Photophysical studies of hetero-bischelated complexes of rhodium(III) containing 2,2′-dipyridylamine

Ruthenium(II)-Polyazine Light Absorbers Bridged to Reactive cis-Dichlororhodium(III) Centers in a Bimetallic Molecular Architecture

“…12 Tseng et al prepared cis-[(bpy)RhCl 2 (HDPA)] + , where HDPA ) bis(2-pyridyl)amine, from K[(bpy)RhCl 4 ] and HDPA in acidified refluxing methanol. 16 The same group prepared cyclometallated complexes cis-[(NN)RhCl 2 (bzpy)], where NN ) bpy or phen and bzpy ) 2-(2-pyridylcarbonyl)phenylate, from a neat molten mixture of the appropriate K[(NN)RhCl 4 ] and Hbzpy. 17 The 3 MLCT excited state of Ru(II) polyazine complexes are known to undergo bimolecular electron transfer quenching with Rh(III) polyazine complexes.…”

“…Syntheses of heteroleptic Rh(III) polyazine complexes have been reported using a [(NN)RhCl 4 ] − starting material reacting with 1 equiv of another polyazine ligand. − Morrison and co-workers recently reported the synthesis of cis- [(phen)RhCl 2 (dppz)] + from K[(phen)RhCl 4 ] and dipyrido[3,2 a -2′,3′ c ]phenazine (dppz) in dimethylformamide (DMF) . Tseng et al prepared cis- [(bpy)RhCl 2 (HDPA)] + , where HDPA = bis(2-pyridyl)amine, from K[(bpy)RhCl 4 ] and HDPA in acidified refluxing methanol .…”

“…Syntheses of heteroleptic Rh(III) polyazine complexes have been reported using a [(NN)RhCl 4 ] − starting material reacting with 1 equiv of another polyazine ligand. − Morrison and co-workers recently reported the synthesis of cis- [(phen)RhCl 2 (dppz)] + from K[(phen)RhCl 4 ] and dipyrido[3,2 a -2′,3′ c ]phenazine (dppz) in dimethylformamide (DMF) . Tseng et al prepared cis- [(bpy)RhCl 2 (HDPA)] + , where HDPA = bis(2-pyridyl)amine, from K[(bpy)RhCl 4 ] and HDPA in acidified refluxing methanol . The same group prepared cyclometallated complexes cis- [(NN)RhCl 2 (bzpy)], where NN = bpy or phen and bzpy = 2-(2-pyridylcarbonyl)phenylate, from a neat molten mixture of the appropriate K[(NN)RhCl 4 ] and Hbzpy …”

Synthesis, structure and luminescence behaviour of a mononuclear cadmium(II) dicyanamide and a coordination polymer of mercury(II) dicyanamide containing 2,2′-dipyridylamine (dpaH) as end-capping ligand/anion of dpaH as binucleating bridge. Variance in coordination numbers, nuclearities and architectures with metal ion templates

“…Upon photoexcitation at 266 nm (for dpaH), 274 nm (for 1) and 275 nm (for 2) in DMF solutions, free ligand exhibits fluorescent emission centered on 345 nm, whereas the corresponding cadmium(II) and mercury(II) dicyanamide complexes show photoluminescence with the main emissions at almost similar position (349 nm for 1 and 339 nm for 2) to that of free dpaH ligand. The appearance of luminescence [52][53][54] in the complexes may be attributed to the intraligand 1 (p-p ⁄ ) fluorescence. The lifetimes of the fluorescence of 1 and 2 are 2.69 ns and 3.14 ns, respectively.…”

Photochemistry and Photophysics of Coordination Compounds: Rhodium

“…A number of analogues of the cis-Rh(NN) 2 Cl 2 + complexes, where the NN represents various bidentate nitrogen donors, such as e.g., 2, 3 behave similarly to cis-Rh(phen) 2 Cl 2 + , i.e., have lowest excited states of MC character and emit accordingly [44,45].…”