Two novel porous materials, namely, Zn₄O(TPB)_4/3(BDC) and chiral Zn₄O(TPB)_4/3(chir-BDC), have been synthesised by copolymerisation of the newly developed triarylborane linker 4,4′4″-boranetriyltris(3,5-dimethylbenzoic acid) (H₃TPB) with the linear 1,4-benzenedicarboxylic acid (H₂BDC) and chir-H₂BDC, respectively. The compounds adopt ith-d topology and are microporous. The BET surface area of Zn₄O(TPB)_4/3(BDC) determined from the nitrogen adsorption isotherm measured at 77 K is 2874 m² g^-1 and both frameworks are accessible to organic dye molecules, the largest being Rhodamine B. Thus, the two compounds are the first examples of non-interpenetrated, highly accessible metal-organic frameworks comprising a triarylborane linker. The framework shows an enhanced isosteric heat of CO₂ adsorption in comparison to the isoreticular DUT-6 compound.