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三齿铁(III)席夫碱化合物中的动态自旋交换

Dynamic spin interchange in a tridentate Fe(iii) Schiff-base compound.

作者信息

Vicente Ana I, Joseph Abhinav, Ferreira Liliana P, de Deus Carvalho Maria, Rodrigues Vítor H N, Duttine Mathieu, Diogo Hermínio P, Minas da Piedade Manuel E, Calhorda Maria José, Martinho Paulo N

机构信息

Centro de Química e Bioquímica , Faculdade de Ciências , Universidade de Lisboa , Campo Grande , 1749-016 Lisboa , Portugal . Email:

BioISI , Faculdade de Ciências , Universidade de Lisboa , Campo Grande , 1749-016 Lisboa , Portugal.

出版信息

Chem Sci. 2016 Jul 1;7(7):4251-4258. doi: 10.1039/c5sc04577k. Epub 2016 Mar 17.

Abstract

The thermosalient effect is still a rare and poorly understood phenomenon, where crystals suddenly jump, bend, twist or explode upon undergoing a thermally activated phase transition. The synthesis and characterisation of the new spin transition Fe(iii) compound [Fe(5-Br-salEen)][ClO] (salEen = -ethyl--(2-aminoethyl)salicylaldiminate) is described and its thermosalient behaviour reported. It is the first example of a thermosalient effect with a spin transition and magnetic, calorimetric, diffraction, microscopy and computational studies are used to characterise these effects. Both thermosalient effect and spin transition occur around 320 K upon heating and are accompanied by an anisotropic unit cell change with conservation of crystal symmetry that causes a large enough stress of the crystal lattice to induce crystal explosion. This stress can ultimately be traced back to a diffusionless and distortive structural perturbation resulting in a coupled spin transition-thermosalient effect.

摘要

热致跃变效应仍然是一种罕见且鲜为人知的现象,在这种现象中,晶体在经历热激活相变时会突然跳跃、弯曲、扭曲或爆炸。本文描述了新型自旋转变铁(III)化合物[Fe(5-Br-salEen)][ClO](salEen = -乙基--(2-氨基乙基)水杨醛亚胺)的合成与表征,并报道了其热致跃变行为。这是具有自旋转变的热致跃变效应的首个实例,利用磁性、量热、衍射、显微镜和计算研究对这些效应进行了表征。加热时,热致跃变效应和自旋转变均在320 K左右发生,并伴随着各向异性晶胞变化,同时晶体对称性保持不变,这会导致晶格产生足够大的应力从而引发晶体爆炸。这种应力最终可追溯到一种无扩散且有畸变的结构微扰,从而导致了自旋转变 - 热致跃变效应的耦合。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6f8a/6013817/50723df18427/c5sc04577k-f1.jpg

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