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Regioselective Photochemical Cycloaddition Reactions of Diolefinic Ligands in Coordination Polymers
Author(s) -
Li NiYa,
Liu Dong,
Lang JianPing
Publication year - 2019
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201900646
Subject(s) - regioselectivity , cycloaddition , chemistry , adipate , ligand (biochemistry) , cyclobutane , adipic acid , photochemistry , medicinal chemistry , stereochemistry , polymer chemistry , organic chemistry , catalysis , ring (chemistry) , biochemistry , receptor
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(NO 3 ) 2 ⋅4 H 2 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.