发光混合铜（I）/铜（II）氰化物配位聚合物的振动-结构联合研究,European Journal of Inorganic Chemistry

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发光混合铜（I）/铜（II）氰化物配位聚合物的振动-结构联合研究
European Journal of Inorganic Chemistry ( IF 2.2 ) Pub Date : 2016-05-17 , DOI: 10.1002/ejic.201600124
Francesca Grifasi ₁ , Emanuele Priola _{1,

2} , Michele R. Chierotti ₁ , Eliano Diana _{1,

2} , Claudio Garino ₁ , Roberto Gobetto ₁

Affiliation

在此，我们报告了一系列具有不同晶体堆积和电子特性的 CuCN 基配位聚合物的表征，即 [Na2Cu(CN)3·3H2O]n (1)、[Cu4(CN)5(NH3)2 (H2O)]n (2), [Cu3(CN)4(NH3)3]n (3), [Cu3(CN)3(O)0.25(NH3)]n (4), [Cu5(CN)6 (NH3)4]n (5) 和 [Cu5(CN)6(NH3)2]n (6)。提供了存在与金属中心配位的氨分子的光谱证据，特别是对于 4，这是一种新结构。已通过单晶 XRD (SCXRD)、显微红外光谱、显微拉曼光谱、差示扫描量热法 (DSC) 和热重分析 (TGA) 进行表征。通过获取发射和激发光谱并评估发射量子产率，通过固态发光光谱研究了光物理特性，这是一种最近在固态领域变得越来越重要的方法。这项工作的目标是 (1) 阐明发光特性与 CuI 或混合 CuI/CuII 氧化态的存在之间的相关性，(2) 评估聚合物中 NH3、H2O 或两者的存在。结合晶体学 - 光谱研究，以及（3）合理化超分子结构及其对产生的发光的影响。

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Vibrational-Structural Combined Study into Luminescent Mixed Copper(I)/Copper(II) Cyanide Coordination Polymers

Herein, we report the characterization of a series of CuCN-based coordination polymers that display different crystal packing and electronic properties, namely, [Na2Cu(CN)3·3H2O]n (1), [Cu4(CN)5(NH3)2(H2O)]n (2), [Cu3(CN)4(NH3)3]n (3), [Cu3(CN)3(O)0.25(NH3)]n (4), [Cu5(CN)6(NH3)4]n (5), and [Cu5(CN)6(NH3)2]n (6). Spectroscopic evidence of the presence of ammonia molecules coordinated to the metal centers is provided, in particular for 4, which is a new structure. The characterization has been performed by single-crystal XRD (SCXRD), micro- IR spectroscopy, micro-Raman spectroscopy, differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). The photophysical properties have been studied through solid-state luminescence spectroscopy by acquiring the emission and excitation spectra and evaluating the emission quantum yields, which is an approach that has recently grown in importance in the solid-state field. The goals of this work are (1) to elucidate the correlation between the luminescence properties and the presence of either CuI or mixed CuI/CuII oxidation states, (2) to evaluate the presence of NH3, H2O, or both in the polymers through a combined crystallographic–spectroscopic study, and (3) to rationalize the supramolecular architecture and its influence on the resulting luminescence.

更新日期：2016-05-17

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