Synthesis and Optoelectronic Features of Rhodamine-Triazole Dyads as Metallochromic Probes for Copper-Selective Chemosensing.

Rhodamine-based chromic materials have attracted significant interest owing to their cation recognition ability with high sensitivity. However, rhodamine chromophores with controllable sensing selectivity towards transition metal species are only at the advent. Herein, three triazole-conjugated rhodamine dyads with different peripheral substituents were synthesized. The key triazole precursors required for the desired chemistry were prepared by adopting our recently developed CTAB catalyzed mechano-click chemistry. Molecular properties derived from photophysics, electrochemistry and surface morphology of the synthesized dyads were analyzed. Furthermore, frontier molecular orbitals, electronic structure and secondary quantum chemical parameters of dyads were also compared. Screening of dyads for their sensing ability towards an array of alkali, alkaline and transition metal ions exhibited a noticeable naked-eye detection of Cu2+ ions and was confirmed by spectrophotometric titration. The specific binding mode of dyads as probable with Cu2+ over other metal ions attributes to the chemoselectivity.

Mechanochemical Access to Functional Clickates with Nitro-Retentive Selectivity via Organocatalyzed Oxidative Azide-Olefin Cycloaddition.

4-Nitro-1,2,3-triazoles are crucial precursors for high energy materials, and their practical synthesis is a long-standing problem. Herein, we communicate a mechanochemical route for the selective synthesis of 4-nitro-1,2,3-triazoles via organocatalyzed oxidative [3 + 2] cycloaddition between ß-nitrostyrenes and organic azides. Our conditions avoid divergent pathways and permit the retention of the valuable NO2 group on the product. Nontoxic catalyst, catalyst recyclability, no rigorous solvent-extraction, no toxic byproducts, atmospheric oxygen, and gram-scale synthesis are some of the salient features.

Azulene Bridged π-Distorted Chromophores: The Influence of Structural Symmetry on Optoelectrochemical and Photovoltaic Parameters.

Conjugated chromophores possessing π-twisted functionality such as tetracyanobutadiene (TCBD) have emerged as promising active layer materials for organic photovoltaics (OPVs). In this study, we disclose the synthesis of two azulenyl chromophores containing one and two TCBD groups. The symmetrical and unsymmetrical structural characteristics of these molecules inflict dissimilar optoelectronic and electrochemical properties. Based on molar absorptivity, aggregation behavior, HOMO-LUMO energies and other quantum chemical parameters, the symmetrical molecule (TATC2) appears to be a better non-fullerene acceptor (NFA) compared to its unsymmetrical counterpart (TATC1). For instance, higher absorptivity and deeper HOMO-LUMO levels for TATC2 (23950 M-1 cm-1 ; -6.01 eV/-3.86 eV) over TATC1 (12200 M1 cm-1 ; -5.46 eV/-3.64 eV) was observed. Validating this structure-property relationship on solar cell prototypes exhibited higher photovoltaic parameters (VOC =0.54 V, FF=0.48, JSC =6.42 mA/cm2 ) for TATC2 than TATC1 (VOC =0.47 V, FF=0.38, JSC =5.77 mA/cm2 ). Though the device parameters are not high, this work uncovers the intrinsic properties of azulene-tethered twisted chromophores as potential π-semiconductor choice for NFA solar cells. In particular, this report explores the utility of azulene-based π-twisted semiconductors as acceptor material for OPVs with cell efficiencies of 1.70 and 1.04 % for TATC2 and TATC1 respectively.

Electropolymerization of thienyl tethered comonomers and application towards the electrocatalytic reduction of nitrobenzene.

The synthesis of different π-spacered thiophene comonomers via Suzuki cross-coupling in good synthetic yields was accomplished. Potentiodynamic electropolymerization of these precursors on ITO electrode by constant potential electrolysis results in the deposition of thin films of polymers between 0.05 and 0.2 µM. Interestingly, the as synthesized π-conjugated polymers exhibit electrochromic behaviour upon electrochemical oxidation. On the application side, the synthesized electropolymers showed catalytic activity better than glassy carbon towards electrochemical reduction of nitrobenzene.

Supercritical water assisted preparation of recyclable gold nanoparticles and their catalytic utility in cross-coupling reactions under sustainable conditions.

Preparation of gold nanoparticles (AuNPs) in environmentally friendly water without using any reducing agents under supercritical conditions is demonstrated. PXRD, XPS, FE-SEM and HR-TEM analysis confirmed the formation of phase-pure and crystalline AuNPs of the size of ∼10-30 nm. The catalytic potential of AuNPs was manifested through a generalized green procedure that could accommodate both Sonogashira as well as Suzuki coupling under aqueous conditions at low catalytic loading (0.1 mol%). The AuNP catalyst was found to be recuperated after the reaction and reused for up to six catalytic cycles with no leaching out of gold species as confirmed through ICP-OES analysis. With no confinement of AuNP catalysis to cross-coupling reaction, synthetic extension to one-flask preparation of π-conjugated semiconductors (4 examples) and their optoelectronic properties were also investigated. Other significant features of the present work include short reaction time, site-selectivity, wide substrate scope, high conversion, good chemical yields and applicability in gram-scale synthesis. Overall, the results of this paper signify an operationally sustainable supercritical fluid processing method for the synthesis of AuNPs and their catalytic application towards cross-coupling reactions in green media.