Copolymerization of CO₂ and epoxides is an industrially relevant means to alleviate anthropogenic carbon emissions and non-degradable plastic pollution. Despite recent advances, few studies have focused on controlling the enchainment of ether and carbonate segments, a process that determines the performance of the material. Here we report precise control of the enchainment of ether and carbonate segments by using a series of well-defined dinuclear organoboron catalysts. By altering the catalyst structure and optimizing reaction conditions, the alternating carbonate content in the propylene oxide/CO₂ copolymer is finely regulated over a wide range of 3.0–95.2%, and the polyether content is arbitrarily varied between <0.1% and 97.0%. A unique microstructure, the -ABB- linkage, is identified by NMR spectroscopy, hydrolysis-derivatization experiments and single-crystal X-ray diffraction. Density functional theory calculations indicate that the -ABB- microstructure originates from a regioselectivity-directed copolymerization process. By analysis of the crystal structures of four catalysts and their catalytic performance, we quantified a correlation between dinuclear organoboron catalyst structure and sequence selectivity (-AB-, -ABB- and -AB_n-, n ≥ 3) in propylene oxide/CO₂ copolymerization, which should enable new catalyst design for this sustainable transformation.

CO ₂和环氧化物的共聚是减轻人为碳排放和不可降解塑料污染的工业相关手段。尽管最近取得了进展，但很少有研究集中在控制醚和碳酸酯链段的链结上，这一过程决定了材料的性能。在这里，我们报告了通过使用一系列明确的双核有机硼催化剂对醚和碳酸酯链段的精确控制。通过改变催化剂结构和优化反应条件，使环氧丙烷/CO _{2中的碳酸盐含量交替变化}共聚物在3.0-95.2%的宽范围内精细调节，聚醚含量在<0.1%至97.0%之间任意变化。通过核磁共振光谱、水解衍生实验和单晶 X 射线衍射鉴定出独特的微结构 -ABB- 键。密度泛函理论计算表明-ABB-微观结构源自区域选择性定向的共聚过程。 通过分析四种催化剂的晶体结构及其催化性能，我们量化了双核有机硼催化剂结构与环氧丙烷/CO ₂中的序列选择性（-AB-、-ABB-和-AB _n-，n≥3 ）之间的相关性。共聚，这应该能够为这种可持续转变设计新的催化剂。