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Research in this dissertation studies the charge dynamics in the MLCT excited states of trans-M2L2L’2 and M2L4 paddlewheel compounds (M = Mo or W) which represent typical TM compounds and have strong light absorption in the UV-visible range. A series of trans-M2L2L’2 and M2L4 compounds are prepared where L is a MLCT-active amidinate, amide or thioamide ligand (L = NN, NO or NS corresponding to (NPh)(X)CC=CPh where X = NPh, O, S, respectively) and L’ is an auxiliary carboxylate ligand which does not allow low energy MLCT transitions. Substitution of the MLCT and auxiliary ligands creates controlled variation in both regio-symmetry and electronic structures of these compounds. The compounds are studied using X-ray single crystallography, steady-state absorption, emission and time-resolved spectroscopy techniques. The charge distribution and charge dynamics in the excited states of these molecules are followed by IR reporters like the ethynyl groups using femtosecond time-resolved infrared spectroscopy (fs-TRIR). The different charge distribution patterns observed in the MLCT states are attributed to tunable inter-ligand electron transfer between acceptor ligands across the L-Msub>2-L chain on the vibrational time-scale (~10-12 s).