Electronic absorption and resonance Raman spectra of tricarbonyl(p-tolyl-1,4-diaza-1,3-butadiene)halorhenium. Evidence for a lowest ligand to ligand charge-transfer (LLCT) transition

Stor, G.J.; Stufkens, Derk J.; Oskam, A.

doi:10.1021/ic00034a005

Cited by 33 publications

(18 citation statements)

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“…a(C-Re) to phen. Similar LLCT electronic transitions placed at higher energies have been identified in other fac-Re(l) tricarbonyl complexes [15][16][17][18]. Since the chromophores in (C) are dicarbonyl complexes, the ionization potential of the LUMO, a a(C-Re) orbital, and therefore the energy of the ligand to ligand charge transfer transition could be smaller than in the tricarbonyl complexes.…”

Section: Discussionsupporting

confidence: 53%

UV Photolysis of a Re(I) Macromolecule, [(4-vinylpyridine)₂(4-vinylpyridineRe(C0)₃(1,10-phenanthroline)⁺]₂₀₀: Addition of C-centered Radicals to Coordinated CO

Wolcan

Ferraudi²,

Feliz

et al. 2003

Supramolecular Chemistry

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Section: Discussionsupporting

confidence: 53%

UV Photolysis of a Re(I) Macromolecule, [(4-vinylpyridine)₂(4-vinylpyridineRe(C0)₃(1,10-phenanthroline)⁺]₂₀₀: Addition of C-centered Radicals to Coordinated CO

Wolcan

Ferraudi²,

Feliz

et al. 2003

Supramolecular Chemistry

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“…Another possible explanation for the significant differences in the excited state lifetimes would be if the ancillary ligand altered the type of excited state populated. ,,, Vlček and co-workers have shown that ancillary ligand variation, where L = Cl – , Br – and I – can alter the nature of the lowest lying emitting state, changing from MLCT to XLCT upon progressing from Cl – to I – . − This increase in halide character was accompanied by an increase of the lifetime. However, in the case of the [Re(L)(CO) 3 (phen-TPA)] n + complexes, interpretation of the dynamic data does not require inclusion of an XLCT state specifically, due to the distinct similarity between the vibrational spectra of all four complexes.…”

Section: Resultsmentioning

confidence: 99%

“…45,46 Another possible explanation for the significant differences in the excited state lifetimes would be if the ancillary ligand altered the type of excited state populated. 6,12,47,48 Vlcěk and coworkers have shown that ancillary ligand variation, where L = Cl − , Br − and I − can alter the nature of the lowest lying emitting state, changing from MLCT to XLCT upon progressing from Cl − to I − . 5−7 This increase in halide character was accompanied by an increase of the lifetime.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Dramatic Alteration of ³ILCT Lifetimes Using Ancillary Ligands in [Re(L)(CO)₃(phen-TPA)]ⁿ⁺ Complexes: An Integrated Spectroscopic and Theoretical Study

et al. 2018

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The ground and excited state photophysical properties of a series of fac-[Re(L)(CO)(α-diimine)] complexes, where L = Br, Cl, 4-dimethylaminopyridine (dmap) and pyridine (py) have been extensively studied utilizing numerous electronic and vibrational spectroscopic techniques in conjunction with a suite of quantum chemical methods. The α-diimine ligand consists of 1,10-phenanthroline with the highly electron donating triphenylamine (TPA) appended in the 5 position. This gives rise to intraligand charge transfer (ILCT) states lying lower in energy than the conventional metal-to-ligand charge transfer (MLCT) state, the energies of which are red and blue-shifted, respectively, as the ancillary ligand, L becomes more electron withdrawing. The emitting state is ILCT in nature for all complexes studied, characterized through transient absorption and emission, transient resonance Raman (TR), time-resolved infrared (TRIR) spectroscopy and TDDFT calculations. Systematic modulation of the ancillary ligand causes unanticipated variation in the ILCT lifetime by 2 orders of magnitude, ranging from 6.0 μs for L = Br to 27 ns for L = py, without altering the nature of the excited state formed or the relative order of the other CT states present. Temperature dependent lifetime measurements and quantum chemical calculations provide no clear indication of close lying deactivating states, MO switching, contributions from a halide-to-ligand charge transfer (XLCT) state or dramatic changes in spin-orbit coupling. It appears that the influence of the ancillary ligand on the excited state lifetime could be explained in terms of energy gap law, in which there is a correlation between ln( k) and E with a slope of -21.4 eV for the ILCT emission.

