Photoactivated linkage isomerism in single crystals of nickel, palladium and platinum di-nitro complexes--a photocrystallographic investigation

Low temperature, single crystal photocrystallographic studies have been carried out on four square planar Group 10 complexes [Ni(PEt(3))(2)(NO(2))(2)] 1, [Pd(PPh(3))(2)(NO(2))(2)] 2, [Pd(AsPh(3))(2)(NO(2))(2)] 3 and [Pt(PPh(3))(2)(NO(2))(2)] 4, in which the two nitro groups adopt the trans configura...

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Bibliographic Details
Published in:Dalton transactions : an international journal of inorganic chemistry 2012-11, Vol.41 (42), p.13173-13179
Main Authors: Warren, Mark R, Brayshaw, Simon K, Hatcher, Lauren E, Johnson, Andrew L, Schiffers, Stefanie, Warren, Anna J, Teat, Simon J, Warren, John E, Woodall, Christopher H, Raithby, Paul R
Format: Article
Language:English
Subjects:
Absorption spectroscopy
Conversion
Correlation
Crystals
Isomerization
Mathematical analysis
Nickel
Single crystals
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Summary:Low temperature, single crystal photocrystallographic studies have been carried out on four square planar Group 10 complexes [Ni(PEt(3))(2)(NO(2))(2)] 1, [Pd(PPh(3))(2)(NO(2))(2)] 2, [Pd(AsPh(3))(2)(NO(2))(2)] 3 and [Pt(PPh(3))(2)(NO(2))(2)] 4, in which the two nitro groups adopt the trans configuration. Irradiation with UV light, at 100 K, of single crystals of complexes 1-3 photoisomerise from the η(1)-NO(2) nitro form to the η(1)-ONO nitrito form occurred. Complex 1 underwent 25% conversion to the nitrito form before crystal decomposition occurred. 2 and 3 underwent 46% and 39% conversion, respectively, to the nitrito form when a photostationary state was reached. While under the same experimental conditions 4 showed no isomerisation. The photocrystallographic results can be correlated with the results of DFT calculations and with the observed trends in the solution UV/visible absorption spectroscopy obtained for these complexes. The results suggest that while steric factors in the isomerization processes are important there may also be a kinetic effect relating to the lability of the metal involved.
ISSN:1477-9226
1477-9234
DOI:10.1039/c2dt30314k