡀᏑᅾࡍࡿࠋࡋ࠿ࡋࠊ⮬ᕫ఍ྜ஧㔞యࡢ༢⤖ᬗ X ⥺ᵓ㐀ゎᯒࡣᡂຌࡋ࡚࠸࡞࠿ࡗࡓࠋ௒ᅇࠊࣅࢫ࣏ࣝࣇ࢕ࣜࣥ⮬ᕫ఍ྜ஧㔞యࡢ༢⤖ᬗᵓ㐀ゎᯒ࡟ᡂຌࡋࠊ⤖ᬗ୰࡟࠾࠸࡚ࡶศᏊ㛫ࡢỈ⣲⤖ྜ࡜ȧ㸫ȧࢫࢱࢵ࢟ࣥࢢ┦஫స⏝࡟ࡼࡾ஧㔞యᵓ㐀ࡀ⥔ᣢࡉࢀ࡚࠸ࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋࡲࡓࠊࣅࢫ࣏ࣝࣇ࢕ࣜࣥࡣ㟁Ꮚ୙㊊࡞ⰾ㤶᪘ศᏊࢆໟ᥋ࡋࠊ࣍ࢫࢺ㸫ࢤࢫࢺ㘒యࢆᙧᡂࡍࡿࠋヲ⣽࡞ศᏊㄆ㆑ᶵᵓࢆ᫂ࡽ࠿࡟ࡍࡿࡓࡵࠊᵝࠎ࡞㟁Ꮚ୙㊊࡞ⰾ㤶᪘ศᏊ࡜ࣅࢫ࣏ࣝࣇ࢕ࣜࣥࡢ఍ྜᣲືࢆ᳨ウࡋࠊ఍ྜ࡟క࠺⇕ຊᏛࣃ࣓࣮ࣛࢱࢆỴᐃࡋࡓࠋࡑࡢ⤖ᯝࠊ஧✀㢮ࡢ࢚ࣥࢱࣝࣆ࣮࢚ࣥࢺࣟࣆ࣮⿵ൾ㛵ಀࡀᡂ❧ࡋ࡚࠸ࡓࠋࡘࡲࡾࠊࣅࢫ࣏ࣝࣇ࢕ࣜࣥࡢศᏊㄆ㆑࡟ࡣࠊ஧✀㢮ࡢໟ᥋ᶵᵓࡀᏑᅾࡍࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋヲ⣽࡞᳨ウࡢ⤖ᯝࠊࣅࢫ࣏ࣝࣇ࢕ࣜࣥ࡜ࢤࢫࢺศᏊࡢᙉ࠸ࢫࢱࢵ࢟ࣥࢢᵓ㐀ࡢᙧᡂ࡟క࠸ࠊໟ᥋㘒యࡢศᏊ㐠ືࡢෆ㒊⮬⏤ᗘࡀ኱ࡁࡃῶᑡࡍࡿໟ᥋ᶵᵓ࡜ࠊໟ᥋㘒యࡀᙧᡂࡋ࡚ࡶࣅࢫ࣏ࣝࣇ࢕ࣜࣥࡸࢤࢫࢺศᏊࡢෆ㒊⮬⏤ᗘࡀࡑࢀ࡯࡝ῶᑡࡋ࡞࠸ໟ᥋ᶵᵓࡀᏑᅾࡍࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࢺࣜࢫ࣏ࣝࣇ࢕ࣜࣥศᏊࡢ༠ྠⓗศᏊㄆ㆑㸸୕ᯛࡢ࣏ࣝࣇ࢕ࣜࣥࢆᯫᶫࡍࡿࡇ࡜࡛஧ࡘࡢࢡࣞࣇࢺᆺ✵Ꮝࢆࡶࡘࢺࣜࢫ࣏ࣝࣇ࢕ࣜࣥࢆྜᡂࡋࡓࠋࢺࣜࢫ࣏ࣝࣇ࢕ࣜࣥ࡜㟁Ꮚ୙㊊࡞ⰾ㤶᪘ศᏊ࡜ࡢ఍ྜᣲືࢆㄪ࡭ࡓ࡜ࡇࢁࠊ୍ẁ㝵┠ࡢ఍ྜࡀ஧ẁ㝵┠ࡢ఍ྜࢆᢚไࡍࡿ㈇ࡢ༠ྠⓗ㘒ᙧᡂࡀ☜ㄆࡉࢀࡓࠋ఍ྜ࡟క࠺⇕ຊᏛⓗࣃ࣓࣮ࣛࢱ࡜ DFT ィ⟬࡟ࡼࡗ࡚ゎᯒࢆ⾜ࡗࡓ࡜ࡇࢁࠊ୍ẁ㝵┠ࡢࢤࢫࢺໟ᥋ࡀ஧ẁ㝵┠ࡢࢤࢫࢺໟ᥋ࡢࢻࢼ࣮࢔ࢡࢭࣉࢱ࣮┦஫స⏝ࢆῶᑡࡉࡏࠊ㈇ࡢ༠ྠᛶࡀ⌧ࢀࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋศᏊ㦵᱁ࡀ୚୚࠼ࡿࣅࢫ࣏ࣝࣇ࢕ࣜࣥ㉸ศᏊ࣏࣐࣮ࣜࡢ㔜ྜᣲື㸸࣍ࢫࢺศᏊ࡜ࢤࢫࢺศᏊࢆ㐃⤖ࡋࡓศᏊࡣศᏊ㛫ࡢ࣍ࢫࢺ㸫ࢤࢫࢺ㘒ᙧᡂࢆ㥑ື࡟㉸ศᏊ࣏࣐࣮ࣜࢆᙧᡂࡍࡿࠋࡇࡢࡼ࠺࡞ศᏊࡢ㉸ศᏊ㔜ྜ࡛ࡣࠊఙ㛗㐣⛬࡟⎔≧ᵓ㐀ࡀ➇ྜࡍࡿࠋᚑࡗ࡚ࠊ㉸ศᏊ࣏࣐࣮ࣜࡢ㔜ྜᗘࡣࠊ㔜ྜ㐣⛬࡟ᣕᢠࡍࡿ⎔