JP3561837B2 - Porphyrin compound in which two or more porphyrins are condensed with each other by three bonds of a meso-meso carbon bond and a bond of two β-β carbons - Google Patents

Description

【０００９】
〔一般式（１）において、Ｒ^１及びＲ^２は、未置換の又は３，５位に置換基を有するフェニル基であり、置官基としてはｔ−ブチル基、ｎは０以上の整数、Ｍは金属原子または水素である。〕
【００１０】
Ｂ．本発明の化合物の製造方法
前記Ａ．に記載の化合物のメゾ位に隣接する２つのβ位の炭素を互いに結合した２つのβ−β結合はメゾーメゾ結合ポルフィリンの酸化により形成される。
ところで、ポルフィリン配列を製造する際、立体配置的に混み合っていない５，１５−ジアリールメタロポルフィリン類は、直接結合したジポルフィリン類、例えば、Ｚｎ（ＩＩ）およびＭｇ（ＩＩ）ポルフィリン類からはメゾーメゾ単結合ジポルフィリン類が合成でき、Ｎｉ（ＩＩ）、Ｃｕ（ＩＩ）、およびＰｄ（ＩＩ）ポルフィリンからは、メゾ−β単結合ジポルフィリン類が合成でき、およびＮｉ（ＩＩ）およびＰｄ（ＩＩ）ポルフィリン類をより強い酸化剤（トリ（ブロモフェニル）アンモニウムヘキサクロロアンチモネート（ＢＡＨＡ：（ｐ−ＢｒＣ_６Ｈ_４）_３ＮＳｂＣｌ_６））で酸化するとメゾ−β二重結合ポルフィリン類を合成できる。
前記調製における、異なった位置選択的（ｒｅｇｉｏｓｅｌｅｃｔｖｉｔｙ）カップリング、すなわちメゾーメゾおよびメゾーβは、関与するＨＯＭＯ軌道に関連して説明することができる。
すなわちＭｇ（ＩＩ）、Ｚｎ（ＩＩ）ポルフィリン類に対してはＡ_２ｕ（メゾ炭素に大きな密度を示すＡ_２ｕＨＯＭＯ）、そしてＮｉ（ＩＩ）、Ｃｕ（ＩＩ）、およびＰｄ（ＩＩ）ポルフィリン類に対してはＡ_１ｕ（β−ピロール炭素に大きな電子密度を示すＡ_１ｕＨＯＭＯ）が対応する。
これらの結果を考慮に入れると、β−ピロール炭素に大きな電子密度を示すＡ_１ｕＨＯＭＯを持つメゾーメゾ結合金属ジポルフィリンは、酸化の際、フリーなβ位置においてカップリング反応が起こるであろうと考える。
従って、前記電子密度を考慮して原料メゾーメゾ結合金属ジポルフィリンを採用するのが好ましい。
【００１１】
本発明の化合物の製造での位置選択的縮合反応は、例えば、メゾーメゾ結合Ｃｕ^ＩＩ−ジポルフィリン化合物１〔前記一般式（１）において、ｎ＝０、Ｒ^１及びＲ^２が３，５−ｔ−ブチルフェニル基、Ｍ＝Ｃｕの化合物〕は、Ｃ_６Ｆ_６中において、２当量の強力な酸化剤であるトリ（ブロモフェニル）アンモニウムヘキサクロロアンチモネート（ＢＡＨＡ：（ｐ−ＢｒＣ_６Ｈ_４）_３ＮＳｂＣｌ_６）で、室温において２日間処理することにより、本発明の化合物の１つである、一般式（２）の三重結合ジポルフィリン化合物において、
【００１２】
【化２】

【００１３】
〔一般式（２）中、Ｒ^１、Ｒ^２、及びＭは、一般式（１）と同じ、Ｒ^３は、Ｈ又はハロゲン、Ｈ^ａはＨである。〕
【００１４】
Ｒ^１＝Ｒ^２＝３，５−ｔ−ブチルフェニル基、Ｍ＝Ｃｕ、及びＲ^３＝Ｈの化合物（化合物２）および化合物（２）のＲ^３をＣｌとした化合物（化合物３）を、それぞれ収率６２および６％で得られる。
これに対して、前記メゾーメゾ結合Ｃｕ^ＩＩ−ジポルフィリン化合物１を、ＣＨＣｌ_３中において前記Ｃ_６Ｆ_６中におけると同様の条件で酸化すると、示量β塩素化により、前記化合物２（８％）及び前記化合物３（２９％）およびジクロル化ジポルフィリン化合物（４３％）からなる生成物が得られる。一方。塩化メチレン中ではこの反応は進行しない。
これらの生成物の違いから、この酸化閉環プロセスにはラジカル的な塩素原子引き抜き反応が関与していることがわかる。Ｃ_６Ｆ_６はβ塩素化を抑制するのに好ましい溶媒であり、他にはトリフルオロメチルベンゼンなどを挙げることができる。
酸化剤としては、前記ＢＡＨＡの代えて、電解酸化やＤＤＱ（ジクロロジシアノーパラベンゾキノン）とスカンジウムトリフラートの組み合わせなどを用いることができる。
【００１５】