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“…In order to illustrate the presence of such correlations, we start by scrutinizing the excited states of the complex [Re(Cl)(CO) 3 (bipy)] (bipy=2,2'-bipyridine); this rhenium carbonyl diimine complex will be more thoroughly examined later in section 4.5. For now, it is su cient to mention that the excited-state characters of this and related complexes are discussed in the literature due to the strong mixing between Re→L and (CO) 3 →L excitations [29,57], and in the case of halogeno-complexes also X→L, with X being the halogen and L the diimine ligand (e.g., bipy) [119,120]. This strong mixing is clearly appreciated in Figure 8, which displays charge transfer numbers for the rst 20 singlets and rst 20 triplets of [Re(Cl)(CO) 3 (bipy)].…”

Section: Correlations Between Charge Transfer Numbersmentioning

confidence: 99%

Quantitative wave function analysis for excited states of transition metal complexes

Mai

Dorn

Fumanal

et al. 2018

Coordination Chemistry Reviews

130

163

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The character of an electronically excited state is one of the most important descriptors employed to discuss the photophysics and photochemistry of transition metal complexes. In transition metal complexes, the interaction between the metal and the di erent ligands gives rise to a rich variety of excited states, including metal-centered, intra-ligand, metal-to-ligand charge transfer, ligand-to-metal charge transfer, and ligand-to-ligand charge transfer states. Most often, these excited states are identi ed by considering the most important wave function excitation coe cients and inspecting visually the involved orbitals. This procedure is tedious, subjective, and imprecise. Instead, automatic and quantitative techniques for excited-state characterization are desirable. In this contribution we review the concept of charge transfer numbers-as implemented in the TheoDORE package-and show its wide applicability to characterize the excited states of transition metal complexes. Charge transfer numbers are a formal way to analyze an excited state in terms of electron transitions between groups of atoms based only on the well-de ned transition density matrix. Its advantages are many: it can be fully automatized for many excited states, is objective and reproducible, and provides quantitative data useful for the discussion of trends or patterns. We also introduce a formalism for spin-orbit-mixed states and a method for statistical analysis of charge transfer numbers. The potential of this technique is demonstrated for a number of prototypical transition metal complexes containing Ir, Ru, and Re. Topics discussed include orbital delocalization between metal and carbonyl ligands, nonradiative decay through metal-centered states, e ect of spin-orbit couplings on state character, and comparison among results obtained from di erent electronic structure methods.

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Electronic absorption and resonance Raman spectra of tricarbonyl(p-tolyl-1,4-diaza-1,3-butadiene)halorhenium. Evidence for a lowest ligand to ligand charge-transfer (LLCT) transition

Cited by 33 publications

References 0 publications

UV Photolysis of a Re(I) Macromolecule, [(4-vinylpyridine)₂(4-vinylpyridineRe(C0)₃(1,10-phenanthroline)⁺]₂₀₀: Addition of C-centered Radicals to Coordinated CO

UV Photolysis of a Re(I) Macromolecule, [(4-vinylpyridine)₂(4-vinylpyridineRe(C0)₃(1,10-phenanthroline)⁺]₂₀₀: Addition of C-centered Radicals to Coordinated CO

Dramatic Alteration of ³ILCT Lifetimes Using Ancillary Ligands in [Re(L)(CO)₃(phen-TPA)]ⁿ⁺ Complexes: An Integrated Spectroscopic and Theoretical Study

Quantitative wave function analysis for excited states of transition metal complexes

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Electronic absorption and resonance Raman spectra of tricarbonyl(p-tolyl-1,4-diaza-1,3-butadiene)halorhenium. Evidence for a lowest ligand to ligand charge-transfer (LLCT) transition

Cited by 33 publications

References 0 publications

UV Photolysis of a Re(I) Macromolecule, [(4-vinylpyridine)2(4-vinylpyridineRe(C0)3(1,10-phenanthroline)+]200: Addition of C-centered Radicals to Coordinated CO

UV Photolysis of a Re(I) Macromolecule, [(4-vinylpyridine)2(4-vinylpyridineRe(C0)3(1,10-phenanthroline)+]200: Addition of C-centered Radicals to Coordinated CO

Dramatic Alteration of 3ILCT Lifetimes Using Ancillary Ligands in [Re(L)(CO)3(phen-TPA)]n+ Complexes: An Integrated Spectroscopic and Theoretical Study

Quantitative wave function analysis for excited states of transition metal complexes

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UV Photolysis of a Re(I) Macromolecule, [(4-vinylpyridine)₂(4-vinylpyridineRe(C0)₃(1,10-phenanthroline)⁺]₂₀₀: Addition of C-centered Radicals to Coordinated CO

UV Photolysis of a Re(I) Macromolecule, [(4-vinylpyridine)₂(4-vinylpyridineRe(C0)₃(1,10-phenanthroline)⁺]₂₀₀: Addition of C-centered Radicals to Coordinated CO

Dramatic Alteration of ³ILCT Lifetimes Using Ancillary Ligands in [Re(L)(CO)₃(phen-TPA)]ⁿ⁺ Complexes: An Integrated Spectroscopic and Theoretical Study