Synthesis of Vinylene-Linked Two-Dimensional Conjugated Polymers via the Horner-Wadsworth-Emmons Reaction.

In this work, we demonstrate the first synthesis of vinylene-linked 2D CPs, namely, 2D poly(phenylenequinoxalinevinylene)s 2D-PPQV1 and 2D-PPQV2, via the Horner-Wadsworth-Emmons (HWE) reaction of C2 -symmetric 1,4-bis(diethylphosphonomethyl)benzene or 4,4'-bis(diethylphosphonomethyl)biphenyl with C3 -symmetric 2,3,8,9,14,15-hexa(4-formylphenyl)diquinoxalino[2,3-a:2',3'-c]phenazine as monomers. Density functional theory (DFT) simulations unveil the crucial role of the initial reversible C-C single bond formation for the synthesis of crystalline 2D CPs. Powder X-ray diffraction (PXRD) studies and nitrogen adsorption-desorption measurements demonstrate the formation of proclaimed crystalline, dual-pore structures with surface areas of up to 440 m2  g-1 . More importantly, the optoelectronic properties of the obtained 2D-PPQV1 (Eg =2.2 eV) and 2D-PPQV2 (Eg =2.2 eV) are compared with those of cyano-vinylene-linked 2D-CN-PPQV1 (Eg =2.4 eV) produced by the Knoevenagel reaction and imine-linked 2D COF analog (2D-C=N-PPQV1, Eg =2.3 eV), unambiguously proving the superior conjugation of the vinylene-linked 2D CPs using the HWE reaction.