title: Rational design and synthesis of hybrid porous polymers derived from polyhedral oligomeric silsesquioxanes via heck coupling reactions.
abstract: Heck coupling reactions are introduced as an efficient method to prepare porous polymers. Novel inorganic-organic hybrid porous polymers (HPPs) were constructed via Heck coupling reactions from cubic functional polyhedral oligomeric silsesquioxanes (POSS), iodinated octaphenylsilsesquioxanes (OPS) and octavinylsilsesquioxanes (OVS) using Pd(OAc)2 /PPh3 as the catalyst. Here, two iodinated OPS were used, IOPS and p-I8 OPS. IOPS was a mixture with 90% octasubstituted OPS (I8 ) and some nonasubstituted OPS (I9 ), while p-I8 OPS was a nearly pure compound with ≥99% I8 and ≥93% para-substitution. IOPS and p-I8 OPS reacted with OVS to produce the porous materials HPP-1 and HPP-2, which exhibited comparable specific surface areas with SBET of 418 ± 20 m(2) g(-1) and 382 ± 20 m(2) g(-1) , respectively, with total pore volumes of 0.28 ± 0.01 cm(3) g(-1) and 0.23 ± 0.01 cm(3) g(-1) , respectively. HPP-1 showed a broader pore size distribution and possessed a more significant contribution from the mesopores, when compared with HPP-2, thereby indicating that IOPS may induce more disorder because of the geometrical asymmetry. HPP-1 and HPP-2 possessed moderate carbon dioxide uptakes of 134 and 124 cm(3) g(-1) at 1 bar at 195 K, making them promising candidates for CO2 capture and storage. The synthesized porous polymers may be easily post-functionalized using the retained ethenylene groups.
authors.affiliation: State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100, PR China.
authors.forename: Dengxu
authors.initials: D
authors.lastname: Wang
authors.forename: Lei
authors.initials: L
authors.lastname: Xue
authors.forename: Liguo
authors.initials: L
authors.lastname: Li
authors.forename: Bei
authors.initials: B
authors.lastname: Deng
authors.forename: Shengyu
authors.initials: S
authors.lastname: Feng
authors.forename: Hongzhi
authors.initials: H
authors.lastname: Liu
authors.forename: Xian
authors.initials: X
authors.lastname: Zhao
mesh_terms: D000327:Adsorption; D002245:Carbon Dioxide / Q000737:chemistry; D002625:Chemistry, Organic / Q000379:methods*; D009682:Magnetic Resonance Spectroscopy; D046529:Microscopy, Electron, Transmission; D009584:Nitrogen / Q000737:chemistry; D011108:Polymers / Q000138:chemical synthesis* / Q000737:chemistry*; D016062:Porosity; D000644:Quaternary Ammonium Compounds / Q000737:chemistry*; D013818:Thermogravimetry
chemical_list: D011108:Polymers; D000644:Quaternary Ammonium Compounds; D002245:Carbon Dioxide; D009584:Nitrogen