標的化合物２（三重結合ポルフィリン二量体）の構造は、その吸収スペクトル（λ_ｍａｘ＝４１１，５７６，および９９７ｎｍ）およびＭＡＬＤＩ−ＴＯＦ ＭＳ（Ｍａｔｒｉｘ ａｓｓｉｓｔｅｄ Ｌａｓｅｒ Ｄｅｓｏｒｐｔｉｏｎ Ｉｏｎｉｚａｔｉｏｎ−Ｔｉｍｅ ｏｆ Ｆｌｉｇｈｔ Ｍａｓｓ Ｓｐｅｃｔｒｕｍ）により得られる、ｍ／ｚ＝１８６６（Ｃ_１２４Ｈ_１３８Ｎ_８Ｃｕに対する計算分子量＝１８６５）にピークを持つ元の分子イオンピークから、推定することができる。中心金属を亜鉛に変換した化合物４〔一般式（２）において、Ｒ^１＝Ｒ^２＝３，５−ｔ−ブチルフェニル基、Ｍ＝Ｚｎ、及びＲ^３＝Ｈの化合物〕では、比較的単純な、対称構造を反映する^１Ｈ−ＮＭＲスペクトル（互いに結合した、７．７５および７．７０ｐｐｍに現れるβプロトンに対する二つのダブレットおよび７．３５ｐｐｍに現れるβプロトン（Ｈ＊）に対するシングレット）および分子量ｍ／ｚ＝１８６８（Ｃ_１２４Ｈ_１３８Ｎ_８Ｚｎ_２に対する計算分子量＝１８９９）からも推定できる。
前記化合物３は、同様な吸収スペクトル（λ_ｍａｘ＝４０９，５７３，および９９０ｎｍ）、およびｍ／ｚ＝１９００（Ｃ_１２４Ｈ_１３７ＣｌＣｕ_２Ｎ_８＝１８９９）の元のピークを示す。
【００１６】
三重結合縮合ジポルフィリンのＸ線構造を確認するために、本発明者は、メゾーメゾＣｕ^ＩＩ−ジポルフィリン化合物５〔一般式（１）において、ｎ＝０、Ｒ^１はフェニル基、Ｒ^２が３，５−ｔ−ブチルフェニル基、Ｍ＝Ｃｕの化合物〕を、三重結合ジポルフィリン化合物６〔一般式（２）において、Ｒ^１＝フェニル基、Ｒ^２＝３，５−ｔ−ブチルフェニル基、Ｍ＝Ｃｕ、Ｒ^３＝Ｈの化合物）〕（ｍ／ｚ＝１６４５，Ｃ_１０８Ｈ_１０６Ｎ_８Ｃｕ_２＝１６４１）および化合物７〔化合物６のＲ^３をＣｌに変えた化合物〕（ｍ／ｚ＝１６７７，Ｃ_１０８Ｈ_１０５Ｎ_８Ｃｕ_２Ｃｌ＝１６７５）に、収率それぞれ７６％および６％で、変換した。
前記化合物６のＸ線による構造を図１に示す。
２つのポルフィリン環は縮合して、図１の上面から見た構造及び側面から見た構造から理解されるように、平均平面の上下にある２５の一団の原子の平均面偏位（０．０２９Å）とほぼ完全な同一平面配座（ｃｏｐｌａｎａｒ ｃｏｎｆｏｍａｔｉｏｎ）を形成し、２つの１．４１Åのβ−β結合および１つの１．４４Åのメゾーメゾ結合を持つ化合物を形成する。
【００１７】
本発明者は、三重結合Ｚｎ^ＩＩ−ジポルフィリン化合物８〔一般式（２）において、Ｒ^１＝フェニル基、Ｒ^２＝３，５−ｔ−ブチルフェニル基、Ｍ＝Ｚｎ、Ｒ^３＝Ｈの化合物〕のＸ線構造を得るのに成功した。前記化合物８は、０．２３Åの平均偏位および１．４４Åの２つのβ−β結合および１．５１Åのメゾーメゾ結合を示す（図２）。
前記化合物８の結晶充填は、約５．４４Åで隔離した交互ポルフィリンの平行シート状の形状である。該形状はポルフィリン結晶においては共通であるが、前記化合物６からは全く異なっている。
【００１８】
【実施例】
実施例１
５０ｍＬの丸ボトル型フラスコに、メゾーメゾ結合Ｃｕ^ＩＩ−ジポルフィリン化合物５（１６ｍｇ，１０μｍｏｌ）をＣ_６Ｆ_６（２０ｍＬ）に分散懸濁液させる。反応容器はフォイルでカバーした。酸化剤であるＢＡＨＡ（１８ｍｇ，２２μｍｏｌ）を一部ずつ加えた。混合物を２日間、室温で撹拌し、該混合物をメタノールおよびテトラヒドロフラン（ＴＨＦ）で希釈する。ロータリーエバポレーターで溶媒を取り除き、残渣をベンゼン−メタノールで処理して一旦沈殿させる。生成物はフラッシュクロマトグラフィーのシリカゲル（ＷａｋｏｇｅｌＣ−４００）カラム上を通して最終分離される。ヘキサン／ジクロロメタン（ＣＨ_２Ｃｌ_２）抽出液で処理すると、最初の画分として未変性の前記原料化合物５（２ｍｇ，１３％）が、第２画分としてモノ塩素化化合物７（１．０ｍｇ，６％）、そして第３画分として非塩素化化合物６（１２．２ｍｇ，７６％）が得られた。
【００１９】
三重結合Ｃｕ^ＩＩ−ジポルフィリン化合物６は、濃硫酸とＴＦＡとの混合物による脱脱金属化（メタルフリー）、およびその後のＺｎ^ＩＩ−イオンの挿入の工程により８０％の収率で対応するＺｎ^ＩＩ−ジポルフィリン化合物８に変換される。
該縮合ポルフィリンは、縮合結合により強制されて平面構造を持ち、これにより極めて非局在化したπ−電子特性を示す。該縮合ポルフィリン配列は、従来報告されているポルフィリン配列の化合物においては極めて限られていた二次あるいは三次の非線形光学素子（ＮＬＰ）または分子ワイヤーとしての応用の面でのより実用的な特性を示す点で興味深いものである。
【００２０】
分析結果：
化合物６：
ＭＡＬＤＩ−ＴＯＦによる分子量は、ＭＳｍ／ｚ１８６６である。
因みに、Ｃ_１２４Ｈ_１３８Ｎ_８Ｃｕ_２に対する計算値は、１８６５である。
ＵＶ／Ｖｉｓ（紫外／可視光）吸収特性は、λｍ＝４１１，５７６，および９９６ｎｍである。
化合物９：^１Ｈ−ＮＭＲ（ＣＤＣｌ_３）、δ １．４１（ｓ，３６Ｈ，ｔ−Ｂｕ），１．４５（ｓ，７２Ｈ，ｔ−Ｂｕ），７．３５（ｓ，４Ｈ，Ｐｏｒ−β），７．５９（ｔ，Ｊ＝１．８Ｈｚ，２Ｈ，Ａｒ−Ｈ），７．６１（ｔ，Ｊ＝１．８Ｈｚ，４Ｈ，Ａｒ−Ｈ），７．６３（ｄ，Ｊ＝１．８Ｈｚ，４Ｈ，Ａｒ−Ｈ），７．６７（ｄ，Ｊ＝１．８Ｈｚ，８Ｈ，Ａｒ−Ｈ），７．７０（ｄ，Ｊ＝４．９Ｈｚ，４Ｈ，Ｐｏｒ−β），および７．７５（ｄ，Ｊ＝４．９，４Ｈ，Ｐｏｒ−β）；
