2,3,9,10,16,17,23·24-Octakis-(9H-carbazol-9-yl) phthalocyaninato zinc(II) (3) and 2,3,9,10,16,17,23·24-octakis-(3,6-di-tert-butyl-9H-carbazole) phthalocyaninato zinc(II) (4) complexes were prepared and characterized by NMR and UV–vis spectroscopies, magnetic circular dichroism (MCD), matrix-assisted laser desorption ionization mass spectrometry, and X-ray crystallography. UV–vis and MCD data are indicative of the interligand charge-transfer nature of the broad band observed in 450–500 nm range for 3 and 4. The redox properties of 3 and 4 were probed by electrochemical and spectro-electrochemical methods, which are suggestive of phthalocyanine-centered first oxidation and reduction processes. Photophysics of 3 and 4 were investigated by steady-state fluorescence and time-resolved transient absorption spectroscopy demonstrating the influence of the carbazole substituents on deactivation from the first excited state in 3 and 4. Protonation of the meso-nitrogen atoms in 3 results in much faster deactivation kinetics from the first excited state. Spectroscopic data were correlated with density functional theory (DFT) and time-dependent DFT calculations on 3 and 4.

中文翻译：

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溶剂变色和电致变色锌八（咔唑基）酞菁中分子内电荷转移性质的评估

2,3,9,10,16,17,23·24-Octakis-（9 H-咔唑-9-基）酞菁锌（II）（3）和2,3,9,10,16,17,23 ·制备了24辛基-（3,6-二叔丁基-9 H-咔唑）酞菁锌（II）（4）配合物，并通过NMR和UV-可见光谱，磁性圆二色性（MCD），基质进行了表征辅助激光解吸电离质谱和X射线晶体学。UV-vis和MCD数据表明在450和500 nm范围内3和4观察到的宽带的配体电荷转移性质。3和4的氧化还原特性用电化学和光谱电化学方法进行了探测，这表明以酞菁为中心的第一氧化和还原过程。通过稳态荧光和时间分辨瞬态吸收光谱法研究了3和4的光物理性质，证明了咔唑取代基对3和4中第一个激发态失活的影响。所述的质子化的内消旋在-氮原子3分在从所述第一激发态快得多失活动力学的结果。光谱数据与密度泛函理论（DFT）以及与时间有关的DFT计算在3和4上相关。