Solvent-driven tuning of the emission properties of dinuclear Cu(I) and Ag(I) pyrazolate-phosphine complexes

IF 5.4 3区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Communications Pub Date : 2025-09-22 DOI:10.1016/j.inoche.2025.115539

Arina P. Olbrykh , Vladislav M. Korshunov , Andrey Yu. Baranov , Alexander S. Goloveshkin , Alexander F. Smol'yakov , Nikita S. Kurochkin , Ilya V. Taydakov , Alexander V. Artem'ev , Oleg A. Filippov , Aleksei A. Titov , Elena S. Shubina

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Abstract

The reaction of cyclic trinuclear copper(I) and silver(I) pyrazolates [MPz]₃ (Pz = 3,5-(CF₃)₂ Pz) with tris(2-pyridyl)phosphine (Py₃P) in a 1:3 stoichiometric ratio in toluene (one phosphorus per metal center) results in the precipitation of binuclear complexes with the general formula [MPz(Py₃P)]₂: 1 (M = Cu), 2 (M = Ag) afforded solvent-incorporated analogues Subsequent crystallization from dichloromethane (DCM) afforded solvent-incorporated analogues: 3 (M = Cu), 4 (M = Ag). Structural analysis reveals fundamentally different solvent interactions: while DCM forms stabilizing CH-π hydrogen bonds in the Cu(I) complex 3 with minimal structural perturbation, the Ag(I) analogue 4 undergoes rapid solvent loss upon air exposure, accompanied by crystal degradation. Notably, the solvated silver(I) complex exhibits a shorter intramolecular Ag┄Ag distance (ca. 0.2 Å) compared to its non-solvated counterpart. All synthesized complexes shows metal- and solvent-dependent luminescence, with 1–3 demonstrating phosphorescence, while complex 4 demonstrates emission typical of thermally activated delayed fluorescence behavior (TADF). These findings underscore the pronounced influence of metal identity and solvent interactions on both structural and photophysical properties in this class of compounds.

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双核铜(I)和银(I)吡唑酸-膦配合物发射性质的溶剂驱动调谐

环三核铜(I)和银(I)吡唑酸盐[MPz]3 （Pz = 3,5-(CF3)2 Pz）与三（2-吡啶基）膦（Py3P）在甲苯中以1:3的化学计量比（每个金属中心一个磷）反应，得到双核配合物，其分子式为[MPz(Py3P)] 2:1 (M = Cu), 2 (M = Ag)，得到溶剂溶出类似物。二氯甲烷（DCM）结晶得到溶剂溶出类似物：3 (M = Cu), 4 （M = Ag）。结构分析揭示了根本不同的溶剂相互作用：DCM在Cu(I)配合物3中以最小的结构扰动形成稳定的CH-π氢键，而Ag(I)类似物4在暴露于空气中时会迅速失去溶剂，并伴有晶体降解。值得注意的是，与非溶剂化的银配合物相比，溶剂化的银(I)配合物表现出更短的分子内Ag的距离（约0.2 Å）。所有合成的配合物都表现出金属和溶剂依赖性发光，其中1-3表现出磷光，而配合物4表现出典型的热激活延迟荧光行为（TADF）。这些发现强调了金属特性和溶剂相互作用对这类化合物的结构和光物理性质的显著影响。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Inorganic Chemistry Communications 化学-无机化学与核化学

CiteScore

5.50

自引率

7.90%

发文量

1013

审稿时长

53 days

期刊介绍： Launched in January 1998, Inorganic Chemistry Communications is an international journal dedicated to the rapid publication of short communications in the major areas of inorganic, organometallic and supramolecular chemistry. Topics include synthetic and reaction chemistry, kinetics and mechanisms of reactions, bioinorganic chemistry, photochemistry and the use of metal and organometallic compounds in stoichiometric and catalytic synthesis or organic compounds.