摘要: The conversion of CO₂ into polymeric materials is a straightforward strategy for stable long-term carbon fixation and possible carbon revitalization if introduced with functionality. Yet, such conversion has long been compromised by expensive catalysts and harsh conditions due to the inactivity of CO₂. In this work, we establish an efficient CuCl/Ph₃P-catalyzed multicomponent polymerization of CO₂, diynes, and dihalides under mild conditions of rt—60 ℃ and atmospheric pressure. The polymerization shows great monomer universality, producing diverse poly(alkynoate)s in yields up to 99% with weight-average molecular weights up to 94 000. Poly(alkynoate)s containing tetraphenylethylene (TPE) moieties show typical aggregation-induced emission features, and can specifically and sensitively detect Fe³⁺ ions with a low limit of detection (LOD) of 1.79×10^-7 M. Notably, owing to lots of activated triple bonds in the main chain of poly(alkynoate)s, N-hydroxyphthalimide derivatives are facilely introduced into this polymerization in situ to establish a ‘one-pot, two-step, four-component' tandem polymerization to produce poly(3a-hydroxyisoxazolo3,2-aisoindol-8(3aH)-ones)s (PHIIOs) with 100% grafting ratio. Interestingly, the fused heterocyclic PHIIO containing TPE could realize the specific and sensitive detection of Ag⁺ ions with a low LOD of 4.90×10^-6 M. This work not only innovatively achieves the direct chemical fixation of CO₂ into functional polymeric materials under relatively low temperatures with low-cost catalysts, but also obtains a series of polymers with controllable structure-function, which can be realized for a wide range of applications.