Heterodimetallic Structures Based on Cyano-Substituted Bis(dithiolene) Complexes and Ni and Cu Cyclam Cations

Five charge‐transfer salts based on the combination of anionic FeIII and CuII bis(dithiolene) complexes containing nitrile groups with [M(cyclam)]2+ (M = Ni, Cu) cations, namely, [Ni(cyclam)]2[Cu(dcbdt)2]2·4DMF (1, dcbdt = 4,5‐dicyanobenzene‐1,2‐dithiolate, DMF = N,N‐dimethylformamide), [Ni(cyclam)]...

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Published in:European journal of inorganic chemistry Vol. 2013; no. 26; pp. 4612 - 4618
Main Authors: Cerdeira, Ana C., Belo, Dulce, Rabaça, Sandra, Pereira, Laura C. J., Coutinho, Joana T., Simão, Dulce, Henriques, Rui T., Jeannin, Olivier, Fourmigué, Marc, Almeida, Manuel
Format: Journal Article
Language:English
Published: Weinheim WILEY-VCH Verlag 03.09.2013
WILEY‐VCH Verlag
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Wiley-VCH Verlag
Subjects:
Atomic structure
Cations
Chemical Sciences
Coordination modes
Crystal structure
Dithiolene ligands
Heterometallic complexes
Hydrogen bonds
Macrocyclic ligands
Magnetic properties
Nickel
Nitriles
Organic chemistry
Solvents
X ray diffraction
Macrocyclic ligands
Dithiolene ligands
Coordination modes
Heterometallic complexes
Magnetic properties
ISSN:1434-1948, 1099-0682
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Summary:Five charge‐transfer salts based on the combination of anionic FeIII and CuII bis(dithiolene) complexes containing nitrile groups with [M(cyclam)]2+ (M = Ni, Cu) cations, namely, [Ni(cyclam)]2[Cu(dcbdt)2]2·4DMF (1, dcbdt = 4,5‐dicyanobenzene‐1,2‐dithiolate, DMF = N,N‐dimethylformamide), [Ni(cyclam)]2[Cu(dcdmp)2]2·4DMF (2, dcdmp = 2,3‐dicyano‐5,6‐dimercaptopyrazine), [Cu(cyclam)]2[Cu(dcdmp)2]2·4DMF (3), [Cu(cyclam)]2[Fe2(cbdt)4]2·4DMF (4, cbdt = 4‐cyanobenzene‐1,2‐dithiolate) and [Ni(cyclam)]2[Fe2(cbdt)4]2·4DMF (5), were prepared and characterised by X‐ray diffraction and magnetisation measurements. The crystal structures of 1–4 were determined by single‐crystal X‐ray diffraction, which revealed that the cyano groups from dithiolene complexes fail to coordinate the metal ions in the cyclam units. Instead, they are coordinated by solvent molecules or by dithiolene S atoms and cyclam N–H groups, which participate in hydrogen bonds to the nitrile and sulfur moieties in the anions. Heterodimetallic structures based on the combination of anionic FeIII and CuII bis(dithiolene) complexes containing nitrile groups with [M(cyclam)]2+ (M = Ni, Cu) cations display a new coordination mode of the dithiolene S atom towards the metal cyclam.
Bibliography:istex:21D36E142ABCD4BD7495E1382BF42A88E3EDF0A7
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ArticleID:EJIC201300490
ObjectType-Article-1
SourceType-Scholarly Journals-1
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ISSN:1434-1948
1099-0682
DOI:10.1002/ejic.201300490