Tetrahedral Tetrakis(p‐ethynylphenyl) Group IV Compounds in Microporous Polymers: Effect of Tetrel on Porosity

Abstract

Three Sonogashira–Hagihara polymerization protocols were applied for the synthesis of conjugated microporous polymers (CMPs) by using group IV tetra(p‐ethynylphenyl) monomers with 1,4‐diiodobenzene or 1,4‐dibromobenzene. The optical properties and surface areas of the CMPs were compared and related to the preparation conditions and the geometry of the tetrahedral building block as obtained after X‐ray analysis. In each series, surface areas decreased—independently from the chosen parameters of catalyst, base, and solvent—from carbon‐centered CMPs (1595 m2 g−1) to silicon‐, germanium‐, and tin‐centered (649 m2 g−1) networks.

Porous organic polymers incorporating BODIPY moieties for efficient removal of organic dyes from aqueous solutions

“…In addition, for BIPOP-2, the single peak at 67 ppm is attributed to a quaternary atom. Moreover, the structure of BIPOP-1 was determined by solid-state 29 Si CP/ MAS NMR (Fig. 1d), where a peak at −15.6 ppm was observed, confirming the presence of silicon atoms from tetrahedral silicon centers.…”

“…2,6-Bromine-1,3,5,7-tetramethyl-8-phenyl-4,4-difluoroboradiazaindacene (also named dibrominated boron dipyrromethenes, M-1), tetrakis(4-ethynylphenyl)silane (M-2), and 2,2′,7,7′-tetraethynyl-9,9′-spirobifluorene (M-3) were synthesized following the procedures in previous studies. 29–31…”

“…2,6-Bromine-1,3,5,7-tetramethyl-8-phenyl-4,4-difluoroboradiazaindacene (also named dibrominated boron dipyrromethenes, M-1), tetrakis(4-ethynylphenyl)silane (M-2), and 2,2′,7,7′-tetraethynyl-9,9′-spirobifluorene (M-3) were synthesized following the procedures in previous studies. [29][30][31] Synthesis of BODIPY-incorporating porous organic polymers (BIPOPs) BIPOP-1. In a three-necked flask, M-1 (840 mg, 2 mmol), M-2 (432.6 mg, 1 mmol), Pd(PPh 3 ) 4 (92.44 mg, 0.08 mmol), CuI (38.1 mg, 0.2 mmol), triethylamine (50 mL) and N,N-dimethylformamide (DMF, 50 mL) were mixed under argon.…”

Amorphous porous organic polymers containing main group elements

“…d Crystal structures of the S-/Si-/Ge-/Sn-monomers for the synthesis of C-P4, Si-P4, Ge-P2, and Sn-P2 (adapted with permission from ref. 79 © 2018 John Wiley and Sons). …”

“…Later, the same group carried out the systematic studies on Group-14 a POPs (Fig. 8c , C-P4, Si-P4, Ge-P2, and Sn-P2) 79 . These a POPs exhibited a decreasing trend of BET surface areas with increasing atomic number of the central atom (C, Si, Ge, Sn).…”