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首页> 外文期刊>Chemistry: A European journal >A p-Quinodimethane-Bridged Porphyrin Dimer
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A p-Quinodimethane-Bridged Porphyrin Dimer

机译：对喹啉甲烷桥连卟啉二聚体

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摘要

A p-quinodimethane (p-QDM)-bridged porphyrin dimer 1 has been prepared for the first time. An unexpected Michael addition reaction took place when we attempted to synthesize compound 1 by reaction of the cross-conjugated keto-linked porphyrin dimers 8a and 8b with alkynyl/aryl Grignard reagents. Alternatively, compound 1 could be successfully prepared by intramolecular Friedel-Crafts alkyl-ation of the diol-linked porphyrin dimer 14 with concomitant oxidation in air. Compound 1 shows intense onephoton absorption (OPA, λ_(max)= 955 nm, ε=45400m~(-1)cm~(-1)) and a large two-photon absorption (TPA) crosssection (σ_(max)~((2))=2080 GM at 1800 nm) in the near-infrared (NIR) region due to its extended p-conjugation and quinoidal character. It also exhibits a short singlet excited-state lifetime of 25 ps. The cyclic voltammogram of 1 displays multiple redox waves with a small electrochemical energy gap of 0.86 eV. The ground-state geometry, electronic structure, and optical properties of 1 have been further studied by density functional theory (DFT) calculations and compared with those of the keto-linked dimer 8b. This research has revealed that incorporation of a p-QDM unit into the porphyrin framework had a significant impact on its optical and electronic properties, leading to a novel NIR OPA and TPA chromophore.
机译：首次制备了对喹啉二甲烷（p-QDM）桥连卟啉二聚体1。当我们试图通过交联的酮基连接的卟啉二聚体8a和8b与炔基/芳基格氏试剂反应来合成化合物1时，发生了意想不到的迈克尔加成反应。或者，化合物1可以通过使二醇连接的卟啉二聚体14进行分子内的Friedel-Crafts烷基化并伴随在空气中氧化而成功制备。化合物1表现出强烈的单光子吸收（OPA，λ_（max）= 955 nm，ε= 45400m〜（-1）cm〜（-1））和大的两光子吸收（TPA）截面（σ_（max）〜（ （2））由于其扩展的p共轭和喹啉特性，因此在近红外（NIR）区域中的1800 nm处的2080 GM）。它还具有25 ps的短单重态激发态寿命。 1的循环伏安图显示多个氧化还原波，其电化学能隙为0.86 eV。 1的基态几何，电子结构和光学性质已通过密度泛函理论（DFT）计算得到了进一步研究，并与酮基连接的二聚体8b进行了比较。这项研究表明，将p-QDM单元并入卟啉骨架对其光学和电子性质产生了重大影响，从而产生了一种新型的NIR OPA和TPA发色团。

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