An unprecedented "strongly" self-catenated MOF containing inclined catenated honeycomb-like units.

A 3D 4-coordinated self-catenated metal-organic framework {[Co(bibp)(1,4-chdc)]·2H2O}n (1) (bibp = 4,4'-bis(1-imidazolyl)biphenyl, 1,4-H2chdc = 1,4-cyclohexanedicarboxylic acid) has been synthesized by hydrothermal reaction and its structure has been determined. This framework buries an unprecedented 4-coordinated self-catenated net that can be represented as an array of honeycomb-like units catenated in an inclined mode, with the highest topological density among the 4-coordinated nets that occur in crystal structures. Additionally, the thermogravimetric, photo-catalytic and electrochemical behaviors have been investigated.