≧ᵓ㐀ࡢᏳᐃᛶ࡟ࡼࡾỴᐃࡉࢀࡿࠋࡋ࠿ࡋࠊ⎔≧ᵓ㐀࡜㔜ྜᵓ㐀ࡢᖹ⾮ࡣ㠀ᖖ࡟」㞧࡛࠶ࡿࡓࡵࠊࡇࢀࡽࡢ⇕ຊᏛⓗᏳᐃᛶࢆᐃ㔞ⓗ࡟㆟ㄽࡋࡓ౛ࡣ࡯࡜ࢇ࡝࡞࠸ࠋࡑࡇ࡛ࠊࣅࢫ࣏ࣝࣇ࢕ࣜࣥ࡜ࢺࣜࢽࢺࣟࣇࣝ࢜ࣞࣀࣥࢆᵝࠎ࡞㛗ࡉࡢ࢔ࣝ࢟ࣝ㙐࡛㐃⤖ࡋࡓศᏊࢆྜᡂࡋࠊࡑࡢ㉸ศᏊ㔜ྜᣲືࢆㄪ࡭ࡓࠋ㧗⃰ᗘࡢ⁐ᾮ୰࡛ࡣࠊ࢔ࣝ࢟ࣝ㙐ࡢ㛗࠸ศᏊࡣ㔜ྜࡀಁ㐍ࡉࢀࠊ࢔ࣝ࢟ࣝ㙐ࡢ▷࠸ศᏊࡣ㔜ྜࡀᢚไࡉࢀ࡚࠸ࡓࠋࡲࡓᕼⷧ⁐ᾮ୰࡛ࡣࠊ࢔ࣝ࢟ࣝ㙐ࡢ㛗࠸ศᏊࡣ⎔≧ࣔࣀ࣐࣮ࠊ࢔ࣝ࢟ࣝ㙐ࡢ▷࠸ศᏊࡣ⎔≧ࢲ࢖࣐࣮ࢆᙧᡂࡋ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡑࡇ࡛ࠊᕼⷧ⁐ᾮ୰ࡢ⎔໬ᖹ⾮ཬࡧศᏊ㛫఍ྜ࡟࠾ࡅࡿ⇕ຊᏛࣃ࣓࣮ࣛࢱࢆ⟬ฟࡋࠊ㔜ྜࡢึᮇẁ㝵ࡢᖹ⾮ࢆ⪃ᐹࡋࡓࠋࡑࡢ⤖ᯝࠊ࢔ࣝ࢟ࣝ㙐ࡢ㛗࠸ศᏊ࡯࡝⎔໬࡟క࠺㓄ᗙ࢚ࣥࢺࣟࣆ࣮ᦆኻࡀ኱ࡁࡃࠊ⎔≧ᵓ㐀ࢆ୙Ᏻᐃ໬ࡋ࡚࠸ࡓࠋࡋࡓࡀࡗ࡚ࠊࣔࣀ࣐࣮ศᏊࡢ⎔໬࡟క࠺㓄ᗙ࢚ࣥࢺࣟࣆ࣮ᦆኻࢆไᚚࡍࡿࡇ࡜࡛ࠊ㉸ศᏊ㔜ྜࢆಁ㐍࡛ࡁࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋ஧✀㢮ࡢ㓟໬㑏ඖ่⃭࡟ࡼࡾᛂ⟅ࡍࡿ㉸ศᏊ࣏࣐࣮ࣜࡢ㛤Ⓨ㸸㟁Ꮚ㇏ᐩ࡞࣏ࣝࣇ࢕ࣜࣥศᏊࡣᐜ᫆࡟㓟໬ࡀྍ⬟࡛࠶ࡾࠊ㟁Ꮚ୙㊊࡞ࢺࣜࢽࢺࣟࣇࣝ࢜ࣞࣀࣥࡣᐜ᫆࡟㑏ඖ࡛ࡁࡿࠋࡑࡇ࡛ࠊࣅࢫ࣏ࣝࣇ࢕ࣜࣥ࡜ࢺࣜࢽࢺࣟࣇࣝ࢜ࣞࣀࣥࢆ㐃⤖ࡋࡓࣔࣀ࣐࣮ศᏊࡢ㓟໬㑏ඖ่⃭࡟క࠺㉸ศᏊ㔜ྜᣲືࢆ᳨ウࡋࡓࠋࡇࡇ࡛ࠊࣔࣀ࣐࣮࡟㓟໬๣࡜㑏ඖ๣ࢆูࠎ࡟ῧຍࡋ࡚⏕ࡌࡿ࣏ࣝࣇ࢕ࣜࣥ㒊఩ࡢ୍㟁Ꮚ㓟໬≧ែ࡜ࢺࣜࢽࢺࣟࣇࣝ࢜ࣞࣀࣥ㒊఩ࡢ୍㟁Ꮚ㑏ඖ≧ែࡣࠊ㟁Ꮚࢫࣆࣥඹ㬆࡟ࡼࡾ☜ㄆࡋࡓࠋᣑᩓಀᩘᐃ࡜⢓ᗘᐃࡼࡾࣔࣀ࣐࣮ࡀ㔜ྜయࢆᙧᡂࡋ࡚࠸ࡿࡇ࡜ࡀ☜ㄆࡉࢀࡓࠋࡇࡢ㔜ྜయࡢ⁐ᾮ࡟㓟໬๣ࡲࡓࡣ㑏ඖ๣ࢆῧຍࡍࡿ࡜ࠊ㉸ศᏊ࣏࣐࣮ࣜࡀゎ㔜ྜࡋ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡋࡓࡀࡗ࡚ࠊࣅࢫ࣏ࣝࣇ࢕ࣜࣥ㒊఩࡜ࢺࣜࢽࢺࣟࣇࣝ࢜ࣞࣀࣥ㒊఩ࡢ㓟໬࡜㑏ඖ཯ᛂ࡟ࡼࡾ㔜ྜ࡜ゎ㔜ྜࢆไᚚ࡛ࡁࡿ่⃭ᛂ⟅ᛶ㉸ศᏊ࣏࣐࣮ࣜࡢ㛤Ⓨ࡟ᡂຌࡋࡓࠋ ௨ୖࠊᑂᰝࡢ⤖ᯝࠊᮏㄽᩥࡢⴭ⪅ࡣ༤ኈ㸦⌮Ꮫ㸧ࡢᏛ఩ࢆᤵ୚ࡉࢀࡿ༑ศ࡞㈨᱁ࡀ࠶ࡿ
