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Membrane‐based gas separations are crucial for an energy‐efficient future. However, it is difficult to develop membrane materials that are high‐performing, scalable, and processable. Microporous organic polymers (MOPs) combine benefits for gas sieving and solution processability. Herein, we report membrane performance for a new family of microporous poly(arylene ether)s (PAEs) synthesized via Pd‐catalyzed C−O coupling reactions. The scaffold of these microporous polymers consists of rigid three‐dimensional triptycene and stereocontorted spirobifluorene, endowing these polymers with micropore dimensions attractive for gas separations. This robust PAE synthesis method allows for the facile incorporation of functionalities and branched linkers for control of permeation and mechanical properties. A solution‐processable branched polymer was formed into a submicron film and characterized for permeance and selectivity, revealing lab data that rivals property sets of commercially available membranes already optimized for much thinner configurations. Moreover, the branching motif endows these materials with outstanding plasticization resistance, and their microporous structure and stability enables benefits from competitive sorption, increasing CO2/CH4 and (H2S+CO2)/CH4 selectivity in mixture tests as predicted by the dual‐mode sorption model. The structural tunability, stability, and ease‐of‐processing suggest that this new platform of microporous polymers provides generalizable design strategies to form MOPs at scale for demanding gas separations in industry. [ABSTRACT FROM AUTHOR]

Although phase transition materials (PTMs) under external stimuli are of great research interest duo to their rich potential applications, it is still challenging to explore multi‐responsive PTMs. Herein, two different phases of organic–inorganic hybrid copper‐based halides, α‐ and β‐Gua3Cu2I5 (Gua+=CN3H6+), were synthesized by solvent evaporation method, which they crystalize in the noncentrosymmetric space group Fdd2 with zero‐dimensional structure and centrosymmetric space group C2/c with one‐dimensional metal‐halogen framework, respectively. Interestingly, it is firstly demonstrated that Gua3Cu2I5 simultaneously possesses reversible PL conversion and NLO switching properties in response to thermal stimulus. Strikingly, apart from heat, its structural phase transition can also be triggered by crystalline‐phase‐recognition (CPR) and mechanical force. These new findings may pave a path for future exploration of PTMs with multiple physical properties. [ABSTRACT FROM AUTHOR]

Metal chalcogenophosphates are receiving increasing interest, specifically as promising infrared nonlinear optical (NLO) candidates. Here, a rare‐earth chalcogenophosphate Eu2P2S6 crystallizing in the monoclinic noncentrosymmetric space group Pn was synthesized using a high‐temperature solid‐state method. Its structure features isolated [P2S6]4− dimer, and two types of EuS8 bicapped triangular prisms. Eu2P2S6 exhibits a phase‐matchable second‐harmonic generation (SHG) response ≈0.9×AgGaS2@2.1 μm, and high laser‐induced damage threshold of 3.4×AgGaS2, representing the first rare‐earth NLO chalcogenophosphate. The theoretical calculation result suggests that the SHG response is ascribed to the synergetic contribution of [P2S6]4− dimers and EuS8 bicapped triangular prisms. This work provides not only a promising high‐performance infrared NLO material, but also opens the avenue for exploring rare‐earth chalcogenophosphates as potential IR NLO materials. [ABSTRACT FROM AUTHOR]

Infrared nonlinear optical (IR NLO) materials are significant in laser technology for civil and military uses. Here, we report the synthesis, structural chemistry and NLO properties of a halogen‐rich chalcohalide Sn7Br10S2. Its noncentrosymmetric (NCS, P63) structure can be considered as partially aliovalent anion substitution of SnBr2 (P63/m) induced centrosymmetric (CS) to NCS structural transformation. The 3D∞[Sn(1)6Sn(2)6Br6X6]6− (X=Br/S) channel framework consists of Sn(1)BrX2 and Sn(2)X3 trigonal pyramids. It exhibits excellent NLO performance, including a strong phase‐matchable NLO response of 1.5 × AgGaS2and high laser‐induced damage threshold of 6.3 × AgGaS2.Investigation of the structure–NLO performance relationship confirms that the effective arrangement of Sn(1)BrX2 and Sn(2)X3 units predominantly contributes to the large SHG response. These results indicate Sn7Br10S2 is a potential IR NLO candidate and provides a new feasible system for promising NLO materials. [ABSTRACT FROM AUTHOR]

