Controlling AxMn[Fe(CN)6] charge transfer pathways through tilt-engineering for enhanced metal-to-metal interactions

被引：1
|
作者：
Regueiro, A. [1 ]
Castells-Gil, J. [2 ]
Shen, C. [3 ]
Mikulska, I. [4 ]
Allen, C. [3 ,5 ]
Bogani, L. [3 ]
Torres-Cavanillas, R. [1 ,3 ]
机构：
[1] Univ Valencia, Inst Ciencia Mol, Catedrat Jose Beltran 2, Paterna 46980, Spain
[2] Univ Birmingham, Sch Chem, Birmingham B15 2TT, England
[3] Univ Oxford, Dept Mat, 21 Banbury Rd, Oxford OX2 6NN, England
[4] Diamond Light Source, Didcot OX11 0DE, Oxon, England
[5] Electron Phys Sci Imaging Ctr, Diamond Light Source, Didcot OX11 0DE, England
来源：
MATERIALS ADVANCES | 2024年 / 5卷 / 18期
关键词：
TRANSFER PHASE-TRANSITION; THERMAL HYSTERESIS LOOP; ELECTRON-TRANSFER; OXIDATION-STATES; SPECTROSCOPY; COMPLEX;
D O I：
10.1039/d4ma00262h
中图分类号：
T [工业技术];
学科分类号：
08 ;
摘要：
The induction of structural distortion in a controlled manner through tilt engineering has emerged as a potent method to finely tune the physical characteristics of Prussian blue analogues. Notably, this distortion can be chemically induced by filling their pores with cations that can interact with the cyanide ligands. With this objective in mind, we optimized the synthetic protocol to produce the stimuli-responsive Prussian blue analogue A(x)Mn[Fe(CN)(6)] with A = K+, Rb+, and Cs+, to tune its stimuli-responsive behavior by exchanging the cation inside pores. Our crystallographic analyses reveal that the smaller the cation, the more pronounced the structural distortion, with a notable 20-degree Fe-CN tilting when filling the cavities with K+, 10 degrees with Rb+, and 2 degrees with Cs+. Moreover, this controlled distortion offers a means to switch on/off its stimuli-responsive behavior, while modifying its magnetic response. Thereby empowering the manipulation of the PBA's physical properties through cationic exchange
引用
收藏
页码：7473 / 7480
页数：8
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