A theoretical study of cis-trans photoisomerization in the bis(glycinato)platinum(II) complex

Richardson, F. S.; Shillady, Donald D.; Waldrop, Alex A.

doi:10.1016/s0020-1693(00)95930-9

Cited by 10 publications

(2 citation statements)

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“…The mechanisms of the cis ⇄ trans photoisomerization of platinum(II) species were discussed previously. Balzani et al and Richardson et al studied the photochemical isomerization of [Pt(gly) 2 ] (gly = glycinato) and concluded the reaction proceeded via tortional twist of the bidentate ligand. Lewis et al reported another mechanism for the photochemical isomerization of bis (b-diketonato)platinum(II) complexes .…”

Section: Resultsmentioning

confidence: 99%

“…The mechanisms of the cis ⇄ trans photoisomerization of platinum(II) species were discussed previously. Balzani et al 66 and Richardson et al 67 studied the photochemical isomerization of [Pt(gly) 2 ] (gly = glycinato) 68 They proposed that one bond cleavage results in the formation of a short-lived three-coordinate intermediate by quantum chemical calculations. We cannot specify the mechanism at this stage, but the fact that photodecomposition product is not observed in the reaction may show that the complete ligand dissociation at the excited states does not occur.…”

Section: Cis-and Trans-[pt(ppy)(l-pbc)]mentioning

confidence: 99%

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Circularly Polarized Luminescence of Cyclometalated Platinum(II) Complex Excimers: Large Difference between Isomers

Morikubo

Tsubomura

2022

Inorg. Chem.

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A series of platinum(II) complexes bearing a chiral β-diketonato ligand and a cyclometalated ligand have been prepared. The platinum(II) complexes, (SP-4-3)-[Pt(ppy)(D-tac)] (ppy = 2-phenylpyridine, D-tac = 3-trifluoroacetyl-(D)-camphor), (SP-4-4)-[Pt(ppy)(D-tac)], (SP-4-3)-[Pt(ppy)(D-pbc)] (D-pbc = 3-perfluorobutyryl-(D)-camphor), and (SP-4-4)-[Pt(ppy)(D-pbc)], and their enantiomers were isolated and characterized by elemental analysis, NMR, and X-ray structural analysis. Photoisomerization between SP-4-3 (trans) and SP-4-4 (cis) isomers was observed. Green emission due to the monomer was observed in diluted solutions for all complexes. Higher quantum yields and longer lifetimes of green emission were observed in nonpolar solvents compared to polar solvents. The two geometrical isomers had surprisingly different excimer formation efficiencies. For the trans isomers, orange emission due to the excimers was observed in nonpolar solvents at high concentrations, whereas negligible intensities of the excimer emission were observed for the cis isomers. The formation of the excimers was evaluated by emission decay and time-resolved emission spectra. For the trans isomers, the green emission due to the monomer showed negligible CPL signals, but the orange emission gave pronounced CPL signals. The dissymmetry factors, g-values, of the excimer CPL (g lum = 0.002) were enhanced over those of the circular dichroism (g abs = 0.0002, g lum/g abs = 10). The intensities of the emission and the CPL of the excimer under oxygen were very small, although those under an argon atmosphere were very strong. Therefore, the emission color of the trans-isomers was changed from green to orange by deoxygenation.

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Section: Resultsmentioning

confidence: 99%