NIR emitting new N, N-diethylaniline based NLOphoric D-π-A and D-A′-π-A dyes: Photophysical properties, viscosity sensitivity and DFT studies

Patil, Dinesh S.; Jadhav, Manoj M.; Avhad, Kiran C.; Gawale, Yogesh; Sekar, Nagaiyan

doi:10.1016/j.jlumin.2018.08.031

Cited by 19 publications

(11 citation statements)

References 58 publications

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“…The resulting data are presented in Table . These NLO parameters were evaluated by experimental and theoretical calculations based on the detailed theory described in the reported literature …”

Section: Resultsmentioning

confidence: 99%

“…These NLO parameters were evaluated by experimental and theoretical calculations based on the detailed theory described in the reported literature. [55][56][57] From Table 5, the theoretically calculated of α 0 , β 0 and γ 0 values for MMR1 are found in the range 100-127 × 10 À 24 esu, 807-2,903 × 10 À 30 esu, and 4,699-25,748 × 10 À 36 esu respectively using these functional. On the other hand, these values are in the range 117-145 × 10 À 24 e.s.u., 705-2,713 × 10 À 30 e.s.u., and 4,674-29,731 × 10 À 36 e.s.u.…”

Section: Polarizability and Hyperpolarizability By Dft Methodsmentioning

confidence: 95%

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Biphenyl‐Amine‐Based D‐π‐A’‐π‐A Sensitizers for DSSCs: Comparative Photo‐Conversion Efficiency in Iodide/triiodide and Cobalt‐Based Redox Electrolyte and DFT Study

et al. 2019

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We have designed and synthesized two dye molecules viz. MMR1 ((E)‐2‐cyano‐3‐(5‐((E)‐1‐cyano‐2‐(4′‐(dimethylamino)‐[1,1′‐biphenyl]‐4‐yl)vinyl)thiophen‐2‐yl)acrylic acid) and MMR2 (2‐((Z)‐5‐((5‐((E)‐1‐cyano‐2‐(4′‐(dimethylamino)‐[1,1′‐biphenyl]‐4‐yl)vinyl)thiophen‐2‐yl)methylene)‐4‐oxo‐2‐thioxothiazolidin‐3‐yl)acetic acid) with D‐π‐A’‐π‐A frameworks. The synthesized interfacial modifiers have dimethyl aniline as the donor group whereas cyanoacetic acid and rhodanine‐3‐acetic acid as the major acceptor groups in MMR1 and MMR2 respectively. The photophysical study in solution medium shows red shifted absorption maxima (λmax) for MMR2 vs MMR1. However, the molar extinction coefficient (ϵmax) for MMR2 is found to be lower than MMR1. The photovoltaic characterization of these molecules was carried out using iodide/triiodide and cobalt (II/III) based redox electrolytes for comparision. The molecules showed improved efficiency with the cobalt based electrolytes where MMR1 showed the highest power conversion efficiency (PCE) of 3.25% (Jsc=7.28 mA/cm2, Voc=0.713 V, FF=0.63). Further to have a deep insight into these synthesized molecules DFT studies were performed. The polarizability and hyperpolarizability values for the interfacial modifiers are calculated using DFT computation and are found to be correlated to the PCE.

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Section: Resultsmentioning

confidence: 99%

Section: Polarizability and Hyperpolarizability By Dft Methodsmentioning

confidence: 95%

Biphenyl‐Amine‐Based D‐π‐A’‐π‐A Sensitizers for DSSCs: Comparative Photo‐Conversion Efficiency in Iodide/triiodide and Cobalt‐Based Redox Electrolyte and DFT Study

et al. 2019

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“…Based on the comprehensive theory outlined in the literature reported, these NLO parameters were evaluated using both experimental and theoretical calculations . The theoretically calculated of α 0 , β 0 and γ 0 values for 5 a‐c using BHHLYP functional are found in the range 77–109 × 10 −24 esu, 187–522 × 10 −30 esu, and 649–2,530 × 10 −36 esu respectively (Table and S14 – S17 ).…”

Section: Resultsmentioning

confidence: 99%

“…Based on the comprehensive theory outlined in the literature reported, these NLO parameters were evaluated using both experimental and theoretical calculations. [127][128][129] The theoretically calculated of α 0 , β 0 and γ 0 values for 5 a-c using BHHLYP functional are found in the range 77-109 × 10 À 24 esu, 187-522 × 10 À 30 esu, and 649-2,530 × 10 À 36 esu respectively ( Table 3 and S14 -S17). These values, on the other hand, with ωB97XD functional are in the range 77-108 × 10 À 24 e.s.u., 196-596 × 10 À 30 e.s.u., and 648-2,237 × 10 À 36 e.s.u.…”

Section: Computational Approachmentioning

confidence: 95%

N‐Ethyl Carbazole Derived D‐π‐A‐π‐D Based Fluorophores: Consolidated Spectroscopic, Viscosity and DFT Studies

