Photocrystallographic identification of metastable nitrito linkage isomers in a series of nickel(II) complexes

Simon K Brayshaw, T L Easun, M W George, A M E Griffin, Andrew L Johnson, Paul R Raithby, T L Savarese, Stefanie Schiffers, John E Warren, Mark R Warren, S J Teat

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Abstract

Single crystal photocrystallographic experiments and solid state Raman spectroscopy have been used to determine the low temperature, metastable structures of the nickel(II) nitrito complexes [Ni(aep)(2)(eta(1)-ONO) 2] 1#O (aep = 1-(2-aminoethyl) piperidine), [Ni(aem)(2)(eta(1)-ONO)(2)] 2#O (aem = 1-(2-aminoethyl)morpholine), and [Ni(aepy)(2)(eta(1)-ONO)(2)] 3#O (aepy = 1-(2-aminoethyl) pyrrolidine and where the #O denotes the oxygen-bound nitrito metastable molecule). These linkage isomers of the equivalent nitro complexes [Ni(aep)(2)(eta(1)-NO(2))(2)] 1, [Ni(aem)(2)(eta(1)-NO(2))(2)] 2 and [Ni(aepy)2(eta(1)-NO(2))(2)] 3 are formed by LED irradiation at temperatures below 120 K. The behavior of the three complexes upon irradiation is generally similar, but some subtle differences have been observed. From the crystallographic studies all three complexes 1-3 exhibit the endo-nitrito linkage isomer upon irradiation, however, for 3# (a crystal structure that contains components of both 3 and 3#O) an exo-nitrito isomer is also observed. Under conditions of 90-100 K, with blue light, the conversion percentages to the nitrito isomers, 1#O, 2#O and 3#O were 16%, 22% and 30%, respectively. At temperatures below 110 K all three nitrito isomers were stable for over four hours but while 2#O and 3#O could be detected at temperatures down to 30 K, at temperatures below 60 K the metastable structure 1#O appeared to be quenched and only the nitro isomer 1 was identified in the crystal. The solid state Raman spectra for 1#, 2# and 3# confirmed the photocrystallographic results with the nitrito isomers being identified from the O-N-O deformation vibrations.
LanguageEnglish
Pages90-97
Number of pages8
JournalDalton Transactions
Volume41
Issue number1
DOIs
StatusPublished - Jan 2012

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Nickel
Isomers
Irradiation
Temperature
Light emitting diodes
Raman spectroscopy
Raman scattering
Crystal structure
Single crystals
Oxygen
Crystals
Molecules
epalrestat
Experiments

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Photocrystallographic identification of metastable nitrito linkage isomers in a series of nickel(II) complexes. / Brayshaw, Simon K; Easun, T L; George, M W; Griffin, A M E; Johnson, Andrew L; Raithby, Paul R; Savarese, T L; Schiffers, Stefanie; Warren, John E; Warren, Mark R; Teat, S J.

In: Dalton Transactions, Vol. 41, No. 1, 01.2012, p. 90-97.

