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Interfacing High-Energy Charge-Transfer States to a Near-IR Sensitizer for Efficient Electron Transfer upon Near-IR Irradiation
Authors:Dilip Pinjari  Ajyal Z Alsaleh  Dr Yuvraj Patil  Prof Dr Rajneesh Misra  Prof Dr Francis D'Souza
Institution:1. Department of Chemistry, Indian Institute of Technology, Indore, 453552 India

These authors contributed equally to this work.;2. Department of Chemistry, University of North Texas, 1155 Union Circle, #305070, Denton, TX, 76203-5017 USA

These authors contributed equally to this work.;3. Department of Chemistry, Indian Institute of Technology, Indore, 453552 India;4. Department of Chemistry, University of North Texas, 1155 Union Circle, #305070, Denton, TX, 76203-5017 USA

Abstract:Push–pull systems comprising of triphenylamine–tetracyanobutadiene (TPA-TCBD), a high-energy charge-transfer species, are linked to a near-IR sensitizer, azaBODIPY, for promoting excited-state CS. These systems revealed panchromatic absorption owing to intramolecular CT and near-IR absorbing azaBODIPY. Using electrochemical and computational studies, energy levels were established to visualize excited state events. Fs-TA studies were performed to monitor excited state CT events. From target analysis, the effect of solvent polarity, number of linked CT entities, and excitation wavelength dependence in governing the lifetime of CS states was established. Electron exchange between two TPA-TCBD entities in 3 seem to prolong lifetime of the CS state. We have been successful in demonstrating efficient CS upon both high-energy CT and low-energy near-IR excitations, signifying importance of these push–pull systems for optoelectronic applications operating in the wide optical window.
Keywords:excited-state charge separation  High-energy charge transfer  near-IR sensitizers  panchromatic absorbance  ultrafast spectroscopy
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