Photochemical and kinetic studies of some metal dithizonate complexes

Geoslin, Christine; Adamson, Arthur W.; Gutierrez, A. R.

doi:10.1016/s0020-1693(00)89661-9

Cited by 31 publications

(23 citation statements)

References 15 publications

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“…We consider that the interaction of alcohol molecules with the central metal in Pd(HD Z ) 2 is operating at a high concentration of alcohols. Geosling et al [4] have suggested that the isomerization rates of dithizonate complexes are related to the nature of the central metal, based on the hard-soft concept. Therefore, it is likely that the coordination of the alcohol molecule to the central metal gives rise to the retardation in return rates.…”

Section: The Isomerization Of Palladium Dithizonate In Toluene-alcohomentioning

confidence: 99%

Kinetic studies of specific solvent effect on the thermal isomerization of palladium dithizonate in toluene-alcohol mixtures

Sueishi

Takashima

Yamamoto

2000

Int. J. Chem. Kinet.

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The kinetics of the thermal isomerization of palladium dithizonate (Pd(HDZ)2) in the binary mixture of toluene and alcohols has been studied. In the solvent effects on the Pd(HDZ)2 isomerization rates, we found that the maximum lies in the range x = 0.02 ∼ 0.2 (x represents the mole fraction of alcohols). The experimental kinetic data for the specific solvent effect with maximum can be reproduced well by taking into account hydrogen bonding and coordination of alcohols with Pd(HDZ)2. The rate constants for the thermal isomerization of Pd(HDZ)2 involving hydrogen bonding and the coordinate interaction with 1‐butanol are evaluated. © 2000 John Wiley & Sons, Inc. Int J Chem Kinet 32: 542–547, 2000

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Section: The Isomerization Of Palladium Dithizonate In Toluene-alcohomentioning

confidence: 99%

Kinetic studies of specific solvent effect on the thermal isomerization of palladium dithizonate in toluene-alcohol mixtures

Sueishi

Takashima

Yamamoto

2000

Int. J. Chem. Kinet.

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“…the reversible interconversion between two molecular forms endowed with different absorption properties, observed both under UV-vis steady illumination 3,4 and laser pulse photolysis. 5 The color change from red to violet blue is usually regarded as an inherent property of the HDz − ligand, since the involved electronic transitions are essentially localized on its molecular orbital system, whereas the nature of metal centers seems to influence only the speed of the interconversion process. 6 The photochromic interconversion opens appealing possibilities for the use of the above complexes in various fields.…”

Section: Introductionmentioning

confidence: 99%

Molecular photochromic systems: a theoretical and experimental investigation on zinc(II) dithizonate

Armelao

Bandoli

Barreca

et al. 2007

Applied Organom Chemis

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Zinc(II)-dithizone based molecular systems [Zn(HDz) 2 ] are intriguing candidates for the development of optical devices thanks to their interesting photochromic and nonlinear optical properties. In the present work, the behavior of Zn(HDz) 2 in different solvents was investigated by a combined theoretical and experimental approach. In particular, solutions of both dithizone (H 2 Dz) and Zn(HDz) 2 were analyzed by optical absorption spectroscopy and nuclear magnetic resonance (NMR) techniques, with particular attention to structure-properties relationships. Density functional and time-dependent density functional calculations were performed on the stable and the activated forms of the complex, obtaining information on the energetics of their interconversion, as well as on the nature of their electronic excitations.

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“…However, an estimate of ca 1700 m 2 mol À1 for the blue forms of the 1:1 organomercury(II) dithizonates reported here is reasonable in view of the values 3900 and 2700 m 2 mol À1 reported for the blue form of the 1:2 mercury(II) bis(dithizonate) in benzene. 8,25 While the half-life of the labile blue form of the parent mercury(II) bis(dithizonate) in chloroform is of the order of 1 min, 7,8,25 the same parameter for the organomercury(II) dithizonates 3a-3e was consistently increased. Difficulty was encountered in obtaining reproducible thermal return rates for these compounds, but a qualitative study indicated that the half-lives increased with increasing chain length of the alkoxy substituent: a maximum value of ca 6 min was recorded for the compound 3e.…”

Section: Photochromic Behaviourmentioning

confidence: 97%

Photochromic long-chain organomercury(II) dithizonate complexes in the azomethine series

Cromhout

Hutton

2000

Appl. Organometal. Chem.

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The synthesis and characterization of a seriesof 4 ‐ (4′‐ n ‐alkoxybenzylideneimino)phenyl‐mercury(II) dithizonates, [CnH2n+1OC6H4CHNC6H4Hg(Hdptc)] (H2dptc = 1,5‐diphenylthiocarbazone = dithizone; n = 1, 4, 12, 14 or 18), is described. The intermediate long‐chain organomercury(II) acetates were obtained by condensation of 4‐aminophenylmercury(II) acetate with the appropriate 4‐n‐alkoxybenzaldehydes. The thermal behaviour of the complexes was studied by polarized optical microscopy and differential scanning calorimetry but revealed no mesophases. All of the complexes, however, were reversibly photochromic (yellow ⇌ blue) upon irradiation of chloroform solutions with visible light, and the half‐lives of the metastable blue forms were substantially increased relative to that of the parent mercury(II) bis(dithizonate). The compounds were not photochromic in the solid state. Copyright © 2000 John Wiley & Sons, Ltd.

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Photochemical and kinetic studies of some metal dithizonate complexes

Cited by 31 publications

References 15 publications

Kinetic studies of specific solvent effect on the thermal isomerization of palladium dithizonate in toluene-alcohol mixtures

Kinetic studies of specific solvent effect on the thermal isomerization of palladium dithizonate in toluene-alcohol mixtures

Molecular photochromic systems: a theoretical and experimental investigation on zinc(II) dithizonate

Photochromic long-chain organomercury(II) dithizonate complexes in the azomethine series

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