Synthesis and Properties of Conjugated Microporous Polymers Bearing Pyrazine Moieties with Macroscopically Porous 3D Networks Structures

Abstract

The N‐containing conjugated microporous polymers (CMPs) are synthesized by 2,5‐dibromopyrazine or its isomeric pyridazine monomer and 1,3,5‐triethynylbenzene via the Pd(0)/Cu(I)‐catalyzed Sonogashira–Hagihara cross‐coupling polycondensation. The resulting CMPs exhibit diverse porosity and morphology, which reveals macroscopically porous 3D networks for BQCMP‐1, agglomerated and amorphous structure for DQCMP‐1, arising from the variation of isomeric monomer. In addition, metal ions adsorption capacity of Zn(II), Cr(VI), Ni(II) have been investigated due to the good porosity of CMPs. Compared with Zn(II) and Cr(VI), the adsorption capacity of Ni(II) for BQCMP‐1 and DQCMP‐1 is maximal, which is 272 mg g−1 and 559 mg g−1. Our study may provide a useful guidance to manipulate CMPs by varying the constitution of isomeric monomer.

Novel thiophene-bearing conjugated microporous polymer honeycomb-like porous spheres with ultrahigh iodine uptake

“…20,21 Also, the high designable flexibility of CMPs makes it possible to exquisitely control both the chemical nature and desired porosity of CMPs by simply varying the molecular structure or chemical constitution of CMP building blocks. [22][23][24][25] Previous studies have proven that both the desired porous features of absorbents and high affinity of host materials to iodine would enhance the iodine uptakes of a porous absorbent. [17][18][19] We have demonstrated that the choice of both monomer structures and solvents should lead to different morphology or pore structures.…”

Ultramicroporous Polyphenylenes via Diels–Alder Polycondensation Approach

“…In this work, we used two multitopic monomers possessing different geometries, namely tetrakis(4-ethynylphenyl)methane and 1,3,5-triethynylbenzene, as the structural units for PPPhs synthesis by the Diels-Alder polycondensation reaction with bulky phenylene-substituted bis(cyclopentadienone)s. Previously, the aforementioned ethynyl-containing compounds were used in the POP synthesis by Sonogashira-Hagihara cross-coupling and Yamamoto polymerization reactions, yielding crosslinked insoluble products [15,17,41,42]. Our approach results in soluble polyphenylenes with SSA up to 751 m 2 /g, which could be effectively controlled during the synthesis.…”

Selective and Reversible Capture of Volatile I2 Modifying As-Synthesized 2D Cd-MOF to 3D

“…On the one hand, silver-based zeolites or aerogels not only have limited available surface areas (low uptake of I 2 ) but also their high cost and adverse environmental impact make these compounds less suitable for I 2 capture. On the other hand, conjugated microporous polymers (CMPs) or porous organic polymers (POPs) show excellent iodine capture due to the presence of a number of N-containing species, at 75–80 °C and at ambient pressure. − But a cumbersome synthesis due to the nonavailability of the monomers is not applicable on an industrial scale.…”