Regioselective Photochemical Cycloaddition Reactions of Diolefinic Ligands in Coordination Polymers

The pure diolefinic ligand 1,4-bis(pyridin-4-yl)-1,3-butadiene (bpbde) is photostable in the crystalline state. With the assistance of coordination-driven metal-organic assemblies, the photoreactivity of this diolefinic ligand can be significantly enhanced. A hydrothermal reaction of bpbde with Cd(NO₃ )₂ ⋅4 H₂ O and the auxiliary ligand adipic acid resulted in the formation of a two-dimensional photoreactive coordination polymer (CP), [Cd(adipate)(bpbde)]_n (1). When the aliphatic carboxylic acid was replaced by pimelic acid, another photoreactive CP [Cd(pimelate)(bpbde)]_n (2) with a three-dimensional framework was obtained. With irradiation of 365 nm UV light, the bpbde ligands in crystalline 1 and 2 underwent a regioselective photochemical [2+2] cycloaddition reaction and converted to 3,4,7,8-tetra(pyridin-4-yl)tricyclo[4.2.0.0^2,5 ]octane (tptco) and 1,3-bis(pyridin-4-yl)-2,4-bis(2-(pyridin-4-yl)vinyl)cyclobutane (bpbpvcb), respectively. The results provide an interesting insight into the rational design of highly regio- or stereoselective photocatalytic reactions for the formation of special organic molecules.