Structure-property relationships and the mechanisms of multistep transitions in spin crossover materials and frameworks

被引:52
作者
Cruddas, Jace [1 ]
Powell, Ben J. [1 ]
机构
[1] Univ Queensland, Sch Math & Phys, Brisbane, Qld 4072, Australia
基金
澳大利亚研究理事会;
关键词
ISING-LIKE MODEL; STATE TRANSITION; 2-STEP; BEHAVIOR; COMPLEX; HYSTERESIS; STEP; POLYMORPHISM; COMPOUND; PHASES;
D O I
10.1039/d0qi00799d
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Spin crossover frameworks and molecular crystals display fascinating collective behaviours. This includes multi-step transitions with hysteresis and a wide variety of long-range ordered patterns of high-spin and low-spin metal centres. From both practical and fundamental perspectives it is important to understand the mechanisms behind these collective behaviours. We study a simple model of elastic interactions and identify thirty six different spin-state ordered phases. We observe spin-state transitions with between one and eight steps. These include both sharp transitions and crossovers, and both complete and incomplete spin crossover. We demonstrate structure-property relationships that explain these differences. These arise because through-bond interactions are antiferroelastic (favour metal centres with different spin-states); whereas, through-space interactions are typically ferroelastic (favour the same spin-state). In general, rigid materials with longer range elastic interactions lead to transitions with more steps and more diverse spin-state ordering, which explains why both are prominent in frameworks.
引用
收藏
页码:4424 / 4437
页数:14
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