Ruthenium complexes containing 2,2'-bipyridine and PTA (PTA = 1,3,5-triaza-7-phosphaadamantane)
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2016-03-06Abstract
The water soluble complexes cis-[Ru(bpy)2(PTA)2]Cl2 (1Cl2), cis-[Ru(bpy)2(PTA)2](PF6)2 (1(PF6)2), trans-[Ru(bpy)2(PTA)2](CF3SO3)2 (2(CF3SO3)2), cis-[Ru(bpy)2(PTA)(H2O)](CF3SO3)2 (3(CF3SO3)2), cis-[Ru(bpy)2(PTAH3)(H2O)](CF3SO3)5 (4(CF3SO3)5), cis-[Ru(bpy)2(PTAH3)2](CF3SO3)8 (5(CF3SO3)8) and trans-[Ru(bpy)2(PTAH3)2](CF3SO3)8 (6(CF3SO3)8) have been synthesized and characterized by elemental analysis, NMR and IR spectroscopy. The crystal structures of 1(PF6)2, 2(CF3SO3)2, 4(CF3SO3)5 were obtained by single-crystal X-ray diffraction. Both experimental and computational techniques were utilized to perform a thorough analysis of the structural and electronic properties of the complexes 1 and 2 in water in both the deprotonated and protonated state and under N2 and air. UV/Visible absorbance spectroscopy revealed the sensitiveness of complex 1 and 2 to the pH. Both Ligand-to-Metal Charge Transfer (LMCT) and Metal-to-Ligand/Ligand-to-Ligand Charge Transfer (MLCT/LLCT) transisions were observed ...
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