Microporous organic polymers (MOP) of a new type have been synthesised in high yields by a simple coordination polymerization of 1,3-diethynylbenzene, 1,4-diethynylbenzene and 4,4'-diethynylbiphenyl catalysed by [Rh(cod)acac] and [Rh(nbd)acac] complexes. The new MOPs are non-swellable polyacetylene-type conjugated networks consisting of ethynylaryl-substituted polyene main chains that are crosslinked by arylene linkers. Prepared MOP samples have a mole fraction of branching units (by (13)C CP/MAS NMR) from 0.30 to 0.47 and exhibit the BET (Brunaer-Emmett-Teller) surface up to 809 m(2) g(-1) and hydrogen uptake up to 0.69 wt% (77 K, H2 pressure 750 torr).

The π-conjugated micro/macroporous polyacetylene-type polyHIPE foams were synthesized for the first time by a chain-growth insertion polymerization of high internal phase emulsions (HIPEs). In the first step, the π-conjugated polyHIPE foams were prepared by polymerization of 1,3-diethynylbenzene HIPEs using [Rh(nbd)acac] complex as a catalyst. The π-conjugated polyHIPE foams consist of ethynylphenyl-substituted polyene main chains which are cross-linked by the 1,3-phenylene linkers. In the second step, the foams were chemically and thermally postmodified by applying the alkyne−azide cycloaddition reaction and the solvent free solid phase hyper-cross-linking at temperature of 280 °C. Thus, obtained polyacetylene-type polyHIPE foams exhibit hierarchically structured micro/macroporous morphology with sizes of the macropores and interconnecting pores of 3.4 ± 0.3 μm (or 4.8 ± 0.8 μm) and 0.96 μm (or 1.1 μm), respectively, wherein a substantial volume of micropores is also found within the macroporous walls as revealed by the calculations from the t-plots. The BET (Brunaer−Emmett−Teller) surface area of up to 110 and 380 m 2 g −1 was determined before and after solid phase hyper-cross-linking, respectively.

Hyperbranched partly cross‐linked polycyclotrimers of 1,4‐diethynylbenzene, 2,6‐diethynyl­naphthalene, and 2,6‐diethynylanthracene, Pc(1,4‐DEB), Pc(2,6‐DEN), and Pc(2,6‐DEA), respectively, are prepared using TaCl5/Ph4Sn catalyst. Brunauer–Emmett–Teller (BET) surface area, microporosity, and maximum sorption capacity for H2 and CO2 decrease in the order of decreasing relative content of branching points in polycyclotrimers Pc(1,4‐DEB) > Pc(2,6‐DEN) > Pc(2,6‐DEA), the highest values for Pc(1,4‐DEB) being SBET = 1299 m2 g−1, aH2 = 1.26 wt% (100 kPa, 77 K), and aCO2 = 10.8 wt% (100 kPa, 273 K). N2 isotherms show that adsorption/desorption hysteresis occurs already at low equilibrium pressures. CO2 isotherms show that the time allotted to the measurement influences both the maximum adsorption capacity and the hysteresis upon desorption.

Chain‐growth polymerization of 1,4‐diethynylbenzene into conjugated crosslinked polyacetylene‐type poly(1,4‐diethynylbenzene)s (PDEBs) is reported. While metathesis catalysts (WCl6/Ph4Sn, MoCl5/Ph4Sn, Mo Schrock carbene) fail in this polymerization, insertion Rh catalysts ([Rh(nbd)acac], [Rh(nbd)Cl]2) provide microporous PDEBs in high yields. The Brunauer–Emmett–Teller (BET) surface, SBET, of PDEBs prepared with [Rh(nbd)acac] increases, in dependence on the polymerization solvent, in the order: THF << pentane < benzene < methanol < CH2Cl2. SBET further increases with both increasing monomer concentration and increasing polymerization temperature and reaction time, reaching a highest value of 1469 m2 g−1. In addition to micropores, PDEBs contain mesopores. The mesopore volume and average mesopore diameter increase with the time and the temperature of the polymerization up to 2.52 cm3 g−1 and 22 nm (72 h, 75 °C). The post‐polymerization thermal treatment of PDEB (280 °C) results in formation of new crosslinks and modification of PDEB texture and sorption behavior manifested mainly by enhancement of H2 adsorption capacity up to 4.55 mmol g−1 (77 K, 750 Torr).

Heterogeneous catalysts based on materials with permanent porosity are of great interest owing to their high specific surface area, easy separation, recovery, and recycling ability. Additionally, porous polymer catalysts (PPCs) allow us to tune catalytic activity by introducing various functional centres. This study reports the preparation of PPCs with a permanent micro/mesoporous texture and a specific surface area S of up to 1000 m g active in acid-catalyzed reactions, namely aldehyde and ketone acetalization and carboxylic acid esterification. These PPC-type conjugated hyper-cross-linked polyarylacetylene networks were prepared by chain-growth homopolymerization of 1,4-diethynylbenzene, 1,3,5-triethynylbenzene and tetrakis(4-ethynylphenyl)methane. However, only some ethynyl groups of the monomers (from 58 to 80 %) were polymerized into the polyacetylene network segments while the other ethynyl groups remained unreacted. Depending on the number of ethynyl groups per monomer molecule and the covalent structure of the monomer, PPCs were decorated with unreacted ethynyl groups from 3.2 to 6.7 mmol g . The hydrogen atoms of the unreacted ethynyl groups served as acid catalytic centres of the aforementioned organic reactions. To the best of our knowledge, this is first study describing the high activity of hydrogen atoms of ethynyl groups in acid-catalyzed reactions.