Premium
Synthesis of the Single‐Crystalline Form and First‐Principles Calculations of Photomagnetic Copper(II) Octacyanidomolybdate(IV)
Author(s) -
Umeta Yoshikazu,
Chorazy Szymon,
Nakabayashi Koji,
Ohkoshi Shinichi
Publication year - 2016
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201500823
Subject(s) - chemistry , tetragonal crystal system , copper , crystallography , ion , single crystal , absorption (acoustics) , crystal structure , anisotropy , absorption band , square pyramidal molecular geometry , optics , organic chemistry , physics
A gel crystallization technique was successfully applied in the pioneering preparation of a single‐crystalline form of the three‐dimensional copper(II) octacyanidomolybdate(IV) network, which is a photomagnetic material. This assembly crystallizes with the formula {[Cu II (H 2 O)] 2 [Mo IV (CN) 8 ]} · 2H 2 O in the tetragonal crystal system and reveals a three‐dimensional cyanido‐bridged framework constructed of five‐coordinate square‐pyramidal [Cu II (H 2 O)(NC) 4 ] 2– complexes and [Mo IV (CN) 8 ] 4– ions of square‐antiprismatic geometry. First‐principles calculations by the GGA + U method indicate that the visible‐light absorption band, crucial for the observation of a photomagnetic effect, is interpreted in terms of Mo IV to Cu II charge transfer, which is enabled owing to the accompanying p z → sp x transition of the nitrogen atoms of the bridging cyanido ligands. The optical transitions in the visible range are anisotropic, and the most efficient light absorption along the [111] direction corresponds to the alignment of the cyanide bridges.