Han Lei, Fan Chunyang, Liu Yawei, Yang Yuhan, Li Haipeng, Tang Luhao, Li Hao, Liu Yanan, Wu Hong, Jiang Zhongyi
School of Chemistry and Chemical Engineering, Hainan University, Hainan, 570228, P. R. China.
Beijing Key Laboratory of Solid State Battery and Energy Storage Process, CAS Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing, 100190, P. R. China.
Small. 2025 Sep;21(35):e2506441. doi: 10.1002/smll.202506441. Epub 2025 Jul 7.
Covalent organic polymer (COP) nanosheets hold great potential for widespread applicability, but their fabrication remains challenging. Here, a dipole-moment-mediation strategy is reported to manipulate solute-solvent interactions, enabling the facile synthesis of COP nanosheets under ambient conditions. Three COPs with different morphologies are synthesized from three amine monomers with ascending dipole moment (Qd: 0.69 D, PDA: 1.46 D, VON: 2.37 D) and 1,3,5-triformylphloroglucinol (TP) in dimethyl sulfoxide (3.93 D). Combined with experimental results and quantitative analysis from DFT calculations, monomers with higher dipole moments generate stronger solute-solvent interactions. The strong solute-solvent interactions (-0.271 eV) significantly disrupt intermolecular interactions (-0.058 eV), suppressing 3D random aggregation in TP-VON, and facilitating in-plane anisotropic growth, producing laterally expanded nanosheets. The TP-VON nanosheets colloidal suspensions are cast into free-standing, continuous, and compact membranes with exceptional chemical stability, achieving a proton conductivity of 176.55 ± 4.31 mS cm (80 °C, 95% relative humidity) and tensile strength of 47.00 MPa after being doped with phosphoric acid. It is believed that this dipole-moment-mediation strategy opens a new paradigm for the synthesis of COP nanosheets.
共价有机聚合物（COP）纳米片具有广泛应用的巨大潜力，但其制备仍然具有挑战性。在此，报道了一种偶极矩介导策略来操纵溶质 - 溶剂相互作用，从而能够在环境条件下轻松合成COP纳米片。由三种偶极矩递增的胺单体（Qd：0.69 D，PDA：1.46 D，VON：2.37 D）和1,3,5 - 三甲酰基间苯三酚（TP）在二甲基亚砜（3.93 D）中合成了三种不同形态的COP。结合实验结果和DFT计算的定量分析，偶极矩较高的单体产生更强的溶质 - 溶剂相互作用。强溶质 - 溶剂相互作用（-0.271 eV）显著破坏分子间相互作用（-0.058 eV），抑制TP - VON中的三维随机聚集，并促进面内各向异性生长，产生横向扩展的纳米片。将TP - VON纳米片胶体悬浮液浇铸成具有优异化学稳定性的独立、连续且致密的膜，在掺杂磷酸后，实现了176.55±4.31 mS cm的质子传导率（80°C，95%相对湿度）和47.00 MPa的拉伸强度。据信，这种偶极矩介导策略为COP纳米片的合成开辟了新的范例。