ＭＡＬＤＩ−ＴＯＦによる分子量は、ＭＳｍ／ｚ１８６７である。
因みに、Ｃ_１２４Ｈ_１３８Ｎ_８Ｚｎ_２に対する計算値は、１８６７である。
ＵＶ／Ｖｉｓ（紫外／可視光）吸収特性は、λｍ＝４１９．５８２，そして１０６８である。
【００２１】
実施例２
更に、メゾーメゾ結合Ｃｕ^ＩＩトリポルフィリン化合物９〔一般式（１）において、ｎ＝１、Ｒ^１＝フェニル基、Ｒ^２＝３，５−ｔ−ブチルフェニル基、Ｍ＝Ｃｕ〕は、Ｃ_６Ｆ_６中で３日間４当量のＢＡＨＡにより酸化すると、３つの結合によって縮合したトリポルフィリン化合物１０
【００２２】
【化３】

【００２３】
〔Ｒ^１＝フェニル基、Ｒ^２＝３，５−ｔ−ブチルフェニル基〕
を３３％の収率で得た。その際原料化合物である化合物９は３０％の回収率で回収された。
縮合トリポルフィリン化合物１０は、ｍ／ｚ＝２３８３（Ｃ_１５６Ｈ_１５２Ｎ_１２Ｃｕ_３に対する計算値２３８２）に親分子ピーク示し、そして１２５１ｎｍに極端なレッドシフトＱ−バンドを示す。
化合物１０の持つ更なる特性の検討は、該化合物が非常に小さい溶解性であるために難しかった。
しかしながら、上記の結果は、この酸化的閉環反応を単分散物〔分子長の揃った化合物類。このような単分散化合物についても、本発明者は既に提案している（特願２０００−２３８７８号）。〕ポリマー（オリゴマーを含む）メゾーメゾ結合ポルフィリン配列類にも敷衍できること示している。
【００２４】
多重結合した本発明の縮合ジポルフィリンの電子的相互作用は極めて強いことは十分に確立されたことであり、レッドシフトした強いＱバンド、および一分子酸化ポテンシャルの低下を起こさせ。
図３には、化合物１、２、９、、１０および１１の吸収スペクトルが示されている。
２つのメゾーβで結合した一般式（３）で表されるＣｕ^ＩＩ−ジポルフィリン化合物１１
【００２５】
【化４】

【００２６】
〔一般式（３）中Ｒ^１、Ｒ^２、及びＭは、一般式（１）と同じ〕
の吸収スペクトルを比較のために記載する。
メゾーメゾ結合ポルフィリン化合物１および９は、先に報告〔Ａ．Ｏｓｕｋａ，Ｈ．Ｓｈｉｍｉｄｚｕ，Ａｎｇｅｗ Ｃｈｅｍ．１９９７，１１１，１４０；Ａｎｇｅｗ．Ｃｈｅｍ．Ｉｎｔ．Ｅｄ．Ｅｎｇｌ．１９９７，３６，１３５． Ｔ．Ｏｇａｗａ，Ｙ．Ｎｉｓｈｉｍｏｔｏ，Ｎ．Ｙｏｓｈｉｄａ，Ｎ．Ｏｎｏ，Ａ．Ｏｓｕｋａ，Ｃｈｅｍ．Ｃｏｍｍｕｎ．１９９８，３３７．〕したような分裂ソーレー帯を示すのに対し、３重に結合したオリゴポルフィリン化合物２および１１は４１１，５７６，および９９６ｎｍ並びに４１３，６５７，および１２５１ｎｍにそれぞれ特徴的な吸収スペクトルを示す。
これらの吸収帯の特定はされていないけれども、縮合結合はｅ_ｇ軌道の縮退を解放して有意の摂動を引き起し、強化されたおよびレッドシフトしたＱ−バンドを引起こす。
一電子酸化電位は、原料のメゾーメゾ結合化合物１では０．６９Ｖであり、化合物１１では０．４７Ｖであるが、３重に結合した化合物２では０．３９Ｖと低下している。
従って、３重結合（２つのβ−β炭素結合および１つのメゾ−メゾ炭素結合）ジポルフィリン化合物２中の電子的相互作用は、従来報告されている縮合ジポルフィリン類（２つのメゾーβ結合により縮合した化合物１１など）における電子的相互作用に比べて極めて強い。
【００２７】
中心金属の効果は、予備的にはＣｕ^ＩＩ−ジポルフィリン化合物６およびＺｎ^ＩＩ−ジポルフィリン化合物８とを対比することにより調べた。
最大のレッドシフトされたＱ−帯は化合物８においては１０６８ｎｍに観察され、化合物６よりも７２ｎｍだけレッドシフトしており、メゾーメゾ結合Ｚｎ−^ＩＩジポルフィリン化合物１２〔一般式（１）において、Ｒ^１＝Ｒ^２＝３，５−ｔ−ブチルフェニル基、Ｍ＝Ｚｎの化合物〕（０．５４Ｖ）の１電子酸化電位は、化合物８では０．１１Ｖまで減少しており、従って、Ｚｎ−^ＩＩ錯体中における電位のシフトはより大きく、このことは三重結合Ｚｎ^ＩＩ−ジポルフィリン類中におけるより大きな電子相互作用を示唆している。
低い一電子酸化電位およびかなりレッドシフトした増加吸収帯により証明されている極端に強い電子的相互作用から、三重結合ポルフィリン配位列は、電子的分子ワイヤーの要素としての利用の面でかなり有望である。
このような合成戦略を、より大きなオリゴマーおよびポリマーポルフィリン配列へ拡張することの可能性も高い。
前記中心金属の効果の検討にもあるように、三重結合ジポルフィリン類の電子的相互作用は中心金属に依存している、このことは、種々の金属をジポルフィリン配位子に導入して見る試みは、極めて興味深いプロジェクトである。