2019

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This article reports design and synthesis of three new fluorophores (5 a‐c) with the donor‐π‐acceptor‐π‐donor motif, where dicyano vinylene group is the central acceptor, N‐ethyl carbazole group is a fixed donor and varying the N‐substituted secondary donors so as to study their photophysical behavior. Based on the systematic photophysical and theoretical reconnaissances, the fluorophores structure‐property relationships are defined. Their spectral and photophysical behaviors are affected by the solvent polarity, with a significant bathochromic shift in emission and large Stoke shifts being observed in polar solvents. Contrary to dipolar asymmetric analogue this system shows an efficient intramolecular charge transfer as observed from various solvent polarity plots. For 5 a, 5 b, and 5 c, the viscosity induced emission studies show respectively 3.78, 6.53, and 6.82 times enhancement in their fluorescence intensity and hence act as a fluorescent molecular rotor (FMR). The structure and electronic properties of these fluorophores were evaluated using density functional theory computations using B3LYP/6‐311++G(d,p). The frontier molecular orbitals and the optimized geometry reveal that secondary donors in each fluorophore donate the electron and not the N‐ethyl carbazole group which is more twisted. The non‐linear and linear optical properties were determined employing solvatochromic and computational methods in solvents of varying polarities with results falling within the expected limiting values. The linear and non‐linear optical properties of the fluorophores change with the strength of different secondary donors used and solvent polarity. The two photon absorption cross‐section described using two level approximation is highest for 5 b (115‐172 GM).

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“…[4,5] Nowadays there is a great deal of interest in the designing chromophores with strong nonlinear optical properties in the red region. [6,7] Due to its high photostability, very high quantum yield and high solubility in organic solvents, a large number of coumarin derivatives are studied as fluorescent probes, [8] fluorescent sensors, [9,10] in cell imaging, [11,12] as well as in the field of nanotechnology, [13] and optoelectronics, [14] Simultaneously they have wide uses in the arena of "Organic Light Emitting Diodes" (OLEDs), [15] "Dye Sensitized Solar Cells" (DSSCs), [16][17][18] dye lasers, [19,20] optical brighteners, [21] non-linear optical (NLO) materials, [22] and in biological labeling, [23,24] Photophysical properties of coumarins can be tuned to red emission by the attachment of electron donating group at 7 positions, [25] electron accepting group at 3 and 4 positions, [26] as well as rigidification ofthe donor or acceptor, [25] and increasing the length of conjugation. [27,28] Coumarin based NLO push-pull system possessing donor at 7 positions and acceptor at 3 positions with thiophene unit as π-spacer were preparedprepared and their NLO characteristics were examined by z scan experiment as well as a computational method.…”

Section: Introductionmentioning

confidence: 99%

Coumarin and Hydroxyl Decorated Viscosity Sensitive Triphenylamine Derivatives: Synthesis, Photophysical Properties, Viscosity Sensitivity, TD‐DFT, and NLO Properties

2019

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Three novel hydroxyl substituted and triphenylamine sidearm coumarin decorated molecules were prepared to examine the effect of adjacent hydroxyl substituent as well as coumarin units on the photophysical linear and nonlinear optical properties. Both hydroxyl function adjacent to the phenyl ring and extra coumarin unit is attributed to the red shifted absorption (435‐487 nm) and emission (496‐578 nm) compared to the plain triphenylamine based coumarin derivatives. Positive solvatochromism around 70 nm was observed in solvents with different polarity polarities and it is reinforced by solvent polarity plots and multilinear regression study. Very high viscosity induced emission enhancement (5.7 – 8.2 fold) was observed for in ethanol/polyethylene glycol‐400 system, highlighting their capability to act as efficient fluorescent molecular rotors (FMRs). The nonlinear optical properties were investigated by solvatochromism as well as a computational method using B3LYP 6–311++G (d, p) basis set. All these compounds exhibited large magnitudes of first order (65‐208x10 −30e.s.u) and second order (560‐2120x10 −36e.s.u) hyperpolarizability.

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NIR emitting new N, N-diethylaniline based NLOphoric D-π-A and D-A′-π-A dyes: Photophysical properties, viscosity sensitivity and DFT studies

Cited by 19 publications

References 58 publications

Biphenyl‐Amine‐Based D‐π‐A’‐π‐A Sensitizers for DSSCs: Comparative Photo‐Conversion Efficiency in Iodide/triiodide and Cobalt‐Based Redox Electrolyte and DFT Study

Biphenyl‐Amine‐Based D‐π‐A’‐π‐A Sensitizers for DSSCs: Comparative Photo‐Conversion Efficiency in Iodide/triiodide and Cobalt‐Based Redox Electrolyte and DFT Study

N‐Ethyl Carbazole Derived D‐π‐A‐π‐D Based Fluorophores: Consolidated Spectroscopic, Viscosity and DFT Studies

Coumarin and Hydroxyl Decorated Viscosity Sensitive Triphenylamine Derivatives: Synthesis, Photophysical Properties, Viscosity Sensitivity, TD‐DFT, and NLO Properties

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