title: In-situ X-ray diffraction snapshotting: determination of the kinetics of a photodimerization within a single crystal.
abstract: In a single-crystal-to-single-crystal (SCSC) transformation, a preformed three-dimensional coordination polymer,[Ni3(oba)2(bpe)2(SO4)(H2O)4]· H2O (H2oba = 4,4'-oxydibenzoic acid; bpe = (E)-1,2-di(pyridin-4-yl)ethane) (1), was shown to undergo a [2+2] cycloaddition reaction upon exposure to UV irradiation. The kinetics of this reaction were followed by taking "snapshots" of the solid state transformation using in situ single crystal X-ray crystallography; a first order process was indicated. The reaction rate was influenced by many factors such as the separation of the sample from the UV light source, the heat produced by the UV irradiation, the light flux of the UV lamp used, the size of the single-crystal and the powder samples. The investigation of the kinetics was complemented by (1)H NMR studies. The results clearly demonstrate that in situ single-crystal X-ray diffraction is able to provide useful insights into the gradual formation of the photoproducts and the reaction processes. The work also offers a clear indication that it is possible to use the technique to study the kinetics of other photocycloaddition reactions and SCSC processes in general.
authors.affiliation: College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, People's Republic of China.
authors.forename: Fei-Long
authors.initials: FL
authors.lastname: Hu
authors.affiliation: College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, People's Republic of China.
authors.forename: Shu-Long
authors.initials: SL
authors.lastname: Wang
authors.affiliation: 1] College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, People's Republic of China [2] State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, People's Republic of China.
authors.forename: Jian-Ping
authors.initials: JP
authors.lastname: Lang
authors.affiliation: School of Chemistry, University of Melbourne, Victoria 3010, Australia.
authors.forename: Brendan F
authors.initials: BF
authors.lastname: Abrahams