Selective separation of acetylene (CH) from carbon dioxide (CO) or ethylene (CH) needs specific porous materials whose pores can realize sieving effects while pore surfaces can differentiate their recognitions for these molecules of similar molecular sizes and physical properties. We report a microporous material [Zn(dps)(SiF)] (UTSA-300, dps = 4,4'-dipyridylsulfide) with two-dimensional channels of about 3.3 Å, well-matched for the molecular sizes of CH. After activation, the network was transformed to its closed-pore phase, UTSA-300a, with dispersed 0D cavities, accompanied by conformation change of the pyridyl ligand and rotation of SiF pillars. Strong C-H···F and π-π stacking interactions are found in closed-pore UTSA-300a, resulting in shrinkage of the structure. Interestingly, UTSA-300a takes up quite a large amounts of acetylene (76.4 cm g), while showing complete CH and CO exclusion from CH under ambient conditions. Neutron powder diffraction and molecular modeling studies clearly reveal that a CH molecule primarily binds to two hexafluorosilicate F atoms in a head-on orientation, breaking the original intranetwork hydrogen bond and subsequently expanding to open-pore structure. Crystal structures, gas sorption isotherms, molecular modeling, experimental breakthrough experiment, and selectivity calculation comprehensively demonstrated this unique metal-organic framework material for highly selective CH/CO and CH/CH separation.

We report herein a simple, metal- and additive-free, photoinduced borylation of haloarenes, including electron-rich fluoroarenes, as well as arylammonium salts directly to boronic acids. This borylation method has a broad scope and functional group tolerance. We show that it can be further extended to boronic esters, and carried out on gram scale as well as under flow conditions.

Boronic acids are centrally important functional motifs and synthetic precursors. Visible lightinduced borylation may provide access to structurally diverse boronates, but a broadly efficient photocatalytic borylation method that can effect borylation of a wide range of substrates, including strong C-O bonds, remains elusive. Herein, we report a general, metal-free visible light-induced photocatalytic borylation platform that enables borylation of electron rich derivatives of phenols and anilines, chloroarenes, as well as other haloarenes. The reaction exhibits excellent functional group tolerance, as demonstrated by the borylation of a range of structurally complex substrates. Remarkably, the reaction is catalyzed by phenothiazine, -a simple organic photocatalyst with MW<200 that mediates the previously unachievable visible light-induced single electron reduction of phenol derivatives with reduction potentials as negative as ~-3 V vs SCE by a proton-coupled electron transfer mechanism. Mechanistic studies point to the crucial role of the photocatalyst-base interaction.

A hydrogen-bonded organic framework (HOF), HOF-7, based on a zinc porphyrin-based building block (ZnTDPP) with diaminotriazine moieties has been successfully constructed and structurally characterized (ZnTDPP = 5,10,15,20-tetrakis(4-(2,4-diaminotriazinyl)phenyl)porphyrinato zinc). Single-crystal X-ray diffraction analysis reveals that HOF-7 is built by the 2D layered subunits connected by the intermolecular hydrogen-bonding and π−π interaction, exhibiting two kinds of micropores with sizes of 3.2 × 4.7 Å 2 and 4.2 × 6.7 Å 2 , respectively. This HOF exhibits permanent porosities as demonstrated in the CO 2 sorption and selective adsorption of CO 2 over N 2 .

A microporous six-fold interpenetrated hydrogen-bonded organic framework for highly selective separation of C2H4/C2H6 Li, P.; He, Y.; Arman, H.D.; Krishna, R.; Wang, H.; Weng, L.; Chen, B.