https://dspace.iiti.ac.in:8080/jspui/handle/123456789/6160 Fri, 15 May 2026 09:03:02 GMT 2026-05-15T09:03:02Z https://dspace.iiti.ac.in:8080/jspui/handle/123456789/18377 Title: NIR-Absorbing TCBD and Expanded TCBD-Functionalized Ferrocene–Phenothiazine Conjugates Authors: Tiwari, Nikhil Ji; Gupta, Deeksha; Misra, Rajneesh Abstract: A set of TCBD- and expanded TCBD-functionalized donor–acceptor ferrocene conjugates Fc2–3 and Fc5–6 were designed and synthesized via Pd-catalyzed Sonogashira cross-coupling, followed by [2 + 2] cycloaddition–retroelectrocyclization reactions. Phenothiazine (PTZ) and ferrocene (Fc) were used as the terminal donor units. The incorporation of cyano-based strong acceptors 1,1,4,4-tetracyanobutadiene (TCBD) and dicyanoquinodimethane (DCNQ) in the ferrocene and ferrocene–phenothiazine conjugates resulted in substantial variation in their photophysical, electrochemical, and thermal behavior. The electronic absorption spectra of the ferrocene derivatives with TCNE (Fc2, Fc5) and TCNQ (Fc3, Fc6) acceptors show bathochromically shifted absorption compared to Fc1 and Fc4 due to a significant intramolecular charge-transfer (ICT) transition. The electrochemical analysis of Fc2–3 and Fc5–6 reveals reduction waves at lower potentials due to the TCBD and DCNQ acceptors. The TCBD-functionalized ferrocene derivative Fc2 shows higher thermal stability compared to other ferrocene conjugates. DFT-optimized geometries and frontier orbital energies of Fc1–6 indicate that increasing the acceptor strength stabilizes the LUMO and reduces the HOMO–LUMO gap. The spectroelectrochemical analyses of Fc2–3 and Fc5–6 revealed substantial spectral changes during the reduction cycle in the NIR region, whereas Fc1 and Fc4 displayed changes during the oxidation cycle in the NIR region. © 2026 American Chemical Society Thu, 01 Jan 2026 00:00:00 GMT https://dspace.iiti.ac.in:8080/jspui/handle/123456789/18377 2026-01-01T00:00:00Z https://dspace.iiti.ac.in:8080/jspui/handle/123456789/18370 Title: Ferrocenyl-dithiolane integrated Cu(i) coordination polymers: framework engineering for synergistic redox activity towards supercapattery applications Authors: Pandey, Dilip; Singh, Mayank K.; Maurya, Sarvesh K.; Ojha, Abhishek; Rai, Dhirendra Kumar; Raghuvanshi, Abhinav Abstract: This work presents the rational design of ferrocene-integrated Cu(i) coordination polymers (CPs) that harness the synergistic redox activity of Fe(ii) and Cu(i) centers for high-performance energy storage. Two new CPs, Fc-Cu1 and Fc-Cu2, were obtained by self-assembly of CuI with (2-methyl-1,3-dithiolan-2-yl)ferrocene and 1,1′-bis(2-methyl-1,3-dithiolan-2-yl)ferrocene, respectively. Both CPs consist of a similar [{Cu2(µ4-I)(µ2-I)}]n array where ferrocene ligands coordinate via sulfur atoms, leading to a one-dimensional polymeric structure for Fc-Cu1 and a layered 2D architecture for Fc-Cu2. The 2D architecture of Fc-Cu2 improves electrical conductivity, charge transport, and ion diffusion compared to its 1D counterpart, resulting in a higher diffusion-controlled charge storage capacity of 450 C g−1 (areal capacity: 855 mC cm−2) at 1 A g−1. A symmetric supercapattery device assembled using Fc-Cu2 electrodes delivers a maximum energy and power density of 14.5 Wh kg−1 and 6 kW kg−1, respectively, and retains 85% of its initial capacity over 10 000 cycles, demonstrating excellent cycling stability. This study underscores the significance of combining multiple redox-active centers with controlled framework dimensionality in the development of next-generation CP/MOF-based energy storage systems. This journal is © The Royal Society of Chemistry, 2026 Thu, 01 Jan 2026 00:00:00 GMT https://dspace.iiti.ac.in:8080/jspui/handle/123456789/18370 2026-01-01T00:00:00Z https://dspace.iiti.ac.in:8080/jspui/handle/123456789/18376 Title: A Sustainable and Catalyst-Free Direct Photochemical Route for the Conversion of Amines to Imines via C–N Coupling Reaction Under Ambient Conditions Authors: Datta, Supritam; Mukherjee, Tushar Kanti Abstract: Amine to imine conversion via C–N coupling pathway is an important class of chemical transformation having tremendous importance in the synthesis of fine chemicals and pharmaceuticals. However, selective conversion of amines to imines requires harsh reaction conditions and/or metal-based catalysts. Here, we report a catalyst-free direct photochemical route for the selective conversion of amines to imines under ambient conditions. The present approach utilizes in situ generated singlet oxygen (1O2) as an oxidizing agent from the solvent–3O2 charge-transfer transition in neat solvent for the conversion of amines to imines under 370–440 nm light irradiation. This conversion proceeds with the generation of ammonia and hydrogen peroxide as byproducts. Detailed mechanistic investigations revealed single electron transfer from amines to 1O2 with the formation of iminium cation intermediate. To our knowledge, this is the first report for an efficient, selective, and sustainable conversion of amines to imines under an ambient atmosphere without any additional catalysts/oxidants. © 2026 Wiley-VCH GmbH. Thu, 01 Jan 2026 00:00:00 GMT https://dspace.iiti.ac.in:8080/jspui/handle/123456789/18376 2026-01-01T00:00:00Z https://dspace.iiti.ac.in:8080/jspui/handle/123456789/18364 Title: Visible-Light-Driven C–S Coupling Reaction Using Covalent Organic Framework Films Authors: Paul, Poulami; Pathak, Biswarup Abstract: A visible-light-driven C–S cross-coupling reaction using covalent organic frameworks (COFs) as heterogeneous photocatalysts is reported. Three β-keto-enamine-linked COFs, TpAzo, TpDPP, and TpBDMe2, were synthesized and systematically evaluated. Among them, TpAzo exhibited superior photocatalytic activity due to its high surface area (1725 m2 g–1), low band gap (1.78 eV), and efficient charge separation. To enhance the reusability and accessibility, a thin-film morphology of TpAzo COF was developed, which facilitated catalyst recovery and sustained performance over multiple cycles. The optimized protocol enabled the arylation of thiols with a wide range of aryl halides, including iodides, bromides, chlorides, tosylates, and mesylates, delivering the corresponding thioethers in good to excellent yields (55–94%) under ambient conditions. This study highlights the potential of COF-based photocatalysts for sustainable C–S bond formation and broadens their application in organic synthesis. © 2026 American Chemical Society Thu, 01 Jan 2026 00:00:00 GMT https://dspace.iiti.ac.in:8080/jspui/handle/123456789/18364 2026-01-01T00:00:00Z