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Synthesis and Crystal Structure of the Azide K 4 [Re 6 Se i 8 (N 3 ) a 6 ]·4H 2 O; Luminescence, Redox, and DFT Investigations of the [Re 6 Se i 8 (N 3 ) a 6 ] 4– Cluster Unit
Author(s) -
Gandubert Aurore,
Brylev Konstantin A.,
Thuong Nguyen Thi,
Naumov Nikolai G.,
Kitamura Noboru,
Molard Yann,
Gautier Régis,
Cordier Stéphane
Publication year - 2013
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201300151
Subject(s) - acetonitrile , azide , crystallography , chemistry , luminescence , crystal structure , bond length , solid state , cluster (spacecraft) , unit (ring theory) , physics , mathematics , optics , programming language , mathematics education , organic chemistry , chromatography , computer science
The reaction of K 4 [Re 6 Se i 8 (OH) a 6 ] · 8H 2 O with NaN 3 in water results in the formation of [Re 6 Se i 8 (N 3 ) a ] 4– units that crystallize with K + and H 2 O to form K 4 [Re 6 Se i 8 (N 3 ) a 6 ] · 4H 2 O [ P 2 1 / c (N°14), a = 9.0595(3) Å, b = 13.2457(4) Å, c = 13.2040(5) Å, β = 94.472(1)°]. In the solid state, the unit is characterized by N 3 linear groups forming bond angles of roughly 120° with the Re 6 cluster. The positions of the ν as and ν sy bands as well as N–N–N deformation modes of the N 3 groups are discussed. Luminescence properties of the [Re 6 Se i 8 (N 3 ) a ] 4– unit were measured in the solid state and in an acetonitrile solution. The redox potential of the [Re 6 Se i 8 (N 3 ) a ] 4– /[Re 6 Se i 8 (N 3 ) a ] 3– system was measured in acetonitrile. Experimental results were analyzed in the light of density functional theory calculations.