Taking advantage of the well-defined geometry of metal centers and highly directional metal-ligand coordination bonds, metal-organic frameworks (MOFs) have emerged as promising candidates for nonlinear optical (NLO) materials. In this work, taking a photoresponsive carboxylate triphenylamine derivative as an organic ligand, a bismuth-based MOF, Bi-NBC, NBC = 4',4‴,4‴″-nitrilotris(([1,1'-biphenyl]-4-carboxylic acid)) is obtained. Structure determination reveals that it is a potential NLO material derived from its noncentrosymmetric structure, which is finally confirmed by its rarely strong second harmonic generation (SHG) effect. Theoretical calculations reveal that the potential difference around Bi atoms is large; therefore, it leads to a strong local built-in electric field, which greatly facilitates the charge separation and transfer and finally improves the photocatalytic performance. Our results provide a reference for the exploration of MOFs with NLO properties.
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