A new three-dimensional coordination framework, [Zn4(tbazip)3(bpe)2(OH)2]·bpe·{solvent} (where bpe = 1,2-di(4-pyridyl)ethene) containing the novel photoactive ligand tbazip (tbazip = 5-((4-tert-butyl)phenylazo)isophthalic acid) has been synthesised and crystallographically characterised. The photoactivity of discrete tbazip was investigated and compared with its photoactivity while incorporated within the framework. The effect of isomerisation of the incorporated azobenzene on the chemical and physical properties of the framework were investigated using UV-vis and Raman spectroscopies. The framework is porous only to hydrogen gas at 77 K, but displayed an appreciable uptake for CO2 at 195 K.