Morphology Tuning via Linker Modulation: Metal-Free Covalent Organic Nanostructures with Exceptional Chemical Stability for Electrocatalytic Water Splitting.

The development of synthetic routes for the formation of robust porous organic polymers (POPs) with well-defined nanoscale morphology is fundamentally significant for their practical applications. The thermodynamic characteristics that arise from reversible covalent bonding impart intrinsic chemical instability in the polymers, thereby impeding their overall potential. Herein, a unique strategy is reported to overcome the stability issue by designing robust imidazole-linked POPs via tandem reversible/irreversible bond formation. Incorporating inherent rigidity into the secondary building units leads to robust microporous polymeric nanostructures with hollow-spherical morphologies. An in-depth analysis by extensive solid-state NMR (1D and 2D) study on 1H, 13C, and 14N nuclei elucidates the bonding and reveals the high purity of the newly designed imidazole-based POPs. The nitrogen-rich polymeric nanostructures are further used as metal-free electrocatalysts for water splitting. In particular, the rigid POPs show excellent catalytic activity toward the oxygen evolution reaction (OER) with long-term durability. Among them, the most efficient OER electrocatalyst (TAT-TFBE) requires 314 mV of overpotential to drive 10 mA cm-2 current density, demonstrating its superiority over state-of-the-art catalysts (RuO2 and IrO2).

Metal Ion Mediated Instant Z → E Isomerization of Azobenzene Macrocycles in the Absence of Light.

The classical photoswitch azobenzenes reversibly interconvert between the E- and the Z-isomers with light. Here, we report a pair of new macrocyclic azobenzenes characterized thoroughly by spectroscopic methods and single crystal X-ray diffraction structures, and one of the compounds displays a quantitative conversion of the E- to the Z-form. These compounds, besides their normal photoswitching behavior, display an unusual instant switching of the Z-form to the E-isomer in the presence of Cu2+ ions in the dark under 273 K. The Cu2+ complex can stay in the Z-form under constant UV radiation. However, it reverts to the E-form as soon as the exposure to the UV is ceased. The same phenomenon is also observed with Ag+ ions albeit it is a bit slower. This unusual instant switching of the azobenzene systems with metal ions prompted the detailed studies to unravel the reason behind this behavior.

A Photoregulated Racemase Mimic.

The racemase enzymes convert L-amino acids to their D-isomer. The reaction proceeds through a stepwise deprotonation-reprotonation mechanism that is assisted by a pyridoxal phosphate (PLP) coenzyme. This work reports a PLP-photoswitch-imidazole triad where the racemization reaction can be controlled by light by tweaking the distance between the basic residue and the reaction centre.

Light-Gated Modulation of Electronic Mobility of a Dihydropyrene-Based Photochromic Coordination Polymer.

Photo-induced modulation of electronic conductance has been achieved by employing an AgI-based two-dimensional coordination polymer (CP) having pyridine-functionalized photochromic dimethyldihydropyrene-cyclophanediene (DHP-CPD) π-switch. Both the coordination polymer and the organic photochromic core were characterized by single-crystal X-ray diffraction studies. The coordination polymer displayed an excellent conductance in the ON state of the switch in the closed form of DHP. Upon exposure to visible light, the π-switch in the CPD form loses its planarity, turning the switch OFF, which is reflected in the drastic reduction of the conductance. Exposure to UV light turns the switch back ON wherein the high electronic conductance of the polymer can be restored.

Switching the recognition ability of a photoswitchable receptor towards phosphorylated anions.

An azobenzene based photoswitchable macrocyclic receptor displays different binding affinities in its E and Z forms towards various phosphorylated coenzymes under physiological conditions with remarkable selectivity for ATP in the E-form and selectivity towards GTP in the photoisomerized Z-form. Linear discriminant analysis clearly separated the analytes using the E-form. An application of this method enabled monitoring the progress of enzymatic phosphorylation using a tyrosine kinase enzyme.

Modulation of Electronic Mobility of a One-Dimensional Coordination Polymeric Molecular Wire with Light.

Metal ions often influence the photoswitching efficiency of a photochromic system. This article reports a one-dimensional polymer having cyclic azobenzenes coordinated to silver ions that are bridged by nitrates. The coordination polymer (CP-2) displays a photoresponsive behavior. The switching ability in the polymer form was faster compared to the parent azobenzene ligand without the metal ions. Azobenzenes are reported to be poorly conducting. Here, although the azobenzene ligand does not show significant electronic mobility, the coordination polymer (CP-2) displays a modest conductivity. The conductance in the cis form of the polymer is significantly higher compared to the trans form. Upon exposure to visible light, the cis form undergoes photoisomerization to the trans form with a drastic drop in the electronic mobility. The trans form can be reverted to the cis form thermally or by using UV light. Thus, this system offers a reversible control of the conductivity using light.

A phototunable anion receptor for C-HX interactions with benzoate anions.

A supramolecular receptor consisting of two anthracene moieties with binding motifs for binding of benzoate anions is reported here. NMR studies indicate that the binding involves π-π interactions and CHX interactions. Upon exposure to >350 nm light, the receptor undergoes a [4 + 4] photoelectrocyclization restricting the access to the binding site for benzoate. The reverse reaction works in the presence of the dual stimuli of 254 nm light and the benzoate anions. The work thus demonstrates a light mediated dynamic control of the binding pocket of a supramolecular anion receptor.

Chloride-Mediated Apoptosis-Inducing Activity of Bis(sulfonamide) Anionophores.

Transmembrane anion transport modality is enjoying a renewed interest because of recent advances toward anticancer therapy. Here we show bis(sulfonamides) as efficient receptors for selective Cl(-) ion binding and transport across lipid bilayer membranes. Anion-binding studies by (1)H NMR indicate a logical correlation between the acidity of sulfonamide N-H proton and binding strength. Such recognition is influenced further by the lipophilicity of a receptor during the ion-transport process. The anion-binding and transport activity of a bis(sulfonamide) system are far superior compared to those of the corresponding bis(carboxylic amide) derivative. Fluorescent-based assays confirm the Cl(-)/anion antiport as the operational mechanism of the ion transport by bis(sulfonamides). Disruption of ionic homeostasis by the transported Cl(-) ion, via bis(sulfonamide), is found to impose cell death. Induction of a caspase-dependent intrinsic pathway of apoptosis is confirmed by monitoring the changes in mitrochondrial membrane potential, cytochrome c leakage, activation of family of caspases, and nuclear fragmentation studies.