Fabrication of covalent organic framework (COF) membranes for molecular transport has excited highly pragmatic interest as a low energy and cost-effective route for molecular separations. However, currently, most COF membranes are assembled via a one-step procedure in liquid phase(s) by concurrent polymerization and crystallization, which are often accompanied by a loosely packed and less ordered structure. Herein, we propose a two-step procedure via a phase switching strategy, which decouples the polymerization process and the crystallization process to assemble compact and highly crystalline COF membranes. In the pre-assembly step, the mixed monomer solution is casted into a pristine membrane in the liquid phase, along with the completion of polymerization process. In the assembly step, the pristine membrane is transformed into a COF membrane in the vapour phase of solvent and catalyst, along with the completion of crystallization process. Owing to the compact and highly crystalline structure, the resultant COF membranes exhibit an unprecedented permeance (water ≈ 403 L m−2 bar−1 h−1 and acetonitrile ≈ 519 L m−2 bar−1 h−1). Our two-step procedure via phase switching strategy can open up a new avenue to the fabrication of advanced organic crystalline microporous membranes.

Mixed matrix membranes (MMMs) have been increasingly utilized in membrane processes. Covalent organic frameworks (COFs) hold great promise as emergent nanofillers to fabricate high-performance MMMs; however, only few studies about COF materials in MMMs have been reported where COFs are all used as nonreactive fillers. Herein, we propose using −NH2-functionalized COF nanosheets as reactive fillers (rCON) to fabricate MMMs. rCON altered the morphology and chemistry of MMMs by controlling the diffusion rate of piperazine through hydrogen bonding prior to the interfacial polymerization process and inducing the creation of ridges in the MMMs with subsequent increase in surface area (∼24%). rCON was chemically cross-linked to the trimesoyl chloride through amide bonding, subsequently elevating the hydrophilicity (∼35%) and fouling resistance of MMMs. The presence of −NH2 groups elevated the rCON–PA compatibility, ensuring the high rCON loading of 5 wt % in the MMMs without sacrificing salt rejection. Accordingly, the PA–rCON MMMs exhibited a flux of 46.5 L m–2 h–1 bar–1, which is 6.8 times higher than that of the pristine PA membrane, with a high rejection rate of 93.5% for Na2SO4.

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A series of thiourea based bifunctional organocatalysts having d-glucose as a core scaffold were synthesized and examined as catalysts for the asymmetric Michael addition reaction of aryl/alkyl trans-β-nitrostyrenes over cyclohexanone and other Michael donors having active methylene. Excellent enantioselectivities (<95%), diastereoselectivities (<99%), and yields (<99%) were attained under solvent free conditions using 10 mol% of 1d. The obtained results were explained through DFT calculations using the B3LYP/6-311G(d,p)//B3LYP/6-31G(d) basic set. The QM/MM calculations revealed the role of cyclohexanone as a solvent as well as reactant in the rate determining step imparting 31.91 kcal mol of energy towards the product formation.

Motion-induced change in emission (MICE) is a phenomenon that can be employed to develop various types of probes, including temperature and viscosity sensors. Although MICE, arising from the conformational motion in particular compounds, has been studied extensively, this phenomenon has not been investigated in depth in mechanically interlocked molecules (MIMs) undergoing coconformational changes. Herein, we report the investigation of a thermoresponsive dynamic homo[2]catenane incorporating pyrene units and displaying relative circumrotational motions of its cyclophanes as evidenced by variable-temperature 1 H NMR spectroscopy and supported by its visualization through molecular dynamics simulations and quantum mechanics calculations. The relative coconformational motions induce a significant change in the fluorescence emission of the homo[2]catenane upon changes in temperature compared with its component cyclophanes. This variation in the exciplex emission of the homo[2]catenane is reversible as demonstrated by four complete cooling and heating cycles. This research opens up possibilities of using the coconformational changes in MIMs-based chromophores for probing fluctuations in temperature which could lead to applications in biomedicine or materials science.