Coordination Polymer-Mediated Molecular Surgery for Precise Interconversion of Dicyclobutane Compounds.

A Cd(II)-based coordination polymer {[Cd2(5-F-1,3-bpeb)2(FBA)4]·H2O}n (CP1) was obtained from Cd(II) salt, 5-fluoro-1,3-bis[2-(4-pyridyl)ethenyl]benzene (5-F-1,3-bpeb), and p-fluorobenzoic acid (HFBA). Within the one-dimensional chain structure of CP1, a pair of 5-F-1,3-bpeb was arranged in a face-to-face style. Upon UV irradiation and heat treatment, multiple cyclobutane isomers, including specific monocyclobutanes (1 with an endo-cyclobutane ring in CP1-1 and 1' with an exo-cyclobutane ring in CP1-1') and dicyclobutanes (endo,endo-dicyclobutane 2α in CP1-2α, exo,endo-dicyclobutane 2β in CP1-2β, and exo,exo-dicyclobutane 2γ in CP1-2γ) were stereoselectively produced. These isomers could be interconverted inside the CP via cutting/coupling specific bonds, which may be regarded as a type of molecular surgery. The precision of cutting/coupling relied on the thermal stability of the cyclobutanes and the alignment of the reactive alkene centers. The conversion processes were tracked through nuclear magnetic resonance, in situ powder X-ray diffraction, and IR spectroscopy. This approach can be considered as skeletal editing to construct complex organic compounds directly from one precursor.