【００２８】
【発明の効果】
以上述べたように、本発明のポルフィリン化合物から誘導される化合物は、低い一電子酸化電位およびかなりレッドシフトした増加吸収帯により証明されている極端に強い電子的相互作用から、三重結合ポルフィリン配位列は、電子的分子ワイヤーの要素としての利用の面でかなり有望である、という優れた効果がもたらされる。
【図面の簡単な説明】
【図１】化合物６のＸ線による構造〔上面から見た構造（上）及び側面から見た構造（下）〕
【図２】化合物８のＸ線による構造〔上面から見た構造（上）及び側面から見た構造（下）〕
【図３】本発明の化合物２，１０、原料化合物１，９、及び２つのメゾーβ結合により縮合した化合物１１の吸収スペクトル
【図４】本発明の化合物、原料化合物及び２つのメゾーβで結合したＣｕ^ＩＩ−ジポルフィリン化合物のまとめ[0001]
TECHNICAL FIELD OF THE INVENTION
TECHNICAL FIELD The present invention relates to a fused porphyrin compound in which two or more porphyrin rings are fused so as to maintain higher planarity and greater electronic conjugation, and more particularly to a fused porphyrin compound in which porphyrin rings are fused to each other by three bonds.
[0002]
[Prior art]
Porphyrin molecules have remarkable absorption, fluorescence, and phosphorescence characteristics, and have a small HOMO-LUMO gap, and thus have high electrical conductivity. In addition, almost all metal elements can be incorporated into the central vacancy as a ligand, and optical properties and oxidation-reduction properties can be adjusted by the incorporated metal, which can meet a wide range of functional material requirements. Have sex. Porphyrins also have various functions such as an electron transfer element in biological processes such as oxidation-reduction catalysis in metabolism and photosynthesis and respiration in vivo. Paying attention to these functions, development as a material having an energy conversion function and a biological oxidation-reduction catalyst is being performed. Recently, many studies have been carried out to review porphyrin multimers as optoelectronic materials.However, porphyrin molecules form polymers and oligomers with rigidity and high stability structure as block units that assemble long π-conjugated structures. There have been many studies focusing on the possibility of light absorption, strong light absorption in the visible light region, fluorescence, phosphorescence, a small HOMO-LUMO energy gap, and the like.
