Department of Chemistry , University of Iowa , Iowa City , Iowa 52242 , United States.
Inorg Chem. 2019 Oct 7;58(19):12497-12500. doi: 10.1021/acs.inorgchem.9b01306. Epub 2019 Sep 25.
A single-crystal-to-single-crystal (SCSC) photodimerization is achieved using Au(I) coordination and aurophilic interactions. The rigid Au(dppbz)(CFCOO) precursor (dppbz = 1,2-bis(diphenylphosphino)benzene) self-assembles with 1,2--bis(4-pyridyl)ethylene (bpe) to afford a discrete [Au(dppbz)(bpe)] macrocycle in the solid state. The alkene undergoes a [2 + 2] photocycloaddition reaction. The photoreaction proceeds via a rare SCSC transformation in quantitative yield that generates [Au(dppbz)(4,4'-tpcb)] (4,4'-tpcb = -tetrakis(4-pyridyl)cyclobutane) stereoselectively. Mechanical strain induced by the photoreaction is evidenced by the formation of ramp features on single-crystal surfaces using scanning electron microscopy.
利用金（I）配位和金键相互作用实现了单晶到单晶（SCSC）光二聚反应。刚性的 Au(dppbz)(CFCOO)前体（dppbz = 1,2-双（二苯基膦基）苯）与 1,2--双（4-吡啶基）乙烯（bpe）自组装，在固态下提供离散的[Au(dppbz)(bpe)]大环。烯烃经历[2 + 2]光环加成反应。光反应通过定量产率的罕见 SCSC 转化进行，立体选择性地生成[Au(dppbz)(4,4'-tpcb)]（4,4'-tpcb = -四（4-吡啶基）环丁烷）。使用扫描电子显微镜在单晶表面形成斜坡特征，证明了光反应引起的机械应变。
