Tetracyanoquinodimethanido Derivatives of (Terpyridine)‐ and (Phenanthroline)metal Complexes − Structural and Magnetic Studies of Radical‐Ion Salts

Autor: Angel Gutiérrez, M. Felisa Perpiñán, Cristina Vico Alonso, Loreto Ballester, M. Teresa Azcondo, Ana Sánchez
Rok vydání: 2005
Předmět:
Zdroj: European Journal of Inorganic Chemistry. 2005:486-495
ISSN: 1099-0682
1434-1948
DOI: 10.1002/ejic.200400540
Popis: Several derivatives of formulae [M(terpy)2](TCNQ)2 or [M(terpy)2](TCNQ)3 (M = Ni, Cu, Zn; terpy = 2,2′:6′,2"-terpyridine; TCNQ= 7,7,8,8-tetracyanoquinodimethane) and [M(phen)3](TCNQ)2 or [M(phen)3](TCNQ)4 (M = Fe, Ni; phen = 1,10-phenanthroline) have been obtained. The crystal structures of [M(terpy)2](TCNQ)2 (M = Ni, Cu) show that the metal is surrounded by the terpyridine nitrogen atoms in a closed octahedral environment and the TCNQ anions are dimerised by π overlap. The cationic [M(terpy)2]2+ and the anionic [TCNQ]22− groups alternate in the crystal. For the derivatives with three TCNQ groups, the existence of a stack of trimeric [TCNQ]32− ions having electronic delocalisation is proposed. The compound [Fe(phen)3](TCNQ)2, which shows a strong interaction between TCNQ anions, led to the formation of a σ bond in the diamagnetic species [TCNQ−TCNQ], while the nickel analogue is expected to have a localised structure formed by alternation of cationic metal complexes and dimeric [TCNQ]22− anions similar to those observed in the analogous terpy derivatives. The derivatives having four TCNQ groups also show electronic delocalisation and a 1D stack based on the magnetic data is proposed. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Databáze: OpenAIRE
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