Luminescent Indium Dicyanoaurate Coordination Polymers with Short Aurophilic Interactions

IF 4.7 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Pub Date : 2025-04-29 DOI:10.1021/acs.inorgchem.5c00453

Leanna M. Karn, Daniel B. Leznoff

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Abstract

A series of coordination polymers were synthesized by combining In(OTf)₃ (OTf = trifluoromethanesulfonate), 2,2’;6’,2”-terpyridine (Terpy) or its substituted analogues 4’-amino-2,2’;6’,2”-terpyridine (NH₂-Terpy), 4’-chloro-2,2’;6’,2”-terpyridine (Cl-Terpy), and 4’-bromo-2,2’;6’,2”-terpyridine (Br-Terpy), with K[Au(CN)₂]. All compounds consist of 1D chains of hydroxy-bridged [In₂(OH)₂(X-Terpy)₂]⁴⁺ dimers connected to a 1D chain of [Au(CN)₂]⁻ units featuring very short aurophilic interactions (3.0106(3)-3.2155(4) Å). The distance of the aurophilic interaction is directly tunable through minor modifications of the ligand, with the Au(I)···Au(I) distance increasing as the size of the substituent on the Terpy ligand increases. The compounds display photoluminescence emission maxima ranging from 600 to 650 nm, which are significantly lower energy than for most [Au(CN)₂]⁻-based materials. The emission maxima shift to higher energy as the aurophilic interactions become longer. These results demonstrate the ability to tune the Au(I)···Au(I) distance, and in turn the luminescence, by varying the size of the substituent on the chelating ligand.

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具有短亲金作用的发光双氰酸铟配位聚合物

将In(OTf)3 （OTf =三氟甲烷磺酸盐）、2,2′；6′，2”-三联吡啶（Terpy）或其取代的类似物4′-氨基-2,2′；6′，2”-三联吡啶（NH2-Terpy）、4′-氯-2,2′；6′，2”-三联吡啶（Cl-Terpy）和4′-溴-2,2′；6′，2”-三联吡啶（Br-Terpy）与K[Au(CN)2]结合，合成了一系列配位聚合物。所有化合物都是由羟基桥接的[In2(OH)2(X-Terpy)2]4+二聚体的一维链连接到具有非常短亲金相互作用的[Au(CN)2]−单元的一维链组成的(3.0106（3)-3.2155(4)Å）。亲金相互作用的距离可以通过配体的微小修饰直接调节，随着Terpy配体上取代基的大小增加，Au(I)··Au(I)的距离也会增加。该化合物的光致发光最大值在600 ~ 650 nm之间，其能量明显低于大多数[Au(CN)2]−基材料。随着亲金相互作用时间的延长，发射最大值向高能量转移。这些结果表明，通过改变螯合配体上取代基的大小，可以调节Au(I)···Au(I)距离，进而调节发光。

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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.