Ligand-to-Metal Charge Transfer Excited States with Unprecedented Luminescence Yield in Fluid Solution

Loukova, G. V.; Hühn, W.; Vasiliev, V. P.; Smirnov, V. A.

doi:10.1021/jp0721797

Cited by 53 publications

(59 citation statements)

References 13 publications

(9 reference statements)

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“…As a result of the hydrolysis processes (4)(5)(6) in Table 1, the complexes Zr(AcAc)(OH) 3 (4), Zr(AcAc) 2 (OH) 2 (5) or Zr 4 (OH) 14 (AcAc) 2 (6) should be obtained. Since the computation of the large tetramer structure is very time-consuming, we divided cluster 6 into three dimer fragments with double hydroxo (OH) bridges linking both Zr atoms: Zr 2 (AcAc)(OH) 5 (OH) 2br (7) and two Zr 2 (AcAc) 2 (OH) 4 (OH) 2br complexes (8,9), where the AcAc ligands are connected to different Zr atoms and to one Zr atom, respectively; see Table 1.…”

Section: Resultsmentioning

confidence: 99%

“…It was established that the monomeric Zr(IV)-AcAc unit is the main source of the photophysical properties of the larger Zr chains or rings in the zirconia sol-gel material. Based on the best congruence between the simulated UV-Vis and IR spectra and the corresponding experimental spectra of the Zr-AcAc sol-gel, the dimeric double hydroxo-bridged species Zr 2 (AcAc) 2 (OH) 4 (OH) 2br (9) and the dimeric monooxo bridged species Zr 2 (AcAc) 2 (OH) 4 O br ·2H 2 O (12) were predicted to be the most likely building blocks for the ZrAcAc gel. In both structures, the two AcAc ligands are coordinated to one Zr atom.…”

Section: Discussionmentioning

confidence: 98%

“…To obtain data on the molecular geometries of Zr(IV)-AcAc complexes formed in butanol/aqueous solution, two groups of model complex structures were considered in the gas phase at the DFT level: monomeric (4, 5) and dimeric double hydroxobridged (7,8,9); see Table 1. Dimeric Zr(IV)-AcAc complexes with double hydroxo bridging have been reported in the literature, and data on their structures are available [39].…”

Section: Dft Modeling and Uv-vis Spectra Simulations [Tddft And Adc(2mentioning

confidence: 99%

“…4), where the Fig. 4 Experimental UV-Vis spectrum of Zr-AcAc sol (n AcAc /n Zr = 0.6) compared to simulated ones of Zr(AcAc) 2 (OH) 2 ⋅2H 2 O (5), Zr 2 (AcAc) 2 (OH) 4 (OH) 2br (9) and Zr 2 (AcAc) 2 (OH) 4 (OH) 2br ·2H 2 O (8). Vertical excitation energies and oscillator strengths were calculated with the RI-ADC(2) method Fig.…”

Section: Dft Modeling and Uv-vis Spectra Simulations [Tddft And Adc(2mentioning

confidence: 99%

“…Recently, we synthesized hybrid zirconia sol-gel materials modified with acetylacetone (AcAc) [7], and demonstrated that modifying agents like AcAc and nitric acid decrease the optical band gap of the sol-gel zirconia from 4.84 eV to about 3 eV. Doping with AcAc leads to yellow-brown materials [7][8][9]. The well-known color of AcAc-containing zirconia sol-gel materials is caused by Zr(IV)-AcAc complex formation during hydrolysis in the liquid (sol) state, which exhibits strong absorption in the UV region and low-intensity absorption in the visible spectral region [7].…”

