Computational study on second-order nonlinear optical (NLO) properties of a novel class of two-dimensional Λ- and W-shaped sandwich metallocarborane-containing chromophores

Na, Na; Yang, Guochun; Sun, Shi Ling; Liu, Chun Guang; Qiu, Y.Q.

doi:10.1016/j.jorganchem.2011.03.004

Cited by 31 publications

(8 citation statements)

References 50 publications

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“…Designing new systems with excellent charge transfer (CT) plays a vital role as improved ICT will further enhance the NLO susceptibility for the designed molecule . Dipolar (D‐ π ‐A) , quadrupolar (D‐ π ‐A‐ π ‐D or A‐ π ‐D‐ π ‐A) or octupolar systems are widely investigated for the applications as NLO materials. As the CT in such systems describes the low energy physics of these molecules and is also responsible for low‐energy excitations with the large transition and/or mesomeric dipole moments .…”

Section: Introductionmentioning

confidence: 99%

NLOphoric Triphenylamine Derived Donor‐π‐Acceptor‐π‐Donor Based Colorants: Synthesis, Spectroscopic, Density Functional Theory and Z‐scan Studies

Raikwar

Mathew²,

Varghese³

et al. 2019

Photochem & Photobiology

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Three Donor-p-Acceptor-p-Donor type styryl dyes (5a-c) with different secondary donors are synthesized and characterized to study their nonlinear and linear optical properties. The structure-property relationships of the dyes are described in the light of systematic photophysical and theoretical investigations. The photophysical characteristics of 5a-c are influenced by the polarity of the medium, with an appreciable bathochromic shift in emission (5b = 81 nm) and large Stoke shifts (5b = 104-173 nm) in polar solvents. 5a-c showed intramolecular charge transfer characteristics recognized with the help of emission solvatochromism, solvent polarity graphs, natural bond orbital analysis and HOMO-LUMO energy difference. The optimized geometry and frontier molecular orbitals reveal that the electron donation takes place from secondary donors and not from a fixed donor (triphenylamine) which is more twisted. The nonlinear optical properties obtained using solvent induced spectral shift and computational methods are found within the limiting values. Z-scan results reveal saturable kind of behavior for 5a, 5b and 5c, whereas 5a and 5b show reverse saturable kind of behavior in acetone and ethanol and hence give optical limiting values. The two-photon absorption cross section described by two-level approximation is highest for 5b (251-300 GM).

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Section: Introductionmentioning

confidence: 99%

NLOphoric Triphenylamine Derived Donor‐π‐Acceptor‐π‐Donor Based Colorants: Synthesis, Spectroscopic, Density Functional Theory and Z‐scan Studies

Raikwar

Mathew²,

Varghese³

et al. 2019

Photochem & Photobiology

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“…Recently multi‐dimensional dipolar chromophores have attracted attention as NLOphoric materials, of which two‐dimensional (2D) chromophores having a D‐π‐A‐π‐D framework are promising candidates as NLO materials with enhanced second‐order hyperpolarizabilities . The systems with D‐π‐A‐π‐D architect have several advantages like improved non‐linearity, noncentrosymmetry and have better phase‐matching because of their larger off‐diagonal component as compared to the dipolar (D‐π‐A) systems . Design and synthesis of push‐pull systems consisting of carbazole unit as D and dicyano vinylene as A to achieve enhanced NLO properties are of contemporary interest .…”

Section: Introductionmentioning

confidence: 99%

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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“…These materials are used in technical applications like lasers, 4 optical data storage devices, biological imaging, 5 signal processing, and in electro-optical modulation as well. 6,7 These materials range from being inorganic to organic to organometallic. 8−11 In order to identify additional and more efficient materials for further NLO applications, many studies were conducted on organic materials, including, for instance, the polycyclic aromatic hydrocarbons (PAH) or, polynuclear aromatic hydrocarbons.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Because of their numerous applications in the areas of photonics and optoelectronics, − various types of NLO active materials have been developed over the recent years. These materials are used in technical applications like lasers, optical data storage devices, biological imaging, signal processing, and in electro-optical modulation as well. , These materials range from being inorganic to organic to organometallic. − In order to identify additional and more efficient materials for further NLO applications, many studies were conducted on organic materials, including, for instance, the polycyclic aromatic hydrocarbons (PAH) or, polynuclear aromatic hydrocarbons. − These latter are a series of hydrocarbons in which carbon atoms are arranged in multiple aromatic rings sharing one or more C–C bond. The resulting structures are molecules wherein all carbon and hydrogen atoms are lying in the same plane.…”

Section: Introductionmentioning

confidence: 99%

Performance of Hybrid DFT Compared to MP2 Methods in Calculating Nonlinear Optical Properties of Divinylpyrene Derivative Molecules

et al. 2016

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A series of divinyl-pyrene derivatives of the form D-vinyl-pyrene-vinyl-A, in which D corresponds to an electron donor group and A to an electron acceptor group, were studied in this work. The first purpose was to determine the optimal HF % exchange as incorporated in a range of hybrid functionals (M06HF, M062X, M06L, CAM-B3LYP, PBE0, BMK, and B3LYP) capable to produce, reliably and as close as possible to those obtained from MP2 calculations, NLO parameters and, in particular, first-order static hyperpolarizabilities. The CAM-B3LYP functional was revealed to be the most suitable one. The pair N(CH)/NO was then determined as the most efficient pair of groups in producing appreciable NLO responses. The effect of the substitution position on the pyrene moiety was also investigated, whereby aligning the two substituents involving the D and A groups in the direction of the dipole moment as in the (1,6 DVP) derivatives was shown to be most favorable for increasing the NLO parameters.

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Computational study on second-order nonlinear optical (NLO) properties of a novel class of two-dimensional Λ- and W-shaped sandwich metallocarborane-containing chromophores

Cited by 31 publications

References 50 publications

NLOphoric Triphenylamine Derived Donor‐π‐Acceptor‐π‐Donor Based Colorants: Synthesis, Spectroscopic, Density Functional Theory and Z‐scan Studies

NLOphoric Triphenylamine Derived Donor‐π‐Acceptor‐π‐Donor Based Colorants: Synthesis, Spectroscopic, Density Functional Theory and Z‐scan Studies

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

Performance of Hybrid DFT Compared to MP2 Methods in Calculating Nonlinear Optical Properties of Divinylpyrene Derivative Molecules

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