Switching Between Giant Positive and Negative Thermal Expansions of a YFe(CN)6‐based Prussian Blue Analogue Induced by Guest Species. (23rd June 2017)

• Record Type: Journal Article
• Authors: Gao, Qilong; Chen, Jun; Sun, Qiang; Chang, Dahu; Huang, Qingzhen; Wu, Hui; Sanson, Andrea; Milazzo, Ruggero; Zhu, He; Li, Qiang; Liu, Zhanning; Deng, Jinxia; Xing, Xianran
• Is Part Of: Angewandte Chemie. Volume 129:Number 31(2017)
• Page Start: 9151
• Page End: 9156
• Publication Date: 2017-06-23
• Subjects: Dichtefunktionaltheorie -- Gitterschwingungen -- Kristallstrukturen -- Negative thermische Ausdehnung -- Preußischblau-Analoga; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201702955
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: The control of thermal expansion of solid compounds is intriguing but remains challenging. The effect of guests on the thermal expansion of open‐framework structures was investigated. Notably, the presence of guest ions (K + ) and molecules (H2 O) can substantially switch thermal expansion of YFe(CN)6 from negative ( α v =−33.67×10 −6 K −1 ) to positive ( α v =+42.72×10 −6 K −1 )—a range that covers the thermal expansion of most inorganic compounds. The mechanism of such substantial thermal expansion switching is revealed by joint studies with synchrotron X‐ray diffraction, X‐ray absorption fine structure, neutron powder diffraction, and density functional theory calculations. The presence of guest ions or molecules plays a critical damping effect on transverse vibrations, thus inhibiting negative thermal expansion. An effective method is demonstrated to control the thermal expansion in open‐framework materials by adjusting the presence of guests.