TOWARD A NEW MAGNETIC, ELECTRONIC, AND OPTICAL-MATERIALS - SYNTHESIS AND CHARACTERIZATION OF NEW BIMETALLIC TETRATHIAFULVALENE TETRATHIOLATE BUILDING-BLOCKS

Metal coordination complexes of tetrathiafulvalene (TTF) have long been proposed to be interesting building blocks to new electronic, optical, and magnetic materials. Presented herein are the synthesis and characterization of the first examples of early and late transition metal homobimetallic coordination complexes of tetrathiafulvalene tetrathiolate (1). We have prepared the compounds Cp2TiS2TTFS2TiCP2 (4), CP2*TiS2TTFS2TiCP2* (5), and (Ph3P)2PtS2TTFS2Pt(PPH3)2 Pt(PPh3)2 (6) and characterized these compounds by H-1 NMR, DNMR, UV-vis-NIR, elemental analysis, FAB-MS, electrochemistry, etc. The electronic spectral data of the Ti complexes indicate a strong LMCT band, which is consistent with the ability of the metal to act as an acceptor and the TTF as a donor. These compounds have been preliminarily shown to form charge-transfer complexes with TCNQ. In addition, complex 4 was also found to undergo an interesting transmetalation reaction with Ni(dppp)Cl2. This type of reaction affords the possible synthesis of heterobimetallic complexes of TTF. Discussion pertaining to the potential of materials based on metal-TTF hybrid molecules is also presented.