✍ Scribed by Cristina Alonso; Loreto Ballester; Angel Gutiérrez; M. Felisa Perpiñán; Ana E. Sánchez; M. Teresa Azcondo
No coin nor oath required. For personal study only.
Several derivatives of formulae M(terpy)~2~~2~ or M(terpy)~2~~3~ (M = Ni, Cu, Zn; terpy = 2,2′:6′,2"‐terpyridine; TCNQ= 7,7,8,8‐tetracyanoquinodimethane) and M(phen)~3~~2~ or M(phen)~3~~4~ (M = Fe, Ni; phen = 1,10‐phenanthroline) have been obtained. The crystal structures of M(terpy)~2~~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]~2~^2−^ groups alternate in the crystal. For the derivatives with three TCNQ groups, the existence of a stack of trimeric [TCNQ]~3~^2−^ ions having electronic delocalisation is proposed. The compound Fe(phen)~3~~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]~2~^2−^ 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)
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