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四核铜(I)-吡唑酸盐大环化合物的刚性变色:三氟甲基的空间拥挤效应

Rigidochromism of tetranuclear Cu(I)-pyrazolate macrocycles: steric crowding with trifluoromethyl groups.

作者信息

Rajagopal Shinaj K, Zeller Matthias, Savikhin Sergei, Slipchenko Lyudmila V, Wei Alexander

机构信息

James and Margaret Tarpo Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, USA.

Department of Physics and Astronomy, Purdue University, West Lafayette, Indiana 47907, USA.

出版信息

Chem Commun (Camb). 2024 Oct 3;60(80):11307-11310. doi: 10.1039/d4cc04259j.

Abstract

Macrocyclic Cu(I)-pyrazolate tetramers (Cupz) can fold into compact structures with luminescent Cu cores whose emission wavelengths are sensitive to steric effects along the periphery of the macrocycle. Introducing CF at the C4 position of 3,5-di-Bu-pyrazolate increases steric crowding that modifies the conformational behavior of the Cupz complex, highlighted by a low-temperature martensitic transition. Variable-temperature analysis of solid-state luminescence reveal an unexpected blueshifting of emission with rising temperature.

摘要

大环铜(I)-吡唑酸盐四聚体(Cupz)可以折叠成具有发光铜核的紧密结构,其发射波长对大环外围的空间效应敏感。在3,5-二丁基吡唑酸盐的C4位置引入CF会增加空间拥挤,从而改变Cupz配合物的构象行为,低温马氏体转变突出了这一点。固态发光的变温分析显示,随着温度升高,发射出现意外的蓝移。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/de0d/11513227/00527b0349da/nihms-2029091-f0001.jpg

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