[0003]
Under such circumstances, the present inventor also uses porphyrin molecules as block units, and oligomers from porphyrin molecules bound up to 300 to 400 units in one direction at each bond of meso-position carbons of each porphyrin molecule (meso-meso carbon bond). , A porphyrin molecule and a porphyrin molecule in which the carbon at the β-position and the carbon at the meso-position of one molecule are bonded to the carbon at the meso- and β-positions of the other molecule, respectively, Condensed porphyrin oligomers linked by bonds have been proposed.
And the meso-meso-bound porphyrin array compounds have their rod-shaped, sufficient, fast, non-coherent energy interactions to cause energy hopping and impede the transfer of energy along the array. Since it has an advantageous feature that there is no energy sink, it has been expected as a promising photon wire or molecular wire. These properties are due to the orthogonal morphology, which tends to minimize electronic interactions between adjacent porphyrins, due to the arrangement being planar and more electronically conjugated. A practical molecular scale conductive molecular wire can be formed. This is because the meso-meso-bound porphyrin sequence has already been obtained as an isolated 128-mer with a molecular length of about 108 nm.
[0004]
However, the meso-meso-binding porphyrin sequence is not a structure in which porphyrins are bonded to each other by two direct bonds (referred to as double bonds or condensation), in other words, does not have a structure constituting a commonly expanded π-electron network. Therefore, it cannot be said that the conductive wire has sufficient properties.
Therefore, the present inventor further proposes a porphyrin compound in which a porphyrin unit is extended in the length direction by two bonds of the meso-β and β-meso, that is, a condensate of the porphyrin compound, and as an electron wire or the like. More practical compounds have been developed.
However, this is still not sufficient from the viewpoint of practicality as an optical wire or a molecular wire.
[0005]
[Problems to be solved by the invention]
An object of the present invention is to develop a π-electron network and a structure for improving the length of delocalization of electrons, which are more commonly expanded, thereby further reducing porphyrin compound derivative molecules that are approaching practical use such as electron wires. To provide.
Since the properties of such a compound are expected to be derived from a chemical structure with a more developed condensed structure, the present inventor diligently studied how to design a compound having such a structure. It has been discovered that a porphyrin compound having a porphyrin unit extended in the length direction by three bonds can be obtained by effectively oxidizing the compound having the meso-meso-carbon-bonded porphyrin sequence at the β-position carbon adjacent to the meso-meso-bonded carbon. And the said subject was solved.
[0006]
The present invention relates to a meso-meso carbon bond in which the porphyrin ring is bonded to the meso-position carbons of each porphyrin ring and two β-β carbon bonds between two β-position carbons adjacent to the meso-position carbon. 3 following the porphyrin ring 2 or the three binding to the extend bonded to each other in one direction, following A. Or a metal-free condensed porphyrin compound coordinated with a metal selected from the group of metal atoms of
A. The group of metal atoms is Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ti, Zr. , Hf, V, Nb, Ta, Th, U, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ab, Au, Cd , Hg, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb, and Bi. Preferably, the condensed porphyrin compound is characterized in that the porphyrin has a meso-position other than a meso-meso bond, and is substituted with an unsubstituted or 3,5-substituted phenyl group. The above-mentioned condensed porphyrin compound, wherein the substituent in the 5-substituted phenyl group is a tert-butyl group, and more preferably, two or more and three or less porphyrin rings are bonded to each other in one direction by a meso-meso bond. The condensed porphyrin compound, which is obtained by oxidizing an oligo or poly (porphyrin) compound to bond two β-position carbons next to the carbon of the meso-meso bond to each other.
[0007]
[Embodiment of the present invention]
The present invention will be described in more detail.
A. As the compound having a meso-meso-binding porphyrin sequence used for producing the compound of the present invention, a known compound can be used. Further, the present inventors have already proposed compounds in which the meso-meso-binding porphyrin sequence has developed to a 9-mer or more (Japanese Patent Application No. 11-248756), and these compounds are also used as raw materials for producing the compounds of the present invention. be able to.
The compound of the starting meso-meso-binding porphyrin sequence can be represented by the general formula (1).
[0008]
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[0009]
[In the general formula (1), R ¹ and R ² are unsubstituted or a phenyl group having a substituent at the 3,5-position, a t-butyl group as a substituent, n is an integer of 0 or more, M is a metal atom or hydrogen. ]
[0010]
B. Method for producing compound of the present invention The two β-β bonds in which two carbons at the β-position adjacent to the meso-position of the compound described in 1) are bonded to each other are formed by oxidation of a meso-meso-bound porphyrin.
