Rational strategies manipulating hydrogen-bonding and metal-coordination interactions accelerate the development of supramolecular materials with unprecedented properties, such as adaptability, self-healing, stimuli-responsiveness, reprocessability and recyclability. Herein, supramolecular interactions of thioureas were fully utilized to design new materials with adjusted mechanical performances and robust reprocessability. A series of polythioureas were facilely synthesized by the co-polycondensation of CS₂ and two diamines, which was an efficient and economical alternative to the isothiocyanate-based polymerization. Hydrogen-bonded polythiourea materials with tunable mechanical performances were achieved by adjusting the density and regularity of thiourea units in the polymer chains. Further incorporating tiny amount of metal salts (CuCl₂, CuCl, CuBr and CuI) resulted in polythiourea materials with enhanced mechanical performances, following the trend determined by the hard-soft acid-base principle. As far as we know, this is the first report of metal-coordinated polythiourea supramolecular materials. The exploration of hard-soft acid-base principle will also provide new inspirations for designing metal-coordinated supramolecular materials.

操纵氢键和金属配位相互作用的合理策略加速了超分子材料的开发，这些材料具有前所未有的特性，例如适应性、自修复性、刺激响应性、可再加工性和可回收性。在此，充分利用硫脲的超分子相互作用来设计具有调整后的机械性能和强大的可再加工性的新材料。通过CS ₂ 和两种二胺的共缩聚，可以方便地合成一系列聚硫脲，这是异硫氰酸酯聚合的有效且经济的替代方案。通过调节聚合物链中硫脲单元的密度和规整性，获得了具有可调机械性能的氢键聚硫脲材料。进一步掺入微量金属盐（CuCl ₂ 、CuCl、CuBr和CuI）可以使聚硫脲材料具有增强的机械性能，遵循软硬酸碱原理确定的趋势。据我们所知，这是金属配位聚硫脲超分子材料的首次报道。硬软酸碱原理的探索也将为设计金属配位超分子材料提供新的灵感。