A Cu‐catalyzed enantioselective hydroamination of α,β‐unsaturated carbonyl compounds for the synthesis of β‐amino acid derivatives was achieved through ligand‐controlled reversal of the hydrocupration regioselectivity. While the hydrocupration of α,β‐unsaturated carbonyl compounds to form α‐cuprated species has been extensively investigated, we report herein that, in the presence of an appropriate ancillary chiral ligand, the opposite regiochemistry can be observed for cinnamic acid derivatives, leading to the delivery of the copper to the β‐position. This copper can react with an electrophilic aminating reagent, 1,2‐benzisoxazole, to provide enantioenriched β‐amino acid derivatives, which are important building blocks for the synthesis of natural products and bioactive small molecules. [ABSTRACT FROM AUTHOR]

A big challenge for nonlinear optical (NLO) materials is the application in high power lasers, which needs the simultaneous occurrence of large second harmonic generation (SHG) and high laser induced damage threshold (LIDT). Herein we report the preparation of a new Ga2Se3 phase, which shows the SHG intensities of around 2.3 times and the LIDT of around 16.7 times those of AgGaS2 (AGS), respectively. In addition, its IR transparent window ca. 0.59–25 μm is also significantly wider than that of AGS (ca. 0.48–≈11.4 μm). The occurrence of the strong SHG responses and good phase‐matching indicate that the structure of the new Ga2Se3 phase can only be non‐centrosymmetric and have a lower symmetry than the cubic γ‐phase. The observed excellent SHG and phase‐matching properties are consistent with our diffraction experiments and can be well explained by using the orthorhombic models obtained through our high throughput simulations. [ABSTRACT FROM AUTHOR]

Abstract: A simple adduct from tin tetraiodide SnI4 and octasulfur S8, SnI4⋅(S8)2 (1), is obtained employing a facile reaction. The combination of Sn4+ ions with d10 electron configuration, acentric SnI4 tetrahedra, and lone‐pair effects of S8, makes 1 a phase‐matchable infrared NLO crystal with a moderate second‐harmonic generation (SHG) response and a very high laser‐induced damage threshold (LIDT), which is well confirmed by the DFT calculations. [ABSTRACT FROM AUTHOR]

A highly stereoselective dynamic kinetic isomerization of Achmatowicz rearrangement products was discovered. This new internal redox isomerization provided ready access to key intermediates for the enantio- and diastereoselective synthesis of a series of naturally occurring sugars. The nature of the de novo synthesis also enables the preparation of both enantiomers. [ABSTRACT FROM AUTHOR]

Leucosceptroids A and B are sesterterpenoids with potent antifeedant and antifungal activities. A more efficient gram-scale total synthesis of leucosceptroid B and the first total synthesis of leucosceptroid A are presented. The key transformations include an aldol reaction between a substituted dihydrofuranone and an ( S)-citronellal-derived aldehyde, a SmI2-mediated intramolecular ketyl-olefin radical cyclization, and final-stage alcohol oxidation. [ABSTRACT FROM AUTHOR]

The first bulk electron-transfer photochromic compound with intrinsic second-order nonlinear optical (NLO) photoswitching properties has been synthesized. This system employs an electron-transfer photoactive asymmetric viologen ligand coordinated to a zinc(II) center. [ABSTRACT FROM AUTHOR]

Metal chalcogenophosphates are receiving increasing interest, specifically as promising infrared nonlinear optical (NLO) candidates. Here, a rare‐earth chalcogenophosphate Eu2P2S6 crystallizing in the monoclinic noncentrosymmetric space group Pn was synthesized using a high‐temperature solid‐state method. Its structure features isolated [P2S6]4− dimer, and two types of EuS8 bicapped triangular prisms. Eu2P2S6 exhibits a phase‐matchable second‐harmonic generation (SHG) response ≈0.9×AgGaS2@2.1 μm, and high laser‐induced damage threshold of 3.4×AgGaS2, representing the first rare‐earth NLO chalcogenophosphate. The theoretical calculation result suggests that the SHG response is ascribed to the synergetic contribution of [P2S6]4− dimers and EuS8 bicapped triangular prisms. This work provides not only a promising high‐performance infrared NLO material, but also opens the avenue for exploring rare‐earth chalcogenophosphates as potential IR NLO materials. [ABSTRACT FROM AUTHOR]