Hatcher Lauren E, Raithby Paul R
Department of Chemistry, University of Bath, Claverton Down, Bath, Avon BA2 7AY, England.
Acta Crystallogr C. 2013 Dec 15;69(Pt 12):1448-56. doi: 10.1107/S010827011303223X. Epub 2013 Nov 30.
Over the last 30 years, the single-crystal photocrystallographic technique has been developed to determine the three-dimensional crystal and molecular structures of metastable species which have been generated in the crystal photochemically. Transition-metal complexes that have been investigated using this methodology include complexes that contain nitrosyl, dinitrogen, sulfur dioxide and nitrite ligands, all of which form new linkage isomers in the solid state when photoactivated by light of the appropriate wavelength. Both steric and electronic factors determine the level of the conversion from the ground-state structure to the metastable isomeric structure, and both the `reaction cavity' size and the nature of the intermolecular interactions are shown to be among the key factors that influence the percentage conversion.
在过去30年里，单晶光结晶学技术得到了发展，用于确定通过晶体光化学产生的亚稳态物种的三维晶体结构和分子结构。使用这种方法研究的过渡金属配合物包括含有亚硝酰基、二氮、二氧化硫和亚硝酸盐配体的配合物，当用适当波长的光进行光活化时，所有这些配体在固态中都会形成新的键连异构体。空间因素和电子因素都决定了从基态结构到亚稳态异构结构的转化程度，并且“反应腔”大小和分子间相互作用的性质都被证明是影响转化百分比的关键因素。
