Competitive energy-transfer and reductive quenching of the CT excited states of copper(l) phenanthrolines

Cunningham, Kurstan L.; Hecker, Clark R.; McMillin, David R.

doi:10.1016/0020-1693(95)04859-6

Cited by 50 publications

(76 citation statements)

References 28 publications

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“…In particular, cuprous diimine complexes have been considered as potential substitutes for ruthenium (II) and osmium(II) systems. 18 McMillin and coworkers 3,[19][20][21][22][23][24] performed pioneering work for elucidating the unique photophysics and photochemistry of [Cu I (NN) 2 ] + complexes and developed a fundamental picture of the photophysics occurring on the nanosecond timescale. 6 Their experimental observations led to remarkable insights into the properties of these systems in their excited states.…”

Section: Introductionmentioning

confidence: 99%

“…McMillin recognized the potential for JahnTeller distortion causing a structural rearrangement from the tetrahedral ground state to square planar or trigonal bipyramidal geometries following a metal-to-ligand-charge-transfer (MLCT) excitation in [Cu I (NN) 2 ] + complexes. 3,[23][24][25] Also, he proposed the model for exciplex quenching by Lewis bases to explain solvent-dependent luminescence and excited state lifetimes. 3,19,26 Despite the lack of any direct structural evidence, the exciplex formation hypothesis was supported by the correlation between accessibility of the cuprous center by the solvent and the luminescence lifetime, and was widely accepted.…”

Section: Introductionmentioning

confidence: 99%

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Ultrafast Structural Rearrangements in the MLCT Excited State for Copper(I) bis-Phenanthrolines in Solution

et al. 2007

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Ultrafast excited state structural dynamics of [Cu I (dmp) 2 ] + (dmp = 2,9-dimethyl-1,10-phenanthroline) have been studied to identify structural origins of transient spectroscopic changes during the photoinduced metal-to-ligand-charge-transfer (MLCT) transition that induces an electronic configuration change from Cu(I) (3d 10 ) to Cu(II) (3d 9 ). This study has important connections with the flattening of the Franck-Condon state tetrahedral geometry and the ligation of Cu(II)* with the solvent observed in the thermally equilibrated MLCT state by our previous laser-initiated time-resolved x-ray absorption spectroscopy (LITR-XAS) results. To better understand the structural photodynamics of

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Ultrafast Structural Rearrangements in the MLCT Excited State for Copper(I) bis-Phenanthrolines in Solution

et al. 2007

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“…This barrier results from the high inner-sphere reorganization energy associated with the repopulation of a ds* orbital. [6,21] On the other hand, oxidative quenching of *[Cu(bfp) 2 ]…”

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confidence: 99%

“…[2h, 21,22] In addition, oxidative quenching with viologens can be anticipated to occur with very high cage-escape yields.…”

mentioning

confidence: 99%

A Photoluminescent Copper(I) Complex with an Exceptionally High CuII/CuI Redox Potential: [Cu(bfp)2]+ (bfp=2,9-bis(trifluoromethyl)-1,10-phenanthroline)

Miller

Gantzel

Karpishin

1998

Angewandte Chemie International Edition

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Unprecedented stabilization of the copper(I) oxidation state is demonstrated for the complex cation [Cu(bfp) ] (1) due to the steric and electronic effects of the CF groups (E (Cu /Cu )=+1.55 V vs. SCE). The redox existence range of the copper(I) species is remarkably high at 2.77 V. It is emissive in solution at room temperature and shows great potential as a photocatalyst; in the excited state it is a very potent photooxidant.

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“…In particular, copper(I) diimine complexes have been considered as potential substitutes for ruthenium(II) and osmium(II) systems. Pioneering work toward elucidation of the unique photophysical and photochemical properties of [Cu I (N^N) 2 ] + complexes has been reported by McMillin and co-workers over the last 35 years [9][10][11][12][13][14][15]. Owing to the significant similarities in absorption spectra and photophysical behavior there have been recent attempt to replace Ru(II) with Cu(I) diimine complexes in dye-sensitized solar cells (DSSCs) [16][17][18][19][20].…”

Section: Introductionmentioning

confidence: 99%

Homoleptic tetraazaphenanthrene-based copper(I) complexes: Synthesis, spectroscopic characterization, crystal structures and computational studies

Kia

Scholz

Raithby

et al. 2014

Inorganica Chimica Acta

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a b s t r a c tThree new Cu(I) complexes containing bidentate N^N donor ligands with the general formula [Cu (N^N) , were prepared by the reaction of [Cu(CH 3 CN) 4 ][PF 6 ] with two equivalents of the N^N ligand. Single-crystal X-ray diffraction analysis confirmed that in each complex the metal displays a distorted tetrahedral geometry surrounded by the four N atoms of the two sterically hindered substituted tetraazaphenanthrene (TAP) ligands. Density functional theory (DFT) and time-dependent density functional theory (TD-DFT), calculations were used to study the ground state properties and interpret the absorption spectra for these Cu(I) complexes. The calculations show that the lowest-energy excitations of all complexes are dominated by dp(Cu) ? p ⁄ (L), metal-to-ligand charge transfer, (MLCT) excitations. Electronic difference density maps (EDDMs) were calculated, indicating the change of electron density in the singlet excited states. The degree of filling of the coordination sphere (G parameter) by the ligands was calculated taking into account the ligand-ligand overlap, and compared to the related bis(2,9-disubstituted phenanthroline) Cu(I) complexes.

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Competitive energy-transfer and reductive quenching of the CT excited states of copper(l) phenanthrolines

Cited by 50 publications

References 28 publications

Ultrafast Structural Rearrangements in the MLCT Excited State for Copper(I) bis-Phenanthrolines in Solution

Ultrafast Structural Rearrangements in the MLCT Excited State for Copper(I) bis-Phenanthrolines in Solution

A Photoluminescent Copper(I) Complex with an Exceptionally High CuII/CuI Redox Potential: [Cu(bfp)2]+ (bfp=2,9-bis(trifluoromethyl)-1,10-phenanthroline)

Homoleptic tetraazaphenanthrene-based copper(I) complexes: Synthesis, spectroscopic characterization, crystal structures and computational studies

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