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DFT study of mixed‐valent Mn(II/III) hexacyanide clusters
Author(s) -
Daul Claude,
Rauzy Cédrick,
Decurtins Silvio,
Franz Patrick,
Hauser Andreas
Publication year - 2004
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.20333
Subject(s) - chemistry , density functional theory , crystallography , cyanide , prussian blue , ion , crystal structure , linkage isomerism , manganese , single crystal , transition metal , quantum chemical , computational chemistry , inorganic chemistry , molecule , metal , catalysis , biochemistry , organic chemistry , electrode , electrochemistry
The cubic Prussian blue analogue Mn 3 [Mn(CN) 6 ] 2 · 15 H 2 O, which has the advantage of being transparent and magnetic ( T N = 35 K) at the same time, has been investigated by density functional theory (DFT) calculations. The three‐dimensional structure is built of Mn II ions linked to Mn III ions by μ‐bridging cyanides, to form a crystal structure, which is related to the NaCl type. In a first step, the relative stabilities of the mononuclear complexes [Mn(CN) 6 ] z− ( z = 2 to 4) have been studied as a function of the oxidation state, spin configuration, and the linkage isomerism of the cyanide ligand. The results we have obtained by this investigation are in good agreement with our chemical expertise. In addition, the calculations have been extended to the dinuclear [Mn 2 (CN) 11 ] z− ( z = 5 and 6) clusters. Furthermore, we used DFT to model the magnetic properties as well as the 3 T 1 → 1 T 2 transition, which has been observed by single‐crystal near‐IR spectra of Mn 3 [Mn(CN) 6 ] 2 · 15 H 2 O. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005