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

Mark R. Warren; Simon K. Brayshaw; Lauren E. Hatcher; Andrew L. Johnson; Stefanie Schiffers; Anna J. Warren; Simon J. Teat; John E. Warren; Christopher H. Woodall; Paul R. Raithby

doi:10.1039/c2dt30314k

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

Mark R. Warren, Simon K. Brayshaw, Lauren E. Hatcher, Andrew L. Johnson, Stefanie Schiffers, Anna J. Warren, Simon J. Teat, John E. Warren, Christopher H. Woodall, Paul R. Raithby^*

^*Corresponding author for this work

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Abstract

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.

Original language	English
Pages (from-to)	13173-13179
Number of pages	7
Journal	Dalton Transactions
Volume	41
Issue number	42
DOIs	https://doi.org/10.1039/c2dt30314k
Publication status	Published - 14 Nov 2012

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Warren, M. R., Brayshaw, S. K., Hatcher, L. E., Johnson, A. L., Schiffers, S., Warren, A. J., Teat, S. J., Warren, J. E., Woodall, C. H., & Raithby, P. R. (2012). Photoactivated linkage isomerism in single crystals of nickel, palladium and platinum di-nitro complexes: A photocrystallographic investigation. Dalton Transactions, 41(42), 13173-13179. https://doi.org/10.1039/c2dt30314k

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title = "Photoactivated linkage isomerism in single crystals of nickel, palladium and platinum di-nitro complexes: A photocrystallographic investigation",

abstract = "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.",

author = "Warren, {Mark R.} and Brayshaw, {Simon K.} and Hatcher, {Lauren E.} and Johnson, {Andrew L.} and Stefanie Schiffers and Warren, {Anna J.} and Teat, {Simon J.} and Warren, {John E.} and Woodall, {Christopher H.} and Raithby, {Paul R.}",

year = "2012",

month = nov,

day = "14",

doi = "10.1039/c2dt30314k",

language = "English",

volume = "41",

pages = "13173--13179",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "42",

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TY - JOUR

T1 - Photoactivated linkage isomerism in single crystals of nickel, palladium and platinum di-nitro complexes

T2 - A photocrystallographic investigation

AU - Warren, Mark R.

AU - Brayshaw, Simon K.

AU - Hatcher, Lauren E.

AU - Johnson, Andrew L.

AU - Schiffers, Stefanie

AU - Warren, Anna J.

AU - Teat, Simon J.

AU - Warren, John E.

AU - Woodall, Christopher H.

AU - Raithby, Paul R.

PY - 2012/11/14

Y1 - 2012/11/14

N2 - 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.

AB - 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.

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U2 - 10.1039/c2dt30314k

DO - 10.1039/c2dt30314k

M3 - Article

AN - SCOPUS:84867366818

SN - 1477-9226

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EP - 13179

JO - Dalton Transactions

JF - Dalton Transactions

IS - 42

ER -

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

Abstract

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