A New Molecular Magnetic Semiconductor Based On Tetrathiafulvalene (ttf) And Oxamato Ligand (opba): [ttf]2[cu(opba)]·h2o

An oxamato-based compound of formula [ttf]2[Cu(opba)] ·H2O, with ttf = tetrathiafulvalene and opba = ortho-phenylenebis(oxamato), has been prepared and characterized. The complex was obtained by metathesis from (ttf)3(BF4)2 and (Bu4N)2[Cu(opba)] in acetonitrile at room temperature. The UV-Vis-NIR spectrum reveals the presence of the radical cation in two forms, (ttf•+) and (ttf•+)2 dimer. The electronic transport properties of [ttf]2[Cu(opba)]·H 2O were studied by impedance spectroscopy (IS) and linear voltammetry (LV), and show a typical semiconductor behavior. The EPR spectra exhibit two superposed lines corresponding to electron spins of CuII ions and ttf•+ radical cations. The dc magnetic properties show a room temperature value of the χMT product close to that expected for three uncoupled S = 1/2 spins and a value of 0.13 emu K mol-1 at low temperature (4 K). The χMT vs. T curve was fitted and the best model consists of a term for a (ttf•+)2 dimer (Bleaney-Bowers, leading to J2 = -186 cm-1) and a second term related to an antiferromagnetic {Cu...ttf•+} chain (J 1 = -10.1 cm-1).21712741282Wudl, F., Smith, G.M., Hufnagel, E.J., (1970) J. Chem. Soc. D, Chem. Commun., p. 1453Wudl, F., Wobschal, D., Hufnagel, E.J., (1972) J. Am. Chem. Soc., 94, p. 670Ferraris, J., Walatka, V., Perlstei, J., Cowan, D.O., (1973) J. Am. Chem. Soc., 95, p. 948Coronado, E., Day, P., (2004) Chem. Rev., 104, p. 5419Williams, J.M., Kini, A.M., Wang, H.H., Carlson, K.D., Geiser, U., Montgomery, L.K., Pyrka, G.J., Whangbo, M.H., (1990) Inorg. Chem., 29, p. 3272Wang, H.H., Schlueter, J.A., Geiser, U., Williams, J.M., Naumann, D., Roy, T., (1995) Inorg. Chem., 34, p. 5552Kahn, O., Stumpf, H., Pei, Y., Sletten, J., (1993) Mol. Cryst. Liq. Cryst., 233, p. 231Stumpf, H.O., Ouahab, L., Pei, Y., Grandjean, D., Kahn, O., (1993) Science, 261, p. 447Pereira, C.L.M., Doriguetto, A.C., Konzen, C., Meira-Belo, L.C., Leitao, U.A., Fernandes, N.G., Mascarenhas, Y.P., Stumpf, H.O., (2005) Eur. J. Inorg. Chem., p. 5018Pereira, C.L.M., Pedroso, E.F., Novak, M.A., Brandl, A.L., Knobel, M., Stumpf, H.O., (2003) Polyhedron., 22, p. 2387Dias, M.C., Knobel, M., Stumpf, H.O., (2001) J. Magn. Magn. Mater., 226, p. 1961Vaz, M.G.F., Knobel, M., Speziali, N.L., Moreira, A.M., Alcantara, A.F.C., Stumpf, H.O., (2002) J. Braz. Chem. Soc., 13, p. 183Vaz, M.G.F., Pedroso, E.F., Speziali, N.L., Novak, M.A., Alcantara, A.F.C., Stumpf, H.O., (2001) Inorg. Chim. Acta, 326, p. 65Cangussu, D., Nunes, W.C., Pereira, C.L.M., Pedroso, E.F., Mazali, I.O., Knobel, M., Alves, O.L., Stumpf, H.O., (2008) Eur. J. Inorg. Chem., p. 3802Pereira, C.L.M., Pedroso, E.F., Stumpf, H.O., Novak, M.A., Ricard, L., Ruiz-Garcia, R., Riviere, E., Journaux, Y., (2004) Angew. Chem. Int. Ed., 43, p. 955Souza, G.P., Konzen, C., Ardisson, J.D., De Abreu, H.A., Duarte, H.A., Alcantara, A.F.C., Nunes, W.C., Stumpf, H.O., (2006) J. Braz. Chem. Soc., 17, p. 1534Baibich, M.N., Broto, J.M., Fert, A., Vandau, F.N., Petroff, F., Eitenne, P., Creuzet, G., Chazelas, J., (1988) Phys. Rev. Lett., 61, p. 2472Moon, K.S., Fontana, R.E., Parkin, S.S.P., (1999) Appl. Phys. Lett., 