By the way, when producing a porphyrin sequence, 5,15-diarylmetalloporphyrins which are not sterically congested are converted from directly bound diporphyrins such as Zn (II) and Mg (II) porphyrins to meso-meso. Single bond diporphyrins can be synthesized, and from Ni (II), Cu (II), and Pd (II) porphyrins, meso-β single bond diporphyrins can be synthesized, and Ni (II) and Pd (II) porphyrins stronger oxidant (tri (bromophenyl) ammonium hexachloroantimonate _{(BAHA: (p-BrC 6} H 4) 3 NSbCl 6)) can be synthesized meso -β double bond porphyrins oxidation with.
The different regioselectivity couplings in the preparation, meso-meso and meso-β, can be explained in relation to the HOMO orbitals involved.
That is, for Mg (II) and Zn (II) porphyrins, A _2u (A _2u HOMO showing large density on _mesocarbon ) and Ni (II), Cu (II) and Pd (II) porphyrins On the other hand, A _1u (A _1u HOMO showing a large electron density in β-pyrrole carbon) corresponds thereto.
Taking these results into account, the Mezomezo bound metal di porphyrin with A _1u HOMO showing a large electron density β- pyrrole carbon, the oxidation, think would coupling reaction occurs in the free β position.
Therefore, it is preferable to use the raw material meso-meso-bonded metal diporphyrin in consideration of the electron density.
[0011]
The regioselective condensation reaction in the production of the compound of the present invention may be, for example, a meso-meso-bonded Cu ^II- diporphyrin compound 1 [in the above general formula (1), n = 0, R ¹ and R ² are 3,5-t -Butylphenyl group, a compound of M = Cu] is tri-bromophenyl) ammonium hexachloroantimonate (BAHA: (p-BrC ₆ H ₄ ) ₃ , which is a strong equivalent oxidant in C ₆ F ₆ NSbCl ₆ ) for 2 days at room temperature to give a triple bond diporphyrin compound of the general formula (2), which is one of the compounds of the present invention.
[0012]
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[0013]
In [Formula ^{(2), R 1, R} 2, and M is the same, ^{R 3} is a general formula (1), H or halogen, is ^{H a} is H. ]
[0014]
A compound (Compound 3) in which R ¹ = R ² = 3,5-t-butylphenyl group, M = Cu, and R ³ = H (Compound 2) and a compound (Compound 3) in which R ³ of Compound (2) is Cl, Obtained in 62 and 6% yield respectively.
On the other hand, when the meso-meso-bound Cu ^II- diporphyrin compound 1 is oxidized in CHCl ₃ under the same conditions as in C ₆ F ₆ , the compound 2 (8%) is obtained by the indicated β chlorination. And a product consisting of the compound 3 (29%) and the dichlorinated diporphyrin compound (43%). on the other hand. This reaction does not proceed in methylene chloride.
The difference between these products indicates that this oxidative ring closure process involves a radical chlorine atom abstraction reaction. C ₆ F ₆ is a preferred solvent for suppressing β-chlorination, and other examples include trifluoromethylbenzene.
As the oxidizing agent, electrolytic oxidation or a combination of DDQ (dichlorodicyanoparabenzoquinone) and scandium triflate can be used in place of the BAHA.
[0015]
The structure of target compound 2 (triple-bond porphyrin dimer) was determined by its absorption spectrum (λ _max = 411, 576 and 997 nm) and MALDI-TOF MS (Matrix assisted Laser Desorption Ionization-Time of Flight Sample). , M / z = 1866 (calculated molecular weight for C ₁₂₄ H ₁₃₈ N ₈ Cu = 1865) from the original molecular ion peak. Compound 4 in which the central metal is converted to zinc [in the general formula (2), a compound in which R ¹ = R ² = 3,5-t-butylphenyl group, M = Zn, and R ³ = H] is relatively simple. ¹ H-NMR spectra reflecting the symmetrical structure (two doublets for the β proton appearing at 7.75 and 7.70 ppm and singlets for the β proton (H *) appearing at 7.35 ppm bound to each other) and the molecular weight m / Z = 1868 (calculated molecular weight for C ₁₂₄ H ₁₃₈ N ₈ Zn ₂ = 1899).
Compound 3 shows a similar absorption spectrum (λ _max = 409,573, and 990 nm) and the original peak at m / z = 1900 (C ₁₂₄ H ₁₃₇ ClCu ₂ N ₈ = 1899).
[0016]
In order to confirm the X-ray structure of the triple bond condensed diporphyrin, the present inventor has proposed a meso-meso-Cu ^II- diporphyrin compound 5 [in the general formula (1), n = 0, R ¹ is a phenyl group, and R ² is 3 , 5-t-butylphenyl group, a compound of M = Cu] with a triple bond diporphyrin compound 6 [in the general formula (2), R ¹ = phenyl group, R ² = 3,5-t-butylphenyl group, M = Cu, R ³ = H compound)] (m / z = 1645, C ₁₀₈ H ₁₀₆ N ₈ Cu ₂ = 1641) and compound 7 [compound in which R ^{3 of} compound 6 was changed to Cl] (m / z = _1677, the _{C 108 H 105 N 8 Cu 2} Cl = 1675), in 76% respectively yield and 6% was converted.
