Electronic structure and photophysics of pseudo-octahedral vanadium(III) oxo complexes

Kittilstved, Kevin R.; Hauser, Andreas

doi:10.1016/j.ccr.2010.02.021

Cited by 15 publications

(10 citation statements)

References 57 publications

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“…Compared to vanadium(III) complexes with oxygen donor ligands, e.g. V(acac) 3 , [37][38][39][40][41]48 the ligand field splitting of [V(ddpd) 2 ] 3+ ( o  23440 cm -1 ) is larger by more than 2500 cm -1 confirming our conceptual approach of using ddpd as strong ligand to prevent back-ISC. 46 Expectedly, the 3 T 1g ground state splits as well, yet the TD-DFT-UKS calculated energy gaps are unreasonably large (Supporting Information, Table S3).…”

Section: Synthesis X-ray Structure and Characterization Of [V III (Ddpd) 2 ] 3+mentioning

confidence: 57%

“…However, the known vanadium(III) compounds display after excitation and intersystem crossing (ISC) only very weak phosphorescence at low temperature, if phosphorescence is observed at all. [37][38][39][40][41] For example, the phosphorescence intensity of V 3+ :Al 2 O 3 is 3-4 orders of magnitude smaller than that of the R lines of ruby (Cr 3+ :Al 2 O 3 ) and the vanadium(III) spin-flip emission has been only detected in the solid state at low temperatures so far. 37,38 Instead, (delayed) fluorescence from vanadium centered 3 T 2g states occurs in compounds with ligand field strengths close to 17.3 B.…”

Section: Introductionmentioning

confidence: 99%

“…[37][38][39][40][41] For example, the phosphorescence intensity of V 3+ :Al 2 O 3 is 3-4 orders of magnitude smaller than that of the R lines of ruby (Cr 3+ :Al 2 O 3 ) and the vanadium(III) spin-flip emission has been only detected in the solid state at low temperatures so far. 37,38 Instead, (delayed) fluorescence from vanadium centered 3 T 2g states occurs in compounds with ligand field strengths close to 17.3 B. 43,44 Consequently, back-ISC from 1 E g / 1 T 2g to 3 T 2g states must be suppressed.…”

Section: Introductionmentioning

confidence: 99%

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A Vanadium(III) Complex with Blue and NIR-II Spin-Flip Luminescence in Solution

et al. 2020

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Luminescence from Earth-abundant metal ions in solution at room temperature is a very challenging objective due to the intrinsically weak ligand field splitting of first row transition metal ions, which leads to efficient non-radiative deactivation via metal-centered states. Only a handful of 3d n metal complexes (n ≠ 10) show sizeable luminescence at room temperature. Luminescence in the near-infrared spectral region is even more difficult to achieve as further non-radiative pathways come into play. No Earth-abundant first-row transition metal complexes display emission > 1000 nm at room temperature in solution up to now. Here we report the vanadium(III) complex mer-[V(ddpd) 2 ][PF 6 ] 3 yielding phosphorescence around 1100 nm in valeronitrile glass at 77 K as well as at room temperature in acetonitrile with 1.810 -4 % quantum yield (ddpd = N,N '-dimethyl-N,N'-dipyridine-2-ylpyridine-2,6-diamine). In addition, mer-[V(ddpd) 2 ][PF 6 ] 3 shows very strong blue fluorescence with 2 % quantum yield in acetonitrile at room temperature. Our comprehensive study demonstrates that vanadium(III) complexes with d 2 electron configuration constitute a new class of blue and NIR-II luminophores, which complement the classical established complexes of expensive precious metals and rare-earth elements.

