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Vinyl functionalized Biphephos ligand, denoted as vinyl biphephos, has been succesfully synthesized.

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A multifunctional copolymer (PyPPh2 -SO3 H@porous organic polymers, POPs) was prepared by combining acidic groups and heterogeneous P,N ligands through the copolymerization of vinyl-functionalized 2-pyridyldiphenylphosphine (2-PyPPh2 ) and p-styrene sulfonic acid under solvothermal conditions. The morphology and chemical structure of the copolymer were evaluated using a series of characterization techniques. Compared with traditional homogeneous Pd(OAc)2 /2-PyPPh2 / p-toluenesulfonic acid catalyst, the copolymer supported palladium catalyst (Pd-PyPPh2 -SO3 H@POPs) exhibited higher activity for alkoxycarbonylation of terminal alkynes under the same conditions. This phenomenon could be attributed to the synergistic effect between the single-site Pd centers, 2-PyPPh2 ligands, and SO3 H groups, the outstanding swelling properties as well as the high enrichment of the reactant concentration by the porous catalyst. In addition, the catalyst could be reused at least 4 times without any apparent loss of activity. The excellent catalytic reactivity and good recycling properties make it an attractive catalyst for industrial applications. This work paves the way for advanced multifunctional porous organic polymers as a new type of platform for heterogeneous catalysis in the future.

Doping carbon materials with p-block elements such as nitrogen is an effective approach to tune electronic properties of the framework and can endow the host's new characters. To date, highly doped carbons with tunable nitrogen speciation are still less explored due to the grand challenge in fabrication; for example, the typical synthesis based on the pyrolysis of nitrogencontaining precursors shows a trade-off between the total nitrogen content and the carbonization temperature, limiting the value to ≈12 wt% at 1073 K. Herein, intensifying ring opening of cross-linked polymers through controlled pre-oxidation followed by conventional pyrolysis is demonstrated as an elegant method to circumvent this challenge. In addition to fine tunability at different nitrogen speciation, this strategy can increase the nitrogen content by two-to threefold (maximum ≈22 wt%) and shows general viability in six different N-bearing (co)polymers. The highly doped pyridinic nitrogen-rich carbons show i) a remarkable capacity of 879 mAh g −1 at 0.1 A g −1 and excellent cycling performance in lithium ion batteries, and ii) significantly boosted catalytic performance in the selective oxidation of diverse substrates. Therefore, this facile synthetic strategy and the tunability at nitrogen functionalities will greatly broaden the applications of this new class of functional materials.

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