Faculty Publications
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Item Effects of substituents on the enrichment of the optical limiting action of novel imidazo[2,1-: B] [1,3,4]thiadiazole fused thiophene-based small molecules(Royal Society of Chemistry, 2019) Kakekochi, V.; Udayakumar, D.; Nikhil, P.P.; Chandrasekharan, K.The imidazo[2,1-b][1,3,4]thiadiazole (ITD) ring is a fused, planar aromatic heterocyclic system consisting of four heteroatoms with a bridgehead nitrogen atom. In this study, three new donor-acceptor-donor (D-A-D)-type organic molecules (ThITD1-ThITD3) were designed and synthesized, wherein ITD was an electron acceptor unit and the thiophene/phenyl moieties were electron donor units that produced a D-A-D configuration. The thiophene-ITD core structure comprises three different groups viz., thiophene-2-acetonitrile (ThITD1), phenylacetonitrile (ThITD2) and rhodanine-3-acetic acid (ThITD3), and the effect of substituents on the optical and electrochemical properties have been discussed based on structural modifications. The third-order nonlinear optical (NLO) properties analyzed by the Z-scan technique reveal that the molecules exhibit effective two photon absorption (TPA) with ThITD3 possessing substantially higher effective TPA coefficient (?eff) than ThITD1 and ThITD2, which is comparable to the reported ?eff values. The results unravel that ITD as an acceptor with an appropriate ?-linker will be a promising candidate for application in the field of optoelectronics/photonics. Herein, the thiophene-ITD ring system was explored for NLO applications and reported for the first time. © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.Item An investigation on photophysical and third–order nonlinear optical properties of novel thermally–stable thiophene–imidazo [2,1-b][1,3,4] thiadiazole based azomethines(Elsevier Ltd, 2019) Kakekochi, V.; Udayakumar, U.; Nikhil, N.P.; Chandrasekharan, K.The use of ?–conjugated semiconducting materials in flexible and large–area optoelectronic devices is proliferated worldwide owing to the easy structural modifications and solution processability possible, leading to the change in opto–electronic properties. In this context, new class of thiophene and imidazo [2,1-b][1,3,4] thiadiazole (ITD) based conjugated azomethines (TI1–TI3) were designed and synthesized. The photophysical and electrochemical properties of the synthesized azomethines (TI1–TI3) were investigated experimentally, which were further validated with the aid of theoretical calculations. Further, the azomethines TI1 and TI2 were subjected to Z–scan analysis to study the nonlinear optical (NLO) properties. The molecules exhibited effective two photon absorption (TPA) with the large nonlinear absorption coefficient (?eff) of the order of 10?10 m W?1. The planar structure of TI1 furnished a better interaction between donor and acceptor moieties and extended the ?–conjugation, providing an improved ?eff (0.81 × 10?10 m W?1) to TI1 compared to that of TI2 (0.55 × 10?10 m W?1). From the results it is inferred that the molecules could be of potential materials to be used in efficient photonic devices. © 2019 Elsevier LtdItem Impact of donor–acceptor alternation on optical power limiting behavior of H–Shaped thiophene–imidazo[2,1-b] [1,3,4]thiadiazole flanked conjugated oligomers(Elsevier Ltd, 2020) Kakekochi, V.; Nikhil, P.; Chandrasekharan, K.; Udayakumar, U.A new series of four D–A–D configured conjugated oligomers with H–type structure, possessing two thiophene–imidazo [2,1-b][1,3,4]thiadiazole branches and thiophene (TIT), thiophene–1,3,4-oxadiazole–thiophene (TITO), thiazolo [5,4-d]thiazole (TITz), phenyl–thiazolo [5,4-d]thiazole–phenyl (TIPTz) units as central core moieties were efficiently synthesized. These core moieties were specifically selected to increase the planarity, rigidity, stability, extend the ?–conjugation and to understand the influence of central core on nonlinear absorption coefficient (?eff) and optical limiting behavior of the synthesized oligomers. The structure-property relationships of these oligomers were established by the optical absorption (UV–Vis), electrochemical (CV) and theoretical (DFT) studies. The “effective two–photon absorption” of oligomers was confirmed by single–beam Z–scan analysis. The exceptional increase in nonlinear response was achieved with the oligomers TITO and TIPTz with nonlinear absorption coefficient (?eff) of 1.62 and 2.71 × 10?10 m W?1, and limiting thresholds of 6.02 and 3.14 J cm?2, respectively, which suggest that these oligomers could be potent materials for practical applications in laser photonics. © 2020 Elsevier LtdItem Facile synthesis and exploration of excited state assisted two-photon absorption properties of D-A-D type thiophene-pyridine derivatives(Royal Society of Chemistry, 2020) Kakekochi, V.; Chatnahalli Gangadharappa, S.; Nikhil, P.P.; Chandrasekharan, K.; Wolcan, E.; Udayakumar, U.K.A series of trigonal-shaped molecules (TPyT and TPyP) and a polymer (P2TPy) with donor-acceptor-donor (D-A-D) structural arrangement were designed with thiophene and 2,4,6-trisubstituted pyridine as the backbone i.e., a 4-(4-(decyloxy)phenyl)-2,6-di(thiophen-2-yl)pyridine core structure, for the first time and synthesized via a microwave assisted one pot reaction. The extension of conjugation of the system by substituting thiophene acrylonitrile (TPyT) and phenyl acrylonitriles (TPyP and P2TPy) via low cost condensation reactions improved the linear optical, electronic and thermal properties of the synthesized compounds. Furthermore, the nonlinear absorption (NLA) was also enriched appreciably by increasing the conjugation. The three compounds showed an "effective two-photon absorption" phenomenon with the NLA coefficient (?eff) of the order of 10-10 m W-1. The suitability to be utilized in the fabrication of all-optical limiting devices is best achieved by polymer P2TPy as it exhibits substantially higher ?eff (7.02 × 10-10 m W-1) and an extremely low optical limiting threshold (1.42 J cm-2). © 2020 The Royal Society of Chemistry and Owner Societies.Item Butterfly-Shaped Thiophene-Pyridine Hybrids: Green Electroluminescence and Large Third-Order Optical Nonlinearities(Wiley-VCH Verlag info@wiley-vch.de, 2020) Kakekochi, V.; Gangadharappa, S.C.; Nikhil, P.P.; Chandrasekharan, K.; Darshan, V.; Narayanan Unni, K.N.; Udayakumar, U.K.A set of four symmetric, butterfly-shaped 4-(4-(decyloxy)phenyl)-2,6-di(thiophen-2-yl)pyridine (TPY) derivatives 2TPA-TPY (TPY center and triphenylamine end groups), 2CBZ-TPY (TPY center and N-ethyl carbazole end groups), 2TPY-TPA (triphenylamine center and TPY at the periphery) and 2TPY-CBZ (N-ethyl carbazole center and TPY at the periphery) was synthesized. The molecules show reverse saturable absorption (RSA) which is consistent with two-photon absorption (2PA) associated with excited-state absorption (ESA) when excited using a 532 nm laser beam. The molecules 2TPA-TPY and 2TPY-TPA possess extremely low limiting thresholds of 1.73 and 2.68 J cm?2, respectively. An organic light-emitting diode (OLED) fabricated from 2TPA-TPY exhibits green emission with a maximum luminance of 207 cd m?2, a current efficiency (?CE) of 1.51cd A?1, a maximum power efficiency (?Pmax) of 0.46 lm W?1 and an external quantum efficiency (?EQE) of 0.48 % at 100 cd m?2. © 2020 Wiley-VCH Verlag GmbH & Co. KGaA, WeinheimItem All-Optical Diode Action through Enhanced Nonlinear Response from Polymeric Photonic Crystal Microcavity(American Chemical Society, 2022) Puthiya Purayil, N.; Kakekochi, V.; Udayakumar, U.K.; Chandrasekharan, C.The search for materials for nanophotonic devices needs a way to overcome the limitations of weak nonlinear optical response due to reduced size. The requirement of a high-power excitation source for inducing nonlinear effects in the active medium poses a hurdle in realizing all-optical and integrated optoelectronic systems. Nanosized optical materials can be embedded in photonic cavities to enhance its optical nonlinear responses through confinement effects. This report systematically investigates the linear and nonlinear optical properties of polymeric 1D-photonic crystals (PhC) with a defect layer incorporated with an imidazo-thiadiazole derivative small molecule. The nonlinear optical studies were carried out by means of a z-scan technique under nanosecond pulse using a Q-switched Nd:YAG laser operating at 532 nm. The resonant excitation creates strong confinement of light in the photonic microcavity and facilitates strong light-matter interaction that induces nonlinear response at low input intensities. A giant enhancement in the nonlinear absorption and optical limiting action was observed for PhC comparing to the bare sample. The significant enhancement in the absorptive nonlinearity is utilized for realizing a practical, on-chip, passive, all-optical diode with a PhC/Au hybrid structure. The asymmetrical nonlinear absorption of the hybrid structure exhibits non-reciprocal light transmission in the nonlinear regime. The high transmittance contrast ratio for forward/reverse bias operation and cost-effective fabrication methods makes our system a potential candidate toward the realization of compact photonic integrated devices. © 2021 American Chemical Society.Item A tale of two organic small molecular hole transporting materials: Showing same extended shelf-life but very different efficiency of inverted MAPbI3 perovskite solar cells(Elsevier B.V., 2022) Kakekochi, V.; Kuo, D.-W.; Chen, C.-T.; Wolcan, E.; Chen, C.-T.; Udayakumar, U.K.This paper mainly discusses the structure-property relationship of two donor-acceptor-donor (D–π–A–π–D) type dopant-free hole transporting materials (HTMs) (TPA-TPy and TPA-Py-PTZ) comprising primarily of 2,4,6-trisubstituted pyridine as the acceptor core and 4,4′-dimethoxytriphenylamine as the peripheral donor groups and their use in p-i-n perovskite solar cells (PVSCs). Compared to inferior TPA-Py-PTZ, TPA-TPy has a superior hole extraction and hole transport at the HTM/perovskite interface. The pinhole-free, smooth and dense, fully covered and well-crystallized MAPbI3 perovskite layer on TPA-TPy reduces the carrier recombination and substantially improves the short circuit current density (JSC), open circuit voltage (VOC), and the fill-factor (FF) of MAPbI3 PVSCs. The PVSC employing TPA-TPy as HTM exhibits a power conversion efficiency (PCE) of 15.33% with a JSC of 23.69 mA cm−2, a VOC of 0.95 V, and a FF of 68.10%. Especially, both TPA-TPy and TPA-Py-PTZ PVSCs exhibit a better moisture stability than that of NiOx PVSCs. It is because of the hydrophobic nature of TPA-TPy and TPA-Py-PTZ, which enables the formation of MAPbI3 perovskite layer having a larger grain-size, a less grain boundary, and a less infiltration of moisture. © 2022 Elsevier B.V.