Crystal engineering based on noncentrosymmetric metal–organic frameworks (MOFs) by using asymmetric bridging ligands as building blocks has attracted much attention owing to its potential applications as second-order nonlinear optical (NLO) materials. 1–4 The utilization of asymmetric bridging ligands can introduce electronic asymmetry (push–pull effect), which is essential for a second harmonic generation (SHG) response. At present, there are numerous ...