Organo Chalcogenone-Triggered Luminescent Copper(I) Clusters for Light Emitting Applications

IF 4.3 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Inorganic Chemistry Pub Date : 2024-06-29 DOI:10.1021/acs.inorgchem.3c04637

Sabari Veerapathiran, Gopendra Muduli, Arushi Rawat, Kumar Siddhant, Joginder Singh, Kohsuke Matsumoto, Osamu Tsutsumi* and Ganesan Prabusankar*,

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Abstract

A novel organo sulfur and selenium-controlled emission behavior in discrete copper(I) clusters has been demonstrated for the first time. The pentanuclear [Cu₅Br₅(L¹)₂] (1), trinuclear [Cu₃Br₃(L²)₂] (2), dinuclear [Cu₂I₂(L¹)₂] (3), and tetranuclear [Cu₄I₄(L²)₂CH₃CN] (4) copper(I) discrete clusters have been synthesized from the reaction between L¹ [L¹ = 1-isopropyl-3-(pyridin-2-yl)-imidazol-2-thione] or L² [L² = 1-isopropyl-3-(pyridin-2-yl)-imidazol-2-selone] chelating ligands and corresponding copper(I) halide salts. These new clusters have been characterized by FT-IR, UV–visible, thermogravimetric analysis, and fluorescence spectroscopy techniques. Single-crystal X-ray diffraction studies reveal that 1–4 consists of abundant d¹⁰–d¹⁰ interactions. The structural and bonding features of clusters have been investigated using density functional theory calculations. Notably, the L²-ligated 2 and 4 are poorly emissive, while L¹-ligated 1 and 3 showed strong emission in the orange and green regions, respectively. The time-dependent density functional theory natural transition orbital calculations of 1 and 3 reveal the nature of the transitions contributed by ³MLCT/³LLCT/³ILCT. Photoluminescence quantum yields of 1 and 3 are 19 and 11%, with average lifetimes of 21.55 and 6.57 μs, respectively. 1 and 3 were coated on prototype LED bulbs for light-emitting performance.

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用于发光应用的有机卤化酮触发发光铜(I)团簇

首次证明了离散铜（I）团簇中由有机硫和硒控制的新型发射行为。五核 [Cu5Br5(L1)2] (1)、三核 [Cu3Br3(L2)2] (2)、双核 [Cu2I2(L1)2] (3)、L1 [L1 = 1-isopropyl-3-(pyridin-2-yl)-imidazol-2-thione] 或 L2 [L2 = 1-isopropyl-3-(pyridin-2-yl)-imidazol-2-selone] 螯合配体与相应的铜（I）卤化物盐反应合成了四核 [Cu4I4(L2)2CH3CN] (4) 离散铜（I）簇。这些新的簇合物已通过傅立叶变换红外光谱、紫外-可见光谱、热重分析和荧光光谱技术进行了表征。单晶 X 射线衍射研究表明，1-4 包含丰富的 d10-d10 相互作用。利用密度泛函理论计算研究了簇合物的结构和成键特征。值得注意的是，L2 配位的 2 和 4 辐射较弱，而 L1 配位的 1 和 3 则分别在橙色和绿色区域显示出较强的辐射。对 1 和 3 进行的随时间变化的密度泛函理论自然过渡轨道计算揭示了 3MLCT/3LLCT/3ILCT 所促成的过渡的性质。1 和 3 的光量子产率分别为 19% 和 11%，平均寿命分别为 21.55 μs 和 6.57 μs。1 和 3 被涂覆在原型 LED 灯泡上，以提高发光性能。

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来源期刊

Inorganic Chemistry 化学-无机化学与核化学

CiteScore

7.60

自引率

13.00%

发文量

1960

审稿时长

1.9 months

期刊介绍： Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.