FIG. 1 shows the structure of the compound 6 by X-ray.
The two porphyrin rings condense to form an average plane displacement (0.029 °) of 25 groups of atoms above and below the average plane, as can be seen from the top and side views of FIG. ) Forms a nearly complete coplanar conformation, forming a compound with two 1.41 ° β-β bonds and one 1.44 ° meso-meso bond.
[0017]
The present inventor has proposed a triple bond Zn ^II -diporphyrin compound 8 [in the general formula (2), R ¹ = phenyl group, R ² = 3,5-t-butylphenyl group, M = Zn, and R ³ = H Compound] was successfully obtained. Said compound 8 shows an average deviation of 0.23 ° and two β-β bonds of 1.44 ° and a meso-meso bond of 1.51 ° (FIG. 2).
The crystal packing of compound 8 is in the form of parallel sheets of alternating porphyrins separated by about 5.44 °. The shape is common in the porphyrin crystals, but is completely different from compound 6.
[0018]
【Example】
Example 1
In a 50 mL round bottle flask, meso-meso-bound Cu ^II- diporphyrin compound 5 (16 mg, 10 μmol) is dispersed and suspended in C ₆ F ₆ (20 mL). The reaction vessel was covered with foil. BAHA (18 mg, 22 μmol) as an oxidizing agent was added portionwise. The mixture is stirred for 2 days at room temperature, and the mixture is diluted with methanol and tetrahydrofuran (THF). The solvent is removed by a rotary evaporator, and the residue is treated with benzene-methanol to precipitate once. The product is finally separated by flash chromatography on a silica gel (Wakogel C-400) column. When treated with a hexane / dichloromethane (CH ₂ Cl ₂ ) extract, the unmodified raw material compound 5 (2 mg, 13%) was used as the first fraction, and the monochlorinated compound 7 (1.0 mg, 6%) and unchlorinated compound 6 (12.2 mg, 76%) as the third fraction.
[0019]
The triple-bonded Cu ^II- diporphyrin compound 6 gives the corresponding Zn ^{II in} a yield of 80% by the steps of demetallation (metal-free) with a mixture of concentrated sulfuric acid and TFA and subsequent insertion of Zn ^II ions. -Converted to diporphyrin compound 8.
The condensed porphyrin has a planar structure forced by a condensed bond, thereby exhibiting a highly delocalized π-electronic characteristic. The condensed porphyrin sequence exhibits more practical properties in terms of application as a second- or third-order nonlinear optical element (NLP) or a molecular wire, which has been extremely limited in the compounds of the porphyrin sequence reported hitherto. Interesting in that respect.
[0020]
result of analysis:
Compound 6:
The molecular weight by MALDI-TOF is MSm / z1866.
Incidentally, the calculated value for C ₁₂₄ H ₁₃₈ N ₈ Cu ₂ is 1865.
UV / Vis (ultraviolet / visible light) absorption characteristics are λm = 411,576, and 996 nm.
Compound 9: ¹ H-NMR (CDCl ₃ ), δ 1.41 (s, 36H, t-Bu), 1.45 (s, 72H, t-Bu), 7.35 (s, 4H, Por-β) ), 7.59 (t, J = 1.8 Hz, 2H, Ar-H), 7.61 (t, J = 1.8 Hz, 4H, Ar-H), 7.63 (d, J = 1. 8 Hz, 4H, Ar-H), 7.67 (d, J = 1.8 Hz, 8H, Ar-H), 7.70 (d, J = 4.9 Hz, 4H, Por-β), and 7. 75 (d, J = 4.9, 4H, Por-β);
The molecular weight by MALDI-TOF is MSm / z 1867.
Incidentally, the calculated value for C ₁₂₄ H ₁₃₈ N ₈ Zn ₂ is 1867.
UV / Vis (ultraviolet / visible light) absorption characteristics are λm = 419.582 and 1068.
[0021]
Example 2
Further, the meso-meso-bonded Cu ^II triporphyrin compound 9 [in the general formula (1), n = 1, R ¹ = phenyl group, R ² = 3,5-t-butylphenyl group, M = Cu] is C ₆ F Oxidation with 4 equivalents of BAHA for 3 days in ₆ gives triporphyrin compound 10 condensed by three bonds
[0022]
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[0023]
[R ¹ = phenyl group, R ² = 3,5-t-butylphenyl group]
Was obtained in a yield of 33%. At that time, compound 9 as a raw material compound was recovered at a recovery rate of 30%.
Condensed triporphyrin compound 10 exhibits a parent molecular peak at m / z = 2383 (calculated for C ₁₅₆ H ₁₅₂ N ₁₂ Cu ₃ 2382) and an extreme red shift Q-band at 1251 nm.
Examining the further properties of compound 10 was difficult due to the very low solubility of the compound.
However, the above results indicate that this oxidative ring closure reaction is a monodisperse [compounds of uniform molecular length. The present inventors have already proposed such a monodisperse compound (Japanese Patent Application No. 2000-23878). ] It can be extended to polymers (including oligomers) meso-meso-bound porphyrin sequences.
