No abstract

A superhydrophobic self-cleaning MOF nanostructure has been synthesized using a unique ligand design strategy and coordination directed self-assembly. The material has hierarchical surface roughness and is stable under extreme corrosive conditions.

Rationalization of structure and properties of amorphous porous solids at the microscopic level is essential in developing advanced materials. We delineate the structural modeling of a designed tetraphenylethene-based amorphous conjugated microporous polymer TPE-CMP (1) and its gas storage and photophysical properties. The polymer 1 exhibits high specific surface area of 854 m 2 /g. 1 showed appreciable CO 2 (32.4 wt %) uptake at 195 K up to 1 atm and 31.6 wt % at 273 K up to 35 bar. The structural model of 1 obtained through computational methods is quantitatively consistent with experimental observations. The microporous structural model of 1 was further validated by a calculation of CO 2 adsorption isotherm obtained through GCMC simulations. Quantum chemical calculations were employed to understand the nature of interactions of CO 2 with the constituents of the framework 1. π−π interaction with strength of 19 kJ/mol was observed between CO 2 and the phenyl rings of TPE. 1 shows strong turn-on greenish-yellow emission due to the restriction of phenyl ring rotation of TPE node. This framework induced emission (FIE) of microporous polymer 1 is further exploited for light-harvesting applications by noncovalent encapsulation of a suitable acceptor dye, rhodamine B (RhB), in the framework.

Donor–acceptor CMPs showing inherent conductivity and electrochemical oxygen reduction.

We report the design and synthesis of two Co2+ and Zn2+ phthalocyanine (PC)-based redox active metal-organic conjugated microporous polymers (MO-CMP), CoCMP and ZnCMP, respectively, obtained by a Schiff base condensation reaction. CoCMP, where Co2+ is stabilized by N4-coordination of PC, has shown stable and efficient electrocatalytic activity towards the OER with a low overpotential of 340 mV.

New flexible MOF (F-MOF)–aminoclay (AC) nanocomposites are synthesized and their tunable gas adsorption/separation properties are reported.

Reversible and selective capture/detection of F(-) ions in water is of the utmost importance, as excess intake leads to adverse effects on human health. Highly robust Lewis acidic luminescent porous organic materials have potential for efficient sequestration and detection of F(-) ions. Herein, the rational design and synthesis of a boron-based, Lewis acidic microporous organic polymer (BMOP) derived from tris(4-bromo-2,3,5,6-tetramethylphenyl)boron nodes and diethynylbiphenyl linkers with a pore size of 1.08 nm for selective turn-on sensing and capture of F(-) ion are reported. The presence of a vacant pπ orbital on the boron center of BMOP results in intramolecular charge transfer (ICT) from the linker to boron. BMOP shows selective turn-on blue emission for F(-) ions in aqueous mixtures with a detection limit of 2.6 μM. Strong B-F interactions facilitate rapid sequestration of F(-) by BMOP. The ICT emission of BMOP can be reversibly regenerated by addition of an excess of water, and the polymer can be reused several times.

We report a novel in situ method for synthesis of metal nanoparticles (NPs)−CMP (conjugated microporous polymer) composites based on a redoxactive, donor−acceptor CMP, tris-(4-aminophenyl)amine (TPA)−perylenediimide (PDI). The TPA−PDI CMP, comprising triphenylamine as an electron donor and PDI as an acceptor, showed stable charge-separated state and semiconducting behavior. Further, TPA−PDI CMP has been exploited for in situ stabilization of metal (Au and Co) NPs, and two novel nanocomposites (Au@TPA−PDI and Co@TPA− PDI) were prepared. The catalytic reduction of nitro aryls to amino aryls was studied using Au@TPA−PDI, which showed excellent yields and fast kinetics. The CMP itself was found to show good activity as a metal-free oxygen reduction reaction (ORR) electrocatalyst with an onset potential of 0.82 V. Stabilizing merely 2.56 wt % Co nanoparticles in the CMP matrix improved the electrochemical ORR activity of as-synthesized TPA−PDI immensely and showed an onset potential of 0.91 V, which has also been supported by density functional theory (DFT) calculations.