74, p. 3690Coronado, E., Falvello, L.R., Galan-Mascaros, J.R., Gimenez-Saiz, C., Gomez-Garcia, C.J., Lauhkin, V.N., Perez-Benitez, A., Veciana, J., (1997) Adv. Mater., 9, p. 984Day, P., Kurmoo, M., Mallah, T., Marsden, I.R., Friend, R.H., Pratt, F.L., Hayes, W., Ducasse, L., (1992) J. Am. Chem. Soc., 114, p. 10722Coronado, E., Galan-Mascaros, J.R., Gomez-Garcia, C.J., Laukhin, V., (2000) Nature, 408, p. 447Graham, A.W., Kurmoo, M., Day, P., (1995) J. Chem. Soc., Chem. Commun., p. 2061Kurmoo, M., Graham, A.W., Day, P., Coles, S.J., Hursthouse, M.B., Caulfield, J.L., Singleton, J., Guionneau, P., (1995) J. Am. Chem. Soc., 117, p. 12209Dias, M.C., Stumpf, H.O., Sansiviero, M.T.C., Pernaut, J.M., Matencio, I., Knobel, M., Cangussu, D., (2007) Quim. Nova, 30, p. 904Wudl, F., (1975) J. Am. Chem. Soc., 97, p. 1962Boukamp, B.A., (1986) Solid State Ionics, 20, p. 31Bozio, R., Zanon, I., Girlando, A., Pecile, C., (1979) J. Chem. Phys., 71, p. 2282Torrance, J.B., Scott, B.A., Welber, B., Kaufman, F.B., Seiden, P.E., (1979) Phys. Rev. B., 19, p. 730Iyoda, M., Hasegawa, M., Miyake, Y., (2004) Chem. Rev., 104, p. 5085Yakushi, K., Nishimura, S., Sugano, T., Kuroda, H., Ikemoto, I., (1980) Acta Crystallogr. Sect. B, Struct. Commun., 36, p. 358Bellitto, C., Bonamico, M., Fares, V., Imperatori, P., Patrizio, S., (1989) J. Chem. Soc., Dalton Trans., p. 719Siedle, A.R., Candela, G.A., Finnegan, T.F., Vanduyne, R.P., Cape, T., Kokoszka, G.F., Woyciejes, P.M., Hashmall, J.A., (1981) Inorg. Chem., 20, p. 2635Kozlov, M.E., Pokhodnia, K.I., Yurchenko, A.A., (1989) Spectrochim. Acta, Part A, 45, p. 437Hasanudin, Kuroda, N., Kagayama, T., Sugimoto, T., Mogi, I., Watanabe, K., Motokawa, M., (2002) High Pressure Res., 22, p. 251Ashcroft, N.W., Mermin, N.D., (1976) Solid State Physics, , Saunder College Publishing: New YorkWest, A.R., (1984) Solid State Chemistry and its Applications, , John Wiley: New YorkStarodub, V.A., Krivoshei, I.V., (1982) Russ. Chem. Rev., 51, p. 764Coronado, E., Galan-Mascaros, J.R., Gimenez-Saiz, C., Gomez-Garcia, C.J., Ruiz-Perez, C., (2003) Eur. J. Inorg. Chem., p. 2290Lacroix, P., Kahn, O., Valade, L., Cassoux, P., Thompson, L.K., (1990) Synth. Met., 39, p. 81Kataev, V., Winkel, G., Knauf, N., Gruetz, A., Khomskii, D., Wohlleben, D., Crump, W., Physica, B., (1992), 179, p. 24Komatsu, T., Kojima, N., Saito, G., (1997) Solid State Commun., 103, p. 519Bencini, A., Gatteschi, D., (1990) Electron. Paramagnetic Resonance of Exchange Coupled Systems, , Springer-Verlag: BerlinDrago, R.S., (1992) Physical Methods for Chemists, , 2nd ed., Saunders College Publishing: New YorkBleaney, B., Bowers, K.D., (1952) Proc. R. Soc. A-Math. Phys. Eng. Sci., 214, p. 451Kahn, O., (1993) Molecular Magnetism, , VCH: New YorkGomez-Garcia, C.J., Gimenez-Saiz, C., Triki, S., Coronado, E., Lemagueres, P., Ouahab, L., Ducasse, L., Delhaes, P., (1995) Inorg. Chem., 34, p. 4139Bonner, J.C., Fisher, M.E., (1964) Phys. Rev., 135, pp. A640Brown, D.B., Donner, J.A., Hall, J.W., Wilson, S.R., Wilson, R.B., Hodgson, D.J., Hatfield, W.E., (1979) Inorg. Chem., 18, p. 2635Cador, O., Vaz, M.G.F., Stumpf, H.O., Mathoniere, C., Kahn, O., (2001) Synth. Met., 122, p. 55