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首页> 外文期刊>Polyhedron: The International Journal for Inorganic and Organometallic Chemistry >A novel complex of zinc tetraphenylporphyrin with two dioxane molecules in a rare attachment. Crystal structure, spectroscopy and theoretical calculations
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A novel complex of zinc tetraphenylporphyrin with two dioxane molecules in a rare attachment. Crystal structure, spectroscopy and theoretical calculations

机译：一种新颖的四苯基卟啉锌与两个二恶烷分子的罕见复合物。晶体结构，光谱学和理论计算

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摘要

We have shown the X-ray crystal structure of a novel ZnTPP-(Dioxane) _2 complex and the results of solution studies by means of steady state absorption and fluorescence as well as time-resolved fluorescence techniques complemented by theoretical DFT and TD DFT B3LYP/6-31G(d,p) calculations. The ZnTPP-(Dioxane)_2 crystallizes in centrosymmetric monoclinic unit cell, space group P21/c and shows a unique structure, with two dioxane molecules in "chair" conformation, placed in equatorial and axial position relative to ZnTPP core. Analysis of TD DFT B3LYP/6-31G(d,p) wave functions of ZnTPP-(Dioxane)_2, allowed us to describe the nature of particular electronic transitions and to identify two bands (LE, CT) absent in its components. The former, results from the symmetry reduction of ZnTPP and the latter, from a mixed character of the HOMO (220) orbital of the complex. A red shift of the Soret and the Q band found in absorption and fluorescence spectra indicating the complex formation in solution is confirmed by the simulated absorption spectra of ZnTPP-(Dioxane)_2 relative to ZnTPP unit both in the gas phase and in dioxane solution by PCM model. The estimated lifetime of the complex (1.75 ns) is shorter than that of free ZnTPP unit (～2 ns).
机译：我们已经显示了新型ZnTPP-（Dioxane）_2配合物的X射线晶体结构，以及通过稳态吸收和荧光以及时间分辨荧光技术和理论DFT和TD DFT B3LYP /互补的溶液研究的结果。 6-31G（d，p）计算。 ZnTPP-（二恶烷）_2在中心对称的单斜晶胞，空间群P21 / c中结晶，并显示出独特的结构，其中两个二恶烷分子呈“椅子”构型，相对于ZnTPP核心位于赤道和轴向位置。分析ZnTPP-（Dioxane）_2的TD DFT B3LYP / 6-31G（d，p）波函数，使我们能够描述特定电子跃迁的性质并确定其成分中不存在的两个谱带（LE，CT）。前者是由于ZnTPP的对称还原而引起的，后者是由于配合物的HOMO（220）轨道的混合特性所致。 ZnTPP-（Dioxane）_2在气相和二恶烷溶液中相对于ZnTPP单元的模拟吸收光谱证实了Soret和在吸收光谱和荧光光谱中发现的Q谱带的红移，表明溶液中有络合物形成。 PCM模型。复合物的估计寿命（1.75 ns）比游离ZnTPP单元的寿命（〜2 ns）短。

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