[0024]
It is well established that the electronic interaction of the fused diporphyrins of the present invention with multiple bonds is very strong, resulting in a strong red-shifted Q band and a reduced unimolecular oxidation potential.
FIG. 3 shows the absorption spectra of Compounds 1, 2, 9, 10, and 11.
Cu ^II -diporphyrin compound 11 represented by the general formula (3) bonded by two meso βs
[0025]
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[0026]
[R ¹ , R ² and M in the general formula (3) are the same as those in the general formula (1)]
Is shown for comparison.
Meso-meso-bound porphyrin compounds 1 and 9 have been previously reported [A. Osuka, H .; Shimidzu, Angew Chem. 1997, 111, 140; Angew. Chem. Int. Ed. Engl. 1997, 36, 135. T. Ogawa, Y .; Nishimoto, N .; Yoshida, N .; Ono, A .; Osuka, Chem. Commun. 1998, 337. Whereas the triple-linked oligoporphyrin compounds 2 and 11 show characteristic absorption spectra at 411, 576 and 996 nm and at 413, 657 and 1251 nm, respectively.
Although certain of these absorption bands are not, condensation bonds cause a significant perturbation to release the degeneracy of the e _g orbit, causing an enhanced and red shifted Q- band.
The one-electron oxidation potential is 0.69 V for the meso-meso-bound compound 1 as a raw material and 0.47 V for the compound 11, but is reduced to 0.39 V for the compound 2 which is triple-bonded.
Accordingly, the electronic interaction in the triple bond (two β-β carbon bonds and one meso-meso carbon bond) diporphyrin compound 2 is due to the previously reported fused diporphyrins (two meso-β bonds). Extremely strong as compared with the electronic interaction in the condensed compound 11).
[0027]
The effect of the central metal was preliminarily investigated by comparing Cu ^II- diporphyrin compound 6 and Zn ^II- diporphyrin compound 8.
The maximum red-shifted Q-band is observed at 1068 nm in compound 8, is red-shifted by 72 nm from compound 6, and has a meso-meso-bound Zn- ^II diporphyrin compound 12 [in the general formula (1), R ¹ = R ² = 3,5-t-butylphenyl group, compound of M = Zn] (0.54 V), the one-electron oxidation potential of compound 8 is reduced to 0.11 V, and therefore, the Zn- ^II complex larger shift of the potential of the medium, this is a triple bond Zn II ^- suggesting a greater electron interaction in the di-porphyrins.
Due to the extremely strong electronic interaction demonstrated by the low one-electron oxidation potential and the significantly red-shifted enhanced absorption band, triple-bonded porphyrin coordination arrays are quite promising for use as elements of electronic molecular wires. is there.
It is also likely that such synthetic strategies will be extended to larger oligomeric and polymeric porphyrin sequences.
As discussed in the discussion of the effect of the central metal, the electronic interaction of triple bond diporphyrins is dependent on the central metal, which can be seen by introducing various metals into the diporphyrin ligand. Attempts are a very interesting project.
[0028]
【The invention's effect】
As mentioned above, compounds derived from the porphyrin compounds of the present invention have triple bond porphyrin coordination due to the extremely strong electronic interaction demonstrated by the low one-electron oxidation potential and the significantly red-shifted increasing absorption band. The advantage of arrays is that they are quite promising for use as elements of electronic molecular wires.
[Brief description of the drawings]
FIG. 1 X-ray structure of compound 6 [structure viewed from above (top) and structure viewed from side (bottom)]
FIG. 2 X-ray structure of compound 8 [structure viewed from the top (top) and structure viewed from the side (bottom)]
FIG. 3 shows absorption spectra of compounds 2 and 10 of the present invention, starting compounds 1 and 9 and compound 11 condensed by two meso-β bonds. FIG. 4 shows a compound of the present invention, starting compounds and two meso-β bonds Of the modified Cu ^II- diporphyrin compound

Claims (4)

A meso-meso carbon bond in which two or more and three or less porphyrin rings are bonded to each other at each meso-position carbon, and two β-βs at which two β-position carbons adjacent to the meso-position carbon are bonded to each other The following porphyrin ring extends in one direction due to three bonds with carbon bonds. Or a metal-free condensed porphyrin compound in which a metal selected from the group of metal atoms is coordinated.
A. The group of metal atoms is Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ti, Zr. , Hf, V, Nb, Ta, Th, U, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ab, Au, Cd , Hg, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb, and Bi. Among the meso-position carbons of the porphyrin, the meso-position carbons other than the carbon that bonds adjacent porphyrin rings to each other by a meso-meso bond are unsubstituted or substituted by a phenyl group having a substituent at the 3,5-position. The condensed porphyrin compound according to claim 1, wherein: 3. The condensed porphyrin compound according to claim 2, wherein the substituent at the 3,5-position is a tert-butyl group. By oxidizing an oligo or poly (meso-meso-bonded porphyrin) compound in which two or more and three or less porphyrin rings are linked to each other by a meso-positioned carbon and extend in one direction, two or more porphyrin rings adjacent to the meso-meso-bonded carbon are oxidized. The condensed porphyrin compound according to claim 1, 2 or 3, which is obtained by bonding two β-position carbons to each other.

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