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

University of Bath
Lawrence Berkeley National Laboratory

Research output: Contribution to journal › Article › peer-review

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

@article{c622cc098dd54c9bb01e86939dfc2b39,

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",

}

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.

UR - https://www.scopus.com/pages/publications/84867366818

U2 - 10.1039/c2dt30314k

DO - 10.1039/c2dt30314k

M3 - Article

AN - SCOPUS:84867366818

SN - 1477-9226

VL - 41

SP - 13173

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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