Emitting state energies and vibronic structure in the luminescence spectra of trans-dioxorhenium(V) complexes

Savoie, Carole; Reber, Christian

doi:10.1016/s0010-8545(98)90059-5

Cited by 31 publications

(31 citation statements)

References 15 publications

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“…In contrast, for many compounds with p-donor ligands, a frequency increase is actually observed in the emitting state, indicating that the offset D ML is negative. 7 The offset along the molybdenum(IV)-oxo normal coordinate is smaller for [MoOF(pyridine) 4 ] + than for [MoOCl(CN-t-Bu) 4 ] + . An This journal is © The Royal Society of Chemistry 2010 important offset along a coordinate with a frequency of 475 cm -1 is observed for [MoOF(pyridine) 4 ] + .…”

Section: Low-temperature Luminescence Spectroscopymentioning

confidence: 99%

“…Transition metal complexes with metal-oxo bonds have a rich variety of excited-state properties, extensively probed in the past mainly for metals of the 5d series. [1][2][3][4][5][6][7][8][9][10][11] One of the key aspects of their low-energy electronic transitions is the influence of strong spin-orbit coupling between the ground state and excited states of identical symmetry, leading to distinct vibronic signatures. 8, 10 Under external pressure, the luminescence band maxima of transdioxo complexes show a red shift and changes in the intensity distribution within the high-frequency vibronic progression involving the symmetric metal-oxo stretching mode, 9,10, 12 whose frequency shows a linear increase with pressure.…”

Section: Introductionmentioning

confidence: 99%

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Pressure-dependent luminescence spectroscopy of molybdenum(iv) oxo complexes

2010

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Luminescence spectra are reported for trans-[MoOCl(CN-t-Bu)(4)]BPh(4) and trans-[MoOF(pyridine)(4)]BPh(4). The maxima of the broad luminescence bands are at energies of 12000 and 13000 cm(-1), respectively. Resolved vibronic structure involves the metal-oxo stretching mode with a vibrational frequency of approximately 950 cm(-1) (Raman) in both compounds. The pressure behavior of the luminescence bands shows a distinct difference: a blue shift of +12 cm(-1) kbar(-1) is observed for [MoOCl(CN-t-Bu)(4)]BPh(4), and a red-shift of -8 cm(-1) kbar(-1) is obtained for [MoOF(pyridine)(4)]BPh(4). At pressures above 25 kbar, the luminescence maximum of [MoOCl(CN-t-Bu)(4)]BPh(4) shows a change from a blue-shift to a red-shift and the Raman peak corresponding to the metal-oxo stretching mode at 954 cm(-1) becomes broad and its maximum decreases with increasing pressure, leading to a strong deviation from the linear increase of +0.24 cm(-1) kbar(-1) observed at pressures below 25 kbar. These unusual pressure effects are rationalized in terms of the influence of pressure on the metal-ligand bonds and oxo-metal-ligand angles using DFT calculations.

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Section: Low-temperature Luminescence Spectroscopymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Pressure-dependent luminescence spectroscopy of molybdenum(iv) oxo complexes

2010

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“…Long-lived phosphorescence from oxido and nitrido complexes featuring M=O, O=M' = O or M'≡N (M = Mo IV ; M' = Tc V , Re V , Os VI ) moieties is well known [148][149][150][151][152][153][154]. Although all of these complexes feature a d 2 electronic configuration, their emission does not arise from an intraconfigurational spin-flip state but rather from an interconfigurational MC states.…”

Section: Spin-flip Emitters Based On Other Transition Metals and Elec...mentioning

confidence: 99%

“…Although all of these complexes feature a d 2 electronic configuration, their emission does not arise from an intraconfigurational spin-flip state but rather from an interconfigurational MC states. The complexes' D 4h symmetry and strong -bonds to the nitrido or oxido ligands give rise to a 1 A 1 ground state with (d xy ) 2 configuration and an emissive 3 E state with (d xy ) 1 (d yz , d xz ) 1 configuration [148][149][150][151][152][153][154], which is distinctly different from the 3 T 1 ground state and 1 T 2 / 1 E spin-flip states expected for octahedral d 2 complexes (Fig. 1a) [50].…”

Section: Spin-flip Emitters Based On Other Transition Metals and Elec...mentioning

confidence: 99%

Spin-flip luminescence

Kitzmann

Moll

Heinze

2022

Photochem Photobiol Sci

149

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In molecular photochemistry, charge-transfer emission is well understood and widely exploited. In contrast, luminescent metal-centered transitions only came into focus in recent years. This gave rise to strongly phosphorescent CrIII complexes with a d3 electronic configuration featuring luminescent metal-centered excited states which are characterized by the flip of a single spin. These so-called spin-flip emitters possess unique properties and require different design strategies than traditional charge-transfer phosphors. In this review, we give a brief introduction to ligand field theory as a framework to understand this phenomenon and outline prerequisites for efficient spin-flip emission including ligand field strength, symmetry, intersystem crossing and common deactivation pathways using CrIII complexes as instructive examples. The recent progress and associated challenges of tuning the energies of emissive excited states and of emerging applications of the unique photophysical properties of spin-flip emitters are discussed. Finally, we summarize the current state-of-the-art and challenges of spin-flip emitters beyond CrIII with d2, d3, d4 and d8 electronic configuration, where we mainly cover pseudooctahedral molecular complexes of V, Mo, W, Mn, Re and Ni, and highlight possible future research opportunities. Graphical abstract

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“…The intensity distribution within this cluster of bands is not identical along the progression. This is an experimental evidence for coupled coordinates, 5,6,14,15 discussed and illustrated in the following discussion.…”

Section: Experimental Section and Spectroscopic Resultsmentioning

confidence: 70%

Vibronic structure in the luminescence spectra of tetragonal d2 and d8 complexes analyzed by wavepacket dynamics on two-dimensional potential surfaces

Triest¹,

Masson²,

Grey³

et al. 2000

PhysChemComm

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The luminescence spectra of the tetragonal trans-ReO 2 (vinylimidazole) 4+ complex and the square planar Pd(SCN) 4 2and Pt(SCN) 42complexes all show vibronic progressions in two predominant vibrational modes. In the first complex, the vibronic progressions involve high-frequency and low-frequency metal-ligand modes. In the square planar complexes, the two vibrational modes have similar frequencies. At the intermediate resolution, often observed experimentally, these compounds provide an example of the missing mode (or MIME) effect. Wavepacket dynamics on two-dimensional surfaces explain in a visual and intuitively appealing way the spectroscopic features. The distinct effects are caused by the different frequency ratios between the two modes of the two-dimensional models describing each complex. The emitting state structure determined from the spectra reveals similar changes along a bending normal coordinate for Pd(SCN) 4 2and Pt(SCN) 4 2-.

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Emitting state energies and vibronic structure in the luminescence spectra of trans-dioxorhenium(V) complexes

Cited by 31 publications

References 15 publications

Pressure-dependent luminescence spectroscopy of molybdenum(iv) oxo complexes

Pressure-dependent luminescence spectroscopy of molybdenum(iv) oxo complexes

Spin-flip luminescence

Vibronic structure in the luminescence spectra of tetragonal d2 and d8 complexes analyzed by wavepacket dynamics on two-dimensional potential surfaces

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