Preparation and characterization of {[M(dmb)(2)]TCNQ center dot xTCNQ degrees}(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

New thermoplastic organometallic materials of the type {[M(dmb)(2)]TCNQ . x TCNQ degrees.y solvent}(n). (M = Cu(I) Ag(I); dmb = 1,8-diisocyano-p-mentha ne; TCNQ = 7,7,8,8-tetracyano-p-quinodimethane, x = 0, 0.5, 1.0, 1.5; solve nt = 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 deg rees}(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 b e a function of the molecular weight and crystallinity. The {[Cu(dmb)(2)]TC NQ . 1.5CNQ}(n) material is also photoconducting, while the Ag analogue is not. Photochemical and luminescence quenching experiments in the solid-stat e established that the Cu+ center and TCNQ degrees act as electron donor an d acceptor, respectively, in this photoprocess. Finally photocells of the t ype glass/SnO2/{[Cu-(dmb)(2)]TCNQ . TCNQ degrees}(n) + 0.5 acceptor/Al (acc eptor = TCNQ degrees, C-60 and TCNN (13,13,14, 14-tetracyano-5,12-naphthace nequinodimethane)) have been designed and characterized. The quantum yields (number of photoproduced electrons/number of photons) are as follows: TCNQ , 1.6 x 10(-4), C-60, 5 x 10(-5), TCNN, 3.0 x 10(-4) at lambda(exc) = 330 n m. X-ray data for {[Ag(dmb)(2)]TCNQ . 2THF}(n): space group P2(1)/c, monocl inic, n = 13.5501(10), b = 9.9045(10), c = 32.564(2) Angstrom, beta = 91.13 0(10)degrees, Z = 4. X-ray data for {[Ag(dmb)(2)]TCNQ . 0.5TCNQ degrees . 0 .5 toluene}(n): space group P2(1)/c, monoclinic, a = 14.3669(19), b = 9.165 9(3), c = 34.012(3) Angstrom, beta = 92.140(8)degrees Z = 4. X-ray data for {[Ag(dmb)(2)]TCNQ . 1.5TCNQ degrees}(n): space group C2/c, monoclinic, a = 25.830(19), b = 9.680(2), c 32.183(19) Angstrom, beta = 103.87(4)degrees, Z = 8. X-ray data for {[Ag(dmb)(2)]DCTC}(n): space group P2(1)/a, monoclini c, a = 26.273(3), b = 9.730(3), c = 31.526(3) Angstrom, beta = 112.12(2)deg rees, Z = 4.