Research output: Contribution to journalArticle

Brayshaw, SK, Easun, TL, George, MW, Griffin, AME, Johnson, AL, Raithby, PR, Savarese, TL, Schiffers, S, Warren, JE, Warren, MR & Teat, SJ 2012, 'Photocrystallographic identification of metastable nitrito linkage isomers in a series of nickel(II) complexes', Dalton Transactions, vol. 41, no. 1, pp. 90-97. https://doi.org/10.1039/c1dt11379h
Brayshaw, Simon K ; Easun, T L ; George, M W ; Griffin, A M E ; Johnson, Andrew L ; Raithby, Paul R ; Savarese, T L ; Schiffers, Stefanie ; Warren, John E ; Warren, Mark R ; Teat, S J. / Photocrystallographic identification of metastable nitrito linkage isomers in a series of nickel(II) complexes. In: Dalton Transactions. 2012 ; Vol. 41, No. 1. pp. 90-97.
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abstract = "Single crystal photocrystallographic experiments and solid state Raman spectroscopy have been used to determine the low temperature, metastable structures of the nickel(II) nitrito complexes [Ni(aep)(2)(eta(1)-ONO) 2] 1#O (aep = 1-(2-aminoethyl) piperidine), [Ni(aem)(2)(eta(1)-ONO)(2)] 2#O (aem = 1-(2-aminoethyl)morpholine), and [Ni(aepy)(2)(eta(1)-ONO)(2)] 3#O (aepy = 1-(2-aminoethyl) pyrrolidine and where the #O denotes the oxygen-bound nitrito metastable molecule). These linkage isomers of the equivalent nitro complexes [Ni(aep)(2)(eta(1)-NO(2))(2)] 1, [Ni(aem)(2)(eta(1)-NO(2))(2)] 2 and [Ni(aepy)2(eta(1)-NO(2))(2)] 3 are formed by LED irradiation at temperatures below 120 K. The behavior of the three complexes upon irradiation is generally similar, but some subtle differences have been observed. From the crystallographic studies all three complexes 1-3 exhibit the endo-nitrito linkage isomer upon irradiation, however, for 3# (a crystal structure that contains components of both 3 and 3#O) an exo-nitrito isomer is also observed. Under conditions of 90-100 K, with blue light, the conversion percentages to the nitrito isomers, 1#O, 2#O and 3#O were 16{\%}, 22{\%} and 30{\%}, respectively. At temperatures below 110 K all three nitrito isomers were stable for over four hours but while 2#O and 3#O could be detected at temperatures down to 30 K, at temperatures below 60 K the metastable structure 1#O appeared to be quenched and only the nitro isomer 1 was identified in the crystal. The solid state Raman spectra for 1#, 2# and 3# confirmed the photocrystallographic results with the nitrito isomers being identified from the O-N-O deformation vibrations.",
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N2 - Single crystal photocrystallographic experiments and solid state Raman spectroscopy have been used to determine the low temperature, metastable structures of the nickel(II) nitrito complexes [Ni(aep)(2)(eta(1)-ONO) 2] 1#O (aep = 1-(2-aminoethyl) piperidine), [Ni(aem)(2)(eta(1)-ONO)(2)] 2#O (aem = 1-(2-aminoethyl)morpholine), and [Ni(aepy)(2)(eta(1)-ONO)(2)] 3#O (aepy = 1-(2-aminoethyl) pyrrolidine and where the #O denotes the oxygen-bound nitrito metastable molecule). These linkage isomers of the equivalent nitro complexes [Ni(aep)(2)(eta(1)-NO(2))(2)] 1, [Ni(aem)(2)(eta(1)-NO(2))(2)] 2 and [Ni(aepy)2(eta(1)-NO(2))(2)] 3 are formed by LED irradiation at temperatures below 120 K. The behavior of the three complexes upon irradiation is generally similar, but some subtle differences have been observed. From the crystallographic studies all three complexes 1-3 exhibit the endo-nitrito linkage isomer upon irradiation, however, for 3# (a crystal structure that contains components of both 3 and 3#O) an exo-nitrito isomer is also observed. Under conditions of 90-100 K, with blue light, the conversion percentages to the nitrito isomers, 1#O, 2#O and 3#O were 16%, 22% and 30%, respectively. At temperatures below 110 K all three nitrito isomers were stable for over four hours but while 2#O and 3#O could be detected at temperatures down to 30 K, at temperatures below 60 K the metastable structure 1#O appeared to be quenched and only the nitro isomer 1 was identified in the crystal. The solid state Raman spectra for 1#, 2# and 3# confirmed the photocrystallographic results with the nitrito isomers being identified from the O-N-O deformation vibrations.

AB - Single crystal photocrystallographic experiments and solid state Raman spectroscopy have been used to determine the low temperature, metastable structures of the nickel(II) nitrito complexes [Ni(aep)(2)(eta(1)-ONO) 2] 1#O (aep = 1-(2-aminoethyl) piperidine), [Ni(aem)(2)(eta(1)-ONO)(2)] 2#O (aem = 1-(2-aminoethyl)morpholine), and [Ni(aepy)(2)(eta(1)-ONO)(2)] 3#O (aepy = 1-(2-aminoethyl) pyrrolidine and where the #O denotes the oxygen-bound nitrito metastable molecule). These linkage isomers of the equivalent nitro complexes [Ni(aep)(2)(eta(1)-NO(2))(2)] 1, [Ni(aem)(2)(eta(1)-NO(2))(2)] 2 and [Ni(aepy)2(eta(1)-NO(2))(2)] 3 are formed by LED irradiation at temperatures below 120 K. The behavior of the three complexes upon irradiation is generally similar, but some subtle differences have been observed. From the crystallographic studies all three complexes 1-3 exhibit the endo-nitrito linkage isomer upon irradiation, however, for 3# (a crystal structure that contains components of both 3 and 3#O) an exo-nitrito isomer is also observed. Under conditions of 90-100 K, with blue light, the conversion percentages to the nitrito isomers, 1#O, 2#O and 3#O were 16%, 22% and 30%, respectively. At temperatures below 110 K all three nitrito isomers were stable for over four hours but while 2#O and 3#O could be detected at temperatures down to 30 K, at temperatures below 60 K the metastable structure 1#O appeared to be quenched and only the nitro isomer 1 was identified in the crystal. The solid state Raman spectra for 1#, 2# and 3# confirmed the photocrystallographic results with the nitrito isomers being identified from the O-N-O deformation vibrations.

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