▎ 摘　　要

The present study introduces the mechanisms for the oriented external electric field (OEEF)-participating cycloadditions of nanographene and the analogous hexagonal boron nitride (h-BN) nanoflakes. Despite the C-C and B-N pairs being isoelectronic, their different ionicities give rise to their distinct response to applied electric fields. For the nanographene models, the Diels-Alder addition obeyed the reaction axis rule and the activation barrier changed under an OEEF perpendicular to the carbon skeleton for enhanced/reduced intermolecular charge transfer, which provides a feasible strategy for the side-selective derivatization of graphene to obtain one-face-only adducts and Janus bifunctional products. By contrast, for the h-BN models, the variation of the activation barrier was pronounced when the electric field was aligned along the in-plane N-B bond rather than the well-accepted reaction axis. Electronic structure analyses indicated that, because of the opposite electron withdrawing/donating nature of the reacting sites of B/N, an OEEF along the N-B bond was capable of further enhancing the polarizationviain-plane intramolecular charge transfer, resulting in a stabilized transition state and notable barrier reduction.