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Preparation and Characterization of {[M(dmb)2]TCNQ·xTCNQ°}n Polymers (M = Cu,Ag; dmb = 1,8-Diisocyano-p-menthane; x = 0, 0.5, 1.0, 1.5; TCNQ = 7,7,8,8-Tetracyano-p-quinodimethane) and Design of New Semi- and Photoconducting Organometallic Materials

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journal contribution
posted on 06.06.2000, 00:00 by Daniel Fortin, Marc Drouin, Pierre D. Harvey
New thermoplastic organometallic materials of the type {[M(dmb)2]TCNQ·xTCNQ°·y solvent}n (M = Cu(I), Ag(I); dmb = 1,8-diisocyano-p-menthane; TCNQ = 7,7,8,8-tetracyano-p-quinodimethane, x = 0, 0.5, 1.0, 1.5; solvent = none, THF or toluene) have been prepared and characterized from X-ray powder diffraction patterns, X-ray crystallography (for some Ag polymers), DSC, and conductivity measurements. While the {[M(dmb)2]TCNQ·xTCNQ°}n polymers (M = Cu,Ag; x = 0, 0.5) are insulating, the others (x = 1.0 and 1.5) are semiconducting, and the relative conductivity is found to be a function of the molecular weight and crystallinity. The {[Cu(dmb)2]TCNQ·1.5TCNQ}n material is also photoconducting, while the Ag analogue is not. Photochemical and luminescence quenching experiments in the solid-state established that the Cu+ center and TCNQ° act as electron donor and acceptor, respectively, in this photoprocess. Finally photocells of the type glass/SnO2/{Cu(dmb)2]TCNQ·TCNQ°}n + 0.5 acceptor/Al (acceptor = TCNQ°, C60 and TCNN (13,13,14,14-tetracyano-5,12-naphthacenequinodimethane)) have been designed and characterized. The quantum yields (number of photoproduced electrons/number of photons) are as follows:  TCNQ, 1.6 × 10-4, C60, 5 × 10-5, TCNN, 3.0 × 10-4 at λexc = 330 nm. X-ray data for {[Ag(dmb)2]TCNQ·2THF}n:  space group P21/c, monoclinic, a = 13.5501(10), b = 9.9045(10), c = 32.564(2) Å, β = 91.130(10)o, Z = 4. X-ray data for {[Ag(dmb)2]TCNQ·0.5TCNQ°·0.5 toluene}n:  space group P21/c, monoclinic, a = 14.3669(19), b = 9.1659(3), c = 34.012(3) Å, β = 92.140(8)o, Z = 4. X-ray data for {[Ag(dmb)2]TCNQ·1.5TCNQ°}n:  space group C2/c, monoclinic, a = 25.830(11), b = 9.680(2), c = 42.183(19) Å, β = 104.87(4)o, Z = 8. X-ray data for {[Ag(dmb)2]DCTC}n:  space group P21/a, monoclinic, a = 26.273(3), b = 9.730(3), c = 31.526(3) Å, β = 112.12(2)o, Z = 4.

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