π-Conjugation modification of photochromic and redox-active dimethyldihydropyrene by phenyland ethynyl-terpyridines and Ru(bis-terpyridine)complexes
π-Conjugation modification of photochromic and redox-active dimethyldihydropyrene by phenyland ethynyl-terpyridines and Ru(bis-terpyridine)complexes
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苯基和乙炔基三联吡啶和 Ru(双三联吡啶)配合物对光致变色和氧化还原活性二甲基二氢芘的 π 共轭修饰
DOI：
10.1039/c4nj01462f
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发表时间：
2014
期刊：
影响因子：
--
通讯作者：
Hiroshi Nishihara
中科院分区：
文献类型：
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作者：
Satoshi Muratsugu;Hiroshi Nishihara
合成了两个π-共轭的二甲基二氢芘（DHP）-双三联吡啶配体（2和3），其中两个三联吡啶部分分别通过苯基和乙炔基连接在DHP（1）的4和9位上。π-共轭连接基的性质影响DHP部分的价轨道，这使DHP部分的氧化还原电位和吸收光谱移动。在3中，与乙炔基连接体相比，DHP部分的氧化还原电位在正方向上移动，并且吸收带大幅红移。在2与苯基接头，位移的DHP部分的氧化还原电位和吸收带是温和的。这些结果得到了支持的价轨道能量计算使用含时密度泛函理论，这使得在每个光谱中的四个主要跃迁的第一次分配。化合物3的荧光强度大于化合物2，具有光致异构性。以2和3为原料合成了两个双核钌（双三联吡啶）配合物（4和5），研究了它们的氧化还原性质和光化学性质。
Two π-conjugated dimethyldihydropyrene (DHP)-bis-terpyridine ligands (2 and 3) were prepared, in which two terpyridine moieties were connected at the 4 and 9 positions of DHP (1) via phenyl and ethynyl linkers, respectively. The nature of the π-conjugated linkers influenced the valence orbitals of the DHP moiety, which shifted the redox potentials of the DHP moiety and the absorption spectra. In 3 with an ethynyl linker, the redox potentials of the DHP moiety were shifted in the positive direction and the absorption band was largely red-shifted compared with 1. In 2 with a phenyl linker, the shifts in the redox potentials of the DHP moiety and in the absorption band were moderate. These results were supported by valence orbital energies calculated using time-dependent density functional theory, which enabled the assignment of the four main transitions in each spectrum for the first time. The fluorescence intensity of 3 was larger than that of 2, which was photoisomerisable. Two dinuclear Ru(bis-terpyridine) complexes (4 and 5) were prepared from 2 and 3, and their redox and photochemical properties were investigated.