A series of heterogeneous metal–organic framework (MOF)-supported rhodium (Rh) hybrid catalysts with varying amounts of Rh are first applied to the coordination polymerization of phenylacetylene and its derivatives with or without cocatalysts in different organic solvents under a nitrogen atmosphere or in water media under an air atmosphere. In comparison with the known homogeneous and heterogeneous Rh catalysts, these MOF-supported Rh catalysts exhibit not only a channel confinement effect on the polymer molecular weight distribution but also a more remarkable cooperation effect, polar solvent acceleration effect, “on water” effect, and cocatalyst acceleration effect on the catalytic activity. As a result, these heterogeneous Rh catalysts have the advantages of an extremely high activity of up to 1.5 × 10⁷ g mol_Rh⁻¹ h⁻¹, cis-selectivity of up to 99%, and reusability of up to 10 times, affording cis-transoidal PPAs and their functional derivatives having single-handed helical conformation or aggregation-induced emission properties with moderate molecular weights and narrow molecular weight distributions. As far as we are aware, such extremely efficient Rh catalysts as well as multiple reusable heterogeneous Rh catalysts have never been reported.

中文翻译：

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基于微孔金属-有机骨架的自支撑铑催化剂，用于苯乙炔及其衍生物的聚合

首先，将一系列具有不同Rh含量的多相金属-有机骨架（MOF）负载的铑（Rh）杂化催化剂用于在氮气氛下或在不同有机溶剂中在有或没有助催化剂的情况下对苯乙炔及其衍生物进行配位聚合。空气中的水介质。与已知的均相和多相Rh催化剂相比，这些MOF负载的Rh催化剂不仅对聚合物分子量分布表现出通道限制作用，而且还表现出更显着的协同作用，极性溶剂促进作用，“对水”作用和助催化剂加速作用对催化活性的影响。结果，这些非均相Rh催化剂具有高达1.5×10 ⁷的极高活性的优点。g mol _Rh ^-1 h ^-1，顺式选择性高达99％，可重复使用性高达10倍，提供具有单手螺旋构象或聚集诱导发射特性且分子中等的顺式-穿环PPA及其功能衍生物分子量和窄分子量分布。据我们所知，从未报道过这种极其有效的Rh催化剂以及多种可重复使用的非均相Rh催化剂。