ࡶࡢ࡜ㄆࡵࡿࠋ බ⾲ㄽᩥ(1) Ring–Chain Competition in Supramolecular Polymerization Directed by Molecular
Recognition of the Bisporphyrin Cleft.
Takehiro Hirao, Naoyuki Hisano, Shigehisa Akine, Shin-ichi Kihara, andTakeharu Haino

Macromolecules 2019, 52, 6160-6168.
(2) A Dual-Redox Responsive Supramolecular Polymer Driven by Molecular
Recognition between Bisporphyrin and Trinitrofluorenone.
Naoyuki Hisano, Takehiro Hirao, and Takeharu Haino

Chemical Communications 2020, 56, 7553-7556.
(3) Self-Complementary Structure of Bisporphyrin Dimer.
Naoyuki Hisano, Takehiro Hirao, and Takeharu Haino

Chemistry Letters 2021, 50, 1844-1847.
(4) Host–Guest Complexation of Bisporphyrin Cleft and Electron-Deficient AromaticGuests.
Naoyuki Hisano and Takeharu Haino

The Journal of Organic Chemistry 2022, 87, 4001-4009.
 ཧ⪃ㄽᩥ
(5) Helicity of a Polyacetylene Directed by Molecular Recognition of Biscalixarene andFullerene.
Takehiro Hirao, Yoshiki Iwabe, Naoyuki Hisano, and Takeharu Haino

Chemical Communications 2020, 56, 6672-6675.