Charge-transfer absorption and emission of Cu(NN)2+ systems

Ichinaga, A. K.; Kirchhoff, Jon R.; McMillin, David R.; Dietrich‐Buchecker, Christiane; Marnot, Pascal A.; Sauvage, Jean Pierre

doi:10.1021/ic00272a030

Cited by 173 publications

(162 citation statements)

References 9 publications

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“…[3] Substituents at the 2 and 9 positions reduce the degree of excited-state distortion, [3,4] leading to room-temperature emission for most copper(i) complexes of 2,9-disubstituted-1,10-phenanthrolines.…”

Section: A Photoluminescent Copper(i) Complex With An Exceptionally Hmentioning

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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Section: A Photoluminescent Copper(i) Complex With An Exceptionally Hmentioning

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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“…Copper(I) diimine coordination complexes (denoted [Cu I (NN) 2 ] + ) have a long, rich history that parallels that of their transition-metal cousins, polypyridyl ruthenium(II) systems [1][2][3][4][5][6][7][8][9][10][11] . Current interest is driven by a desire to employ transition metal coordination complexes in applications from solar energy conversion 12 to chemical sensing 13,14 and molecular devices.…”

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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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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“…p ⁄ transitions [52][53][54]. The higher energy region is dominated by an intense UV band at 275 nm for 1 and 2 which is assigned to p ?…”

Section: Characterizationmentioning

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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Charge-transfer absorption and emission of Cu(NN)2+ systems

Abstract: Supplementary Material Available: Tables of coordinates and isotropic thermal parameters for hydrogen atoms and anisotropic thermal parameters (2 pages); listings of observed and calculated structure factors (14 pages). Ordering information is given on any current masthead page.

Cited by 173 publications

References 9 publications

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

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

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

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

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