Section: Introductionmentioning

confidence: 99%

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DFT modeling, UV-Vis and IR spectroscopic study of acetylacetone-modified zirconia sol-gel materials

et al. 2011

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Theoretical and spectroscopic studies of a series of monomeric and dimeric complexes formed through the modification of a zirconium butoxide precursor with acetylacetone and subsequent hydrolysis and/or condensation have been performed by applying DFT/B3LYP/6-31++G(d) and highly accurate RI-ADC(2) methods as well as IR and UV-Vis transmittance and diffuse reflectance spectroscopies. Based on DFT model calculations and simulated and experimental UV-Vis and IR spectra of all the studied structures, the most probable building units of the Zr(IV)-AcAc gel were predicted: the dimeric double hydroxo-bridged complex Zr(2)(AcAc)(2)(OH)(4)(OH)(2br) 9 and the monooxo-bridged complex Zr(2)(AcAc)(2)(OH)(4)O(br)·2H(2)O 12. In both structures, the two AcAc ligands are coordinated to one Zr atom. It was shown that building units 9 and 12 determine the photophysical and vibrational properties of the gel material. The observed UV-Vis and IR spectra of Zr(IV)-AcAc gel were interpreted and a relation between the spectroscopic and structural data was derived. The observed UV-Vis bands at 315 nm and 298/288 nm were assigned to partial ligand-metal transitions and to intra-/inter-AcAc ligand transitions, respectively.

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Section: Resultsmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 98%

Section: Dft Modeling and Uv-vis Spectra Simulations [Tddft And Adc(2mentioning

confidence: 99%

Section: Dft Modeling and Uv-vis Spectra Simulations [Tddft And Adc(2mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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DFT modeling, UV-Vis and IR spectroscopic study of acetylacetone-modified zirconia sol-gel materials

et al. 2011

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Photoluminescence and mechanoluminescence of solid‐state zirconocene dichlorides

et al. 2021

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Spectral-luminescence properties of 23 samples of zirconium complexes were studied. Mechanoluminescence spectra of 10 complexes were obtained. The solid-state component of the mechanoluminescence spectrum, that is the luminescence of the crystal itself, coincided with the photoluminescence spectra of these complexes, which indicated identical emission from the same excited states in mechanoluminescence and photoluminescence, despite the different ways of excitation. The luminescence maximum was red shifted as substituents appeared in the ligand, in particular in the presence of a bridging group connecting π-ligands (ansa-complexes) and also for a substituted bis-indenyl complex rac-Me 2 Si(2-Me-4-Ph-5-OMe-6-Bu t -Ind) 2 ZrCl 2 ). It was found that mechanical destruction of the rac-isomer of complex Mе 2 С(2-Me-4-Bu t -C 5 H 2 ) 2 ZrCl 2 , unlike that of the meso-isomer, was accompanied by a more than a 10-fold increase in intensity and by a shift in the mechanoluminescence spectrum to longer wavelengths.

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Early–Late Heterometallic Complexes of Gold and Zirconium: Photoluminescence and Reactivity

Bestgen

Schoo

Zovko

et al. 2016

Chemistry A European J

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OH functionalized triarylphosphines were used to assemble zirconocene-based metalloligands with phosphine donor sites in varying positions. These complexes were subsequently treated with different gold precursors to obtain early-late heterometallic compounds in which the metal atoms exhibit different intermetallic distances. All compounds were fully investigated by spectroscopic techniques, photoluminescence measurements and single crystal X-ray diffraction. Quantum chemical calculations were also performed. Some compounds show bright emission even at room temperature with quantum yields of up to 19 % (excitation at 350 nm). Furthermore, the reactivity of dimethyl zirconocene derivatives towards gold complexes was investigated, revealing simultaneous ligand exchange and transmetallation reactions.

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Ligand-to-Metal Charge Transfer Excited States with Unprecedented Luminescence Yield in Fluid Solution

Cited by 53 publications

References 13 publications

DFT modeling, UV-Vis and IR spectroscopic study of acetylacetone-modified zirconia sol-gel materials

DFT modeling, UV-Vis and IR spectroscopic study of acetylacetone-modified zirconia sol-gel materials

Photoluminescence and mechanoluminescence of solid‐state zirconocene dichlorides

Early–Late Heterometallic Complexes of Gold and Zirconium: Photoluminescence and Reactivity

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