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Item Meso-tris(2-furyl/2-thienyl) substituted porphyrin-ferrocene ‘click’ conjugates: synthesis, experimental, and computational studies(Royal Society of Chemistry, 2024) Shet, S.N.; Patil, M.; Shetti, V.S.The chemical synthesis of 5-(4-azidophenyl)-10,15,20-tris(2-furyl/2-thienyl)porphyrins and their utilization in a Cu(i) catalyzed alkyne-azide ‘click’ reaction (CuAAC) with ethynylferrocene to obtain the hitherto unknown meso-tris(2-furyl/2-thienyl) substituted porphyrin-ferrocene ‘click’ conjugates are reported. These new ‘click’ conjugates were studied along with the reference ‘click’ conjugates containing all-meso-aryl substituted porphyrins by experimental and computational methods. Compared to the reference, the new conjugates displayed red-shifted absorption/emission bands, easier porphyrin ring reduction, and an efficient photoinduced electron transfer (PET) process from ferrocene to a porphyrin unit. Density functional theory (DFT) calculations performed on these conjugates revealed a good correlation with the experimental results. © 2024 The Royal Society of Chemistry.Item Porphyrin-azoheteroarenes: synthesis, photophysical, and computational studies(Royal Society of Chemistry, 2025) Shet, S.N.; Bhat, V.G.; Swathi, S.G.; Udayakumar, U.; Shetti, V.S.Azobenzenes (Ph-N = N-Ph) are well-known photochromic compounds with widespread applications. Replacing one or both phenyl rings of azobenzenes with heteroarenes leads to a new class of compounds known as azoheteroarenes (Het-N N-Ph/Het). Azoheteroarenes have gained attention as promising alternatives to traditional azobenzenes in the field of photopharmacology due to their ability to undergo photoswitching under visible light. Interestingly, the chemistry of porphyrin-containing azoheteroarenes has been underexplored. In this study, we present the synthesis of hitherto unknown hybrid molecules: porphyrin-azopyrroles (porphyrin-N N-pyrrole) and porphyrin-azoindoles (porphyrin-N N-indole), which also feature porphyrins with five-membered meso-substituents, such as 2-furyl and 2-thienyl groups. The porphyrin-azoheteroarenes with meso-tris(2-furyl/2-thienyl) substitutions demonstrate red-shifted absorption and emission bands, more significant Stokes shifts, and smaller optical bandgaps compared to hybrids containing only meso-aryl groups. Additionally, these porphyrin-azoheteroarenes exhibit higher fluorescence emission intensities than their corresponding precursor porphyrins. © 2025 The Royal Society of Chemistry.Item Synthesis, Optoelectronic, and Photoelectrochemical Properties of an Azulene-Bridged Porphyrin Dimer(American Chemical Society, 2025) Shet, S.N.; Murthy, D.H.K.; Chandrappa, S.; Galbao, S.J.; Patil, M.; Shetti, V.S.Although azulene-incorporated porphyrin analogues, referred to as ?azuliporphyrins”, are well documented in the literature, the studies available on covalently tethered azulene–porphyrin hybrid molecules are limited. This work reports the synthesis of 1,3-azulene-bridged porphyrin dimers 3 and 4, achieved through the Suzuki–Miyaura cross-coupling reaction. The optoelectronic properties, photophysical behavior, excited-state dynamics, and potential application of dimer 4 in photoelectrochemical water splitting (PEC-WS) are investigated. Dimer 4 exhibits a smaller HOMO–LUMO gap and a lower ionization potential than the corresponding monomer 5. However, despite having an extended ?-conjugation, the V-shaped geometry of the dimer restricts its long-range aggregation and charge/exciton delocalization in comparison to its corresponding monomer. The computational electronic structure analysis complements the experimental findings. The results presented in this paper provide rational insights into the structure–property correlation within the less explored azulene–porphyrin hybrid systems. © 2025 The Authors. Published by American Chemical Society