Gaining mechanistic insights into the structure-performance relationship connecting the donor and acceptor is essential to the rational design of high performance nonlinear optics (NLO) materials. Here, intramolecular boron/nitrogen (B/N)-locking strategies in combination with various electron-withdrawing groups, R (R = TXO, DPzS, TTR, DPyS, DTC, DSCZ, DMPS and TXO2), are proposed to address this issue. With the decreasing of torsion angles (θ