1. Novel mixed-valence Cu compounds formed by Cu(II) dimers with double oximato bridges: in situ formation of anionic layer [Cu2(SCN)3]n(n-)
- Author
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Samiran Mitra, Piu Dhal, Ennio Zangrando, Madhusudan Nandy, Guillaume Pilet, Dipali Sadhukhan, Carlos J. Gómez-García, Dhal, Piu, Nandy, Madhusudan, Sadhukhan, Dipali, Zangrando, Ennio, Pilet, Guillaume, Gómez García, Carlos J, Mitra, Samiran, Department of Chemistry, Jadavpur University, Departement of Chemical and Pharmaceutical Sciences, Laboratoire des Multimatériaux et Interfaces (LMI), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Instituto de Ciencia Molecular (ICMol), and Universitat de València (UV)
- Subjects
In situ ,Anions ,Models, Molecular ,Stereochemistry ,Anion ,chemistry.chemical_element ,Infrared spectroscopy ,010402 general chemistry ,Crystallography, X-Ray ,Copper ,Dimerization ,Molecular Structure ,Organometallic Compounds ,Oximes ,Thiocyanates ,01 natural sciences ,Inorganic Chemistry ,Oxime ,Models ,[CHIM.CRIS]Chemical Sciences/Cristallography ,Molecule ,[CHIM]Chemical Sciences ,Group 2 organometallic chemistry ,Organometallic Compound ,Crystallography ,Valence (chemistry) ,010405 organic chemistry ,Cationic polymerization ,Molecular ,[CHIM.MATE]Chemical Sciences/Material chemistry ,0104 chemical sciences ,chemistry ,X-Ray ,Single crystal - Abstract
Two new N3O donor ketoxime Schiff bases (HL(1) and HL(2)) have been synthesized by condensing N,N-dimethylethylenediamine with diacetylmonoxime and benzilmonoxime, respectively in a 1:1 ratio. Reaction of Cu(ClO4)2·6H2O with HL(1) resulted in a discrete oximato-bridged dinuclear Cu(II) complex [Cu2(L(1))2(H2O)2](ClO4)2 (1). The same reaction in presence of NaSCN affords the complex {[Cu(II)2(L(1))2][Cu(I)4(μ(1,3)-SCN)4(μ(1,1,3)-SCN)2]}n (2), where partial Cu(II)→Cu(I) reduction is observed. In 2, arrays of [Cu(II)2(L(1))2](2+) cationic units are inserted in between 2D {[Cu(I)4(SCN)6](2-)}n layers and connected via μ(1,1,3)-SCN(-) links, thus forming a 3D network. On the other hand, reaction of Cu(CH3COO)2 and HL(2) in the presence of NaSCN gave rise to a mixed-valence pentanuclear cluster {[Cu(II)2(L(2))2(NCS)]2[Cu(I)(SCN)(μ(1,1)-SCN)(μ(1,3)-SCN)]} (3) where Cu(II) is also partly reduced to Cu(I). In compound 3, two cationic [Cu(II)2(L(2))2(NCS)](+) units are bridged by the anionic [Cu(I)(SCN)3](2-) unit through long Cu-SCN linkages. The ligands and the complexes have been characterized by elemental analysis, UV/Vis and IR spectroscopy. The complexes are further characterized by single crystal X-ray diffraction and variable temperature magnetic (VTM) studies. Finally a complete magneto-structural correlation has been established between compounds 1-3 and all the characterized Cu dimers with a double NO bridge.
- Published
- 2013