TY - JOUR AU - Jia, Chunyang AU - Ding, Jie AU - Liu, Shi-Xia AU - Labat, Gaël AU - Neels, Antonia AU - Hauser, Andreas AU - Decurtins, Silvio TI - A Pt(II) complex with both a phenanthroline and a tetrathiafulvalene-extended dithiolate ligand: Synthesis, crystal structure, electro-chemical and spectroscopic properties PY - 2013 JF - Polyhedron JA - Polyhedron SN - 0277-5387 VL - 55 SP - 87 EP - 91 L1 - http://www.sciencedirect.com/science/article/pii/S0277538713001666/pdfft?md5=c1e88a3d7526a37577c2c41e00c3b67f&pid=1-s2.0-S0277538713001666-main.pdf L2 - http://www.sciencedirect.com/science/article/pii/S0277538713001666 L4 - http://www.unige.ch/sciences/chifi/publis/pics/double/ref01385.png M3 - 10.1016/j.poly.2013.02.064 UR - http://dx.doi.org/10.1016/j.poly.2013.02.064 KW - tetrathiafulvalene KW - intramolecular charge-transfer KW - spectroelectrochemistry N2 - The reaction of 4,5-bis(2\'-cyano-ethylsulfanyl)-4\',5\'-dipropylthiotetrathiafulvalene with [Pt(phen)Cl2] (phen = 1,10-phenanthroline) with CsOH as base in CH3OH–THF affords the target complex 1 in 44% yield. This complex crystallizes in the monoclinic space group P21/c, M = 790.01, a = 12.1732(12), b = 15.851(2), c = 14.5371(16) Å, b = 107.693(12)˚, V = 2672.4(5) Å3 and Z = 4. It undergoes two reversible single-electron oxidation and two irreversible reduction processes. An intense electronic absorption band at 15200 cm-1 (658 nm) in CH2Cl2 is assigned to the intramolecular mixed metal/ligand-to-ligand charge transfer (LLCT) from a tetrathiafulvalene-extended dithiolate-based HOMO to a phenanthroline-based LUMO. This band shifts hypsochromically with increasing solvent polarity. Systematic changes in the optical spectra upon oxidation allow precise tuning of the oxidation states of 1 and reversible control over its optical properties. Irradiation of 1 at 15625 cm-1 (640 nm) in glassy solution below 150 K results in emission from the 3LLCT excited state. ID - 1385 ER -