Donor-acceptor type A2B2 porphyrins: synthesis, energy transfer, computational and electro- chemical studies
Donor-acceptor type A2B2 porphyrins: synthesis, energy transfer, computational and electro- chemical studies
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A2B2 型供体-受体型卟啉：合成、能量转移、计算和电化学研究
DOI：
10.1039/c6qi00558f
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发表时间：
2017
影响因子：
7
通讯作者：
Shigeki Mori and Iti Gupta
中科院分区：
文献类型：
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作者：
Sudipta Das;Haamid R. Bhat;Naresh Balsukuri;Prakash C. Jha;Yutaka Hisamune;Masatoshi Ishida;Hiroyuki Furuta;Shigeki Mori and Iti Gupta
合成了一系列给体-受体型反式-A_2B_2卟啉及其Zn（Ⅱ）和Pd（Ⅱ）配合物5-13，并通过各种光谱技术进行了表征。供体部分（例如，N-丁基咔唑、N-丁基吩噻嗪和三苯胺）对卟啉光谱性质的影响。结构的变化确实影响了这些卟啉的光学和电化学性质。较高的能量位移的Soret带观察卟啉后，不同的供体部分。所有的衍生物的电化学研究表明，供体基团和卟啉核之间的相互作用增加，这反过来又反映在其还原电位的阳极位移。稳态和时间分辨荧光研究都揭示了从卟啉5-10中的供体基团到卟啉核心的有效能量转移（EET;高达87%）。钯（II）卟啉配合物11-13在近红外区显示出特征磷光。密度泛函理论（DFT）研究支持卟啉核和meso-取代基之间存在给体-受体相互作用。密度泛函理论（DFT）和含时密度泛函理论（TD-DFT）研究表明，5、8和11的吸收跃迁为π → π* 型，而6、7、9、10、12和13的最高吸收跃迁均涉及分子内电荷转移（ICT）.
A series of donor–acceptor type trans-A2B2 porphyrins and their Zn(II) and Pd(II) complexes 5–13 have been synthesized and characterized by various spectroscopic techniques. The effect of the donor moieties (e.g., N-butylcarbazole, N-butylphenothiazine, and triphenylamine) on the spectroscopic properties of the porphyrins has been studied. The structural changes indeed affected the optical and electrochemical properties of these porphyrins. Higher energy shifts of the Soret bands were observed for porphyrins upon varying the donor moieties. The electrochemical studies of all the derivatives indicated increased interactions between the donor groups and the porphyrin core, which in turn are reflected in the anodic shifts in their reduction potentials. Both steady-state and time-resolved fluorescence studies revealed effective energy transfer (EET; up to 87%) from donor groups to the porphyrin core in the porphyrins, 5–10. The palladium(II) porphyrin complexes, 11–13, showed characteristic phosphorescence in the near IR region. Density functional theory (DFT) studies support the presence of donor–acceptor interaction between the porphyrin core and the meso-substituents in the dyads. Density functional theory (DFT) and time dependent-density functional theory (TD-DFT) studies showed that in 5, 8 and 11, the transitions are of π → π* type; whereas in the other molecules viz.6, 7, 9, 10, 12 and 13 intramolecular charge transfer (ICT) is involved in all the respective highest intensity absorption transitions.