Projects per year
Abstract
At temperatures below 150K, the photoactivated metastable endo-nitrito linkage isomer [Ni(Et4dien)(η2-O,ON)(η1-ONO)] (Et4dien=N,N,N',N'-tetraethyldiethylenetriamine) can be generated with 100% conversion from the ground state nitro-(η1-NO2) isomer on irradiation with 500nm light, in the single crystal by steady-state photocrystallographic techniques. Kinetic studies show the system is no longer metastable above 150K, decaying back to the ground state nitro-(η1-NO2) arrangement over several hours at 150K. Variable-temperature kinetic measurements in the range of 150-160K show that the rate of endo-nitrito decay is highly dependent on temperature, and an activation energy of Eact=+48.6(4)kJmol-1 is calculated for the decay process. Pseudo-steady-state experiments, where the crystal is continually pumped by the light source for the duration of the X-ray experiment, show the production of a previously unobserved, exo-nitrito-(η1-ONO) linkage isomer only at temperatures close to the metastable limit (ca. 140-190K). This exo isomer is considered to be a transient excited-state species, as it is only observed in data collected by pseudo-steady-state methods.
Original language | English |
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Pages (from-to) | 3128-3134 |
Number of pages | 7 |
Journal | Chemistry - A European Journal |
Volume | 20 |
Issue number | 11 |
Early online date | 12 Feb 2014 |
DOIs | |
Publication status | Published - 10 Mar 2014 |
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Dive into the research topics of 'Steady-state and pseudo-steady-state photocrystallographic studies on linkage isomers of [Ni(Et4dien)(η2-O,ON)(η1-NO2)]: Identification of a new linkage isomer'. Together they form a unique fingerprint.Projects
- 3 Finished
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Applying Long-Lived Metastable States in Switchable Functionality via Kinetic Control of Molecular Assembly
Raithby, P. (PI), Burrows, A. (CoI), Lewis, D. (CoI), Marken, F. (CoI), Parker, S. (CoI), Walsh, A. (CoI) & Wilson, C. (CoI)
Engineering and Physical Sciences Research Council
1/11/12 → 30/04/18
Project: Research council
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Dynamic Structural Science at the RC@H
Raithby, P. (PI)
Engineering and Physical Sciences Research Council
1/03/11 → 31/08/16
Project: Research council
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NON-AMBIENT STUDIES ON OPTO-ELECTRONIC MATIERALS
Raithby, P. (PI)
Engineering and Physical Sciences Research Council
1/10/08 → 30/09/12
Project: Research council
Equipment
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MC2- X-ray diffraction (XRD)
Material and Chemical Characterisation (MC2)Facility/equipment: Technology type