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Section: Synthesis X-ray Structure and Characterization Of [V III (Ddpd) 2 ] 3+mentioning

confidence: 57%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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A Vanadium(III) Complex with Blue and NIR-II Spin-Flip Luminescence in Solution

et al. 2020

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“…While the broad bands at 742, 1040 nm for 1 and 742, 1100 nm for 2 are assigned to the d-d transition of the vanadium atom. 24,34 The absorption bands of the complex 2 relative to 1 appeared slightly red-shift, which may be attributed to the different ligands and coordination environment.…”

Section: Uv-vis Spectramentioning

confidence: 99%

Novel vanadium(iii) complexes with rigid phenylpolycarboxylate ligands: synthesis, structures and application in C–H bond activation

et al. 2013

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Two novel vanadium(III) complexes: V(dipic)(Hbdc)(H2O)2 (1) and [V2(dipic)2(H2btec)(H2O)4]·2H2O (2) (H2dipic = 2,6-pyridinedicarboxylic acid, H2bdc = 1,3-benzene-dicarboxylic acid, H4btec = 1,2,4,5-benzenetetracarboxylic acid) are synthesized by the reaction of V2(SO4)3, 2,6-pyridinedicarboxylic acid and 1,3-benzene-dicarboxylic acid (for 1) or 1,2,4,5-benzenetetracarboxylic acid (for 2) under hydrothermal condition at 120 °C for 3 days. They were characterized by elemental analysis, IR, UV-Vis, single crystal X-ray diffraction analysis and thermogravimetric analyses (TG). Structural analyses show that the vanadium atoms in the complexes 1 and 2 are both in a pentagonal-bipyramidal coordination environment with the NO6 donor set, and there is intermolecular hydrogen bonding in each complex. Research results found that the complexes exhibited bromination catalytic activity in the single-pot reaction of the conversion of phenol red to bromophenol blue in the mixed solution of H2O-DMF at the constant temperature of 30 ± 0.5 °C with pH = 5.8, and catalytic C-H bond cleavage activity for the peroxidative oxidation (with hydrogen peroxide) of cyclohexane to cyclohexanol and cyclohexanone (the maximum total turnover number is 395) under the mild conditions.

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“…A qualitative conclusion can be drawn from the zfs parameters given in were so helpful in understanding V III complexes with more optically transparent ligands [72,80,121]. Highly recommended in this context is the review in this journal by Kittilstved and Hauser on the electronic structure and photophysics of pseudo-octahedral vanadium(III) oxo complexes [132]. band) EPR spectroscopy since there is always the allowed (M S = ± 1) transition within the M S = ±1/2 Kramers doublet, i.e.…”

Section: (Insert Figure 5 Here)mentioning

confidence: 99%

High-frequency and -field electron paramagnetic resonance of vanadium(IV, III, and II) complexes

Krzystek

Ozarowski

Telser

et al. 2015

Coordination Chemistry Reviews

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In this Review, we discuss the advantages of performing electron paramagnetic resonance (EPR) on coordination and metalloorganic complexes containing various oxidation states of vanadium, from +4 to +2, using the high-frequency and-field version of this technique, known as HFEPR. Thus, HFEPR is advantageous in investigating (S = 1/2) V(IV) species due to its higher g-factor resolution over conventional EPR, albeit at the price of losing the hyperfine structure resolution due to g-strain. It is very much desirable in characterizing (S = 3/2) V(II) complexes since it is capable of precisely and accurately measuring the zero-field splitting present in these species. Finally, HFEPR is indispensable in investigating (S = 1) V(III) species, which in conventional conditions are often "EPR-silent" due to the combination of their large zero-field splitting and integer spin number. The use of HFEPR thus can provide additional information regarding the oxidation state of the metal and the coordination geometry.

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Electronic structure and photophysics of pseudo-octahedral vanadium(III) oxo complexes

Cited by 15 publications

References 57 publications

A Vanadium(III) Complex with Blue and NIR-II Spin-Flip Luminescence in Solution

A Vanadium(III) Complex with Blue and NIR-II Spin-Flip Luminescence in Solution

Novel vanadium(iii) complexes with rigid phenylpolycarboxylate ligands: synthesis, structures and application in C–H bond activation

High-frequency and -field electron paramagnetic resonance of vanadium(IV, III, and II) complexes

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