Herein we report selective P–C and P–N chemistry as a new synthetic tool for constructing phosphorus (P)-chromophores with rich chemical structures. Our studies reveal that isomeric structures significantly influence the chemical structure and electronic communication of P-heteropines, which results in efficient tunability of the photophysical properties. In particular, isomeric P-chromophores with a protic N–H (indole) are also capable of participating in intramolecular H bonding, offering a new strategy to access a near-infrared chromophore.

Porous organic polymers (POPs) have drawn significant attention in diverse applications. However, factors affecting the heterogeneous polymerization and porosity of POPs are still not well understood. Herein, we report a new strategy to construct porous organophosphorus polymers (POPPs) with high surface areas (1283 m2/g) and ultramicroporous structures (0.67 nm). The strategy harnesses an efficient transition-metal-catalyzed phosphorus–carbon (P–C) coupling reaction at the trigonal pyramidal P-center, which is distinct from the typical carbon–carbon coupling reaction utilized in the synthesis of POPs. As the first kinetic study on the coupling reaction of POPs, we uncovered a self-accelerating reaction characteristic, which is controlled by the choice of bases and catalysts. The self-accelerating characteristic of the P–C coupling reaction is beneficial for the high surface area and uniform ultramicroporosity of POPPs. The direct crosslinking of the P-centers allows 31P solid-state (ss)­NMR experiments to unambiguously reveal the crosslinking environments of POPPs. Leveraging on the kinetic studies and 31P ssNMR studies, we were able to reveal the kinetic effects of the P–C coupling reaction on both the crosslinking environments and the porous structures of POPPs. Furthermore, our studies show that the CO2 uptake capacity of POPPs is highly dependent on their porous structures. Overall, our studies paves the way to design new POPs with better controlled chemical and ultramicroporous structures, which have potential applications for CO2 capture and separation.

Conjugated porous polymers (CPPs) have drawn significant attention in materials science. We envisioned that simple building blocks may provide a more general platform for constructing functional CPPs. Herein, we report a new synthetic strategy to incorporate a simple boron element building block into CPPs by using efficient boron/tin (B/Sn) exchange reaction, which is distinct from the commonly employed Pd-catalyzed C–C coupling toward CPPs in the literature. More importantly, this synthetic strategy allows us to construct the first example of the CPPs having the nonprotected B-centers and the highest B-content reported to date, which is beneficial for strong Lewis acid–base interactions. The boron (B)-CPPs exhibit the well-defined chemical structures and the microsized porous structures. This synthetic protocol also allows us to access the B-CPPs having the smallest aromatic linker between the B-centers, which can enhance the electronic communications of the adjacent B-centers and increase Lewis acidity of the B-centers. Because of the strong electronic communications of the adjacent B-centers via the p−π* coupling, the B-CPPs exhibit higher Lewis acidity compared to that of the B-monomer. Combining the high microporosity, the high Lewis acidity, and small steric protection of the B-centers endows these B-CPPs with excellent triethylamine and pyridine sensing and absorptivity properties.

Due to the efficient intersystem crossing (ISC), combined with efficient non-radiative processes of the triplet excited state, oligothiophenes generally exhibit very weak photoluminescence. Phosphorus (P)-bridged terthiophenes (P-terThs) and phosphorus (P)-bridged...