Synthesis and Study of Polyazine Bridged Mixed Metal Dyads: Electrochemical, Photophysical, and Photochemical Properties of a New Supramolecular Architecture
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摘要: A series mixed metal supramolecular complexes were synthesized and studied by electrochemistry, photophysics photochemistry. The consisted of a single Ru or Os polyazine light absorber bound to cis-RhCl2 moiety through bridging ligand. related class supramolecule is known perform photoinitiated electron collection, photocatalysis hydrogen from water, DNA photomodification kill mammalian cells; all with visible irradiation. herein, [(bpy)2Ru(bpm)RhCl2(phen)](PF6)3, [(bpy)2Ru(dpp)RhCl2(phen)](PF6)3, [(bpy)2Os(dpp)RhCl2(phen)](PF6)3, [(tpy)OsCl(dpp)RhCl2(phen)](PF6)2 in moderate yields (54-84%) reaction the appropriate monometallic absorbing subunit slight excess K[(phen)RhCl4]·3H2O (bpy = 2,2'-bipyridine, bpm 2,2'bipyrimidine, 1,10-phenanthroline, dpp 2,3-bis(2-pyridyl)pyrazine, tpy 2,2':6',2"terpyridine). Voltammetric analysis [(bpy)2Ru(bpm)RhCl2(phen)](PF6)3 revealed reversible oxidation at 1.76 V (vs. Ag/AgCl) (Ru). reduction −0.14 (bpm), quasi-reversible reductions −0.77 −0.91 each corresponded one process, bpm, Rh Rh. electrochemistry [(bpy)2Ru(dpp)RhCl2(phen)](PF6)3 showed 1.61 (Ru), −0.39 V, −0.74 −0.98 V. first two reductive couples electrons, consistent reduction. exhibited similar bridged Ru,Rh dyad, but based oxidations 1.24 0.83 respectively. [{(bpy)2Ru(bpm)}2RhCl2](PF6)5 display Ru(dπ)→bpm(π*) CT (MLCT) transitions 581 nm 594 nm, bimetallic Ru,Rh,Ru trimetallic Ru(dπ)→dpp(π*) 509 518 Similarly, [(bpy)2Os(dpp)RhCl2(phen)](PF6)3 absorbs strongly 520 versus 534 for [{(bpy)2Os(dpp)}2RhCl2](PF6)5, both low energy tails 800 indicative centered MLCT transitions. Overlapping Os(dπ)→dpp(π*) Os(dπ)→tpy(π*) occur 536
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