The new members of the series of 2,5-disubstituted DCNQIs, temperatures, except [1d (Cl/OMe)] 2 Cu which undergoes a sharp phase transition to an insulating state[M Ǟ I]. By 1d (Cl/OMe), 1e (Br/OMe), 1j (Cl/I), 1k (Br/I), 1l (I/I), form conducting charge-transfer complexes with TTF variation of the ligands or their ratios in conducting alloys of DCNQI-Cu salts temperature-dependent conductivities can (tetrathiofulvalene) which are comparable to known DCNQI/ TTFs. From these DCNQIs highly conducting radical-anion be tuned from M Ǟ I to M. In addition, alloying three ligands produced for the first time a radical salt with temperature-salts [2-X, 5-Y-DCNQI] 2 M (M = Li, Na, K, NH 4 , Tl, Rb, Ag, Cu) can also be prepared either from the DCNQIs and MI independent conductivity from 5 to 300 K. Most remarkably, alloys of the type [(2,5-Me 2 DCNQI) m ] Cu/[{2,5-(CD 3 ) 2 -(not AgI), on a metal wire (Ag, Cu), or by electrocrystallization (M = Tl, Ag,Cu). For better crystals a method DCNQI} n ] 2 Cu which exhibit a sharp M Ǟ I phase transition on further cooling reenter the conducting state by an I Ǟ M using periodical switching between reduction and partial oxidation has been developed. With CF 3 (large, strongly transition, with changes of ca. 10 8 Scm -1 both ways. For the first time in the field of organic metals crystal structures of electron-attracting) as the substituent in DCNQIs 1m (OMe/ CF 3 ) and 1n (Me/CF 3 ), conducting TTF complexes remain DCNQI-copper salts have been determined by X-ray powder diffraction methods and refined by Rietveld analysis. Unit whereas only 1n yields an insulating copper salt. DCNQI-Cu salts with high conductivities are obtained with alloys cell data, coordination angles and distances of the π planes are in excellent agreement with the single-crystal X-ray data. containing two or three different DCNQIs. The temperaturedependent conductivities of DCNQI-M salts (other than However, bond lengths and angles of the ligands are to be less accurate. This powder method proves to be most copper) are similar to those of metal-like semiconductors. All new DCNQI-Cu salts are metallic [M] down to low valuable if only microcrystalline material is available.
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DCNQIs presented here produce charge-transfer complexes