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Third-Order Nonlinear Optical Properties of One-Dimensional Quinoidal Oligothiophene Derivatives Involving Phenoxyl Groups.

ABSTRACT: The diradical characters (y) and third-order nonlinear optical (NLO) properties of open-shell quinoidal oligothiophene derivatives with phenoxyl groups, and the corresponding reduced (hydrogenated)-state oligomers, are investigated by using the broken-symmetry density functional theory method. The oxidized (dehydrogenated) states are predicted to have an open-shell singlet ground state and their y values increase with the number of units. Static second hyperpolarizabilities (?) of the open-shell oligomers with intermediate y are shown to be enhanced significantly compared with those of the closed-shell analogues. Furthermore, owing to the effective diradical distances, the ? values of open-shell oligomers are found to exceed that of s-indaceno[1,2,3-cd;5,6,7-c'd']diphenalene, which is known as an organic molecule with the largest two-photon absorption cross-section in this size of the pure hydrocarbons. This feature extends the range of efficient open-shell third-order NLO materials to a novel class of one-dimensional conjugated oligomers with redox-based high tunability of third-order NLO properties.

SUBMITTER: Kishi R

PROVIDER: S-EPMC5542765 | biostudies-literature | 2017 Aug

REPOSITORIES: biostudies-literature

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Third-Order Nonlinear Optical Properties of One-Dimensional Quinoidal Oligothiophene Derivatives Involving Phenoxyl Groups.

Kishi Ryohei R Katsurayama Tsubasa T Ochi Shoki S Makino Akihiro A Matsushita Naoyuki N Saito Michika M Nagami Takanori T Fujiyoshi Jun-Ya JY Nakano Masayoshi M

ChemistryOpen 20170703 4

The diradical characters (y) and third-order nonlinear optical (NLO) properties of open-shell quinoidal oligothiophene derivatives with phenoxyl groups, and the corresponding reduced (hydrogenated)-state oligomers, are investigated by using the broken-symmetry density functional theory method. The oxidized (dehydrogenated) states are predicted to have an open-shell singlet ground state and their y values increase with the number of units. Static second hyperpolarizabilities (γ</ ...[more]

PMID: 28794945

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Project description:In the present investigation, quantum chemical calculations have been performed in a systematic way to explore the optoelectronic, charge transfer, and nonlinear optical (NLO) properties of different bis(dicyanomethylene) end-functionalized quinoidal oligothiophenes. The effect of different conformations (linking modes of thiophene rings) on conformational, optoelectronic, and NLO properties are studied from the best-performed dimer to octamer. The optical and NLO properties of all the selected systems (1-7) are calculated by means of density functional theory (DFT) methods. Among all the designed compounds, the largest linear isotropic (αiso) polarizability value of 603.1 × 10-24 esu is shown by compound 7 which is ∼12, ∼16, ∼9, ∼11, ∼10, and ∼4 times larger as compared to compounds 1-6, respectively. A relative investigation is performed considering the expansion in third-order NLO polarizability as a function of size and conformational modes. Among all the investigated systems, system 7 shows the highest value of static second hyperpolarizability ⟨γ⟩ with an amplitude of 7607 × 10-36 esu at the M06/6-311G** level of theory, which is ∼521, ∼505, ∼38, ∼884, ∼185, and ∼15 times more than that of compounds 1-6, respectively. The extensively larger ⟨γ⟩ amplitude of compound 7 with higher oscillator strength and lower transition energy indicates that NLO properties are remarkably dependent upon linking modes of thiophene rings and its chain length. Furthermore, to trace the origin of higher nonlinearities, TD-DFT calculations are also performed at the same TD-M06/6-311G** level of theory. Additionally, a comprehensive understanding of the effect of structure/property relationship on the NLO polarizabilities of these investigated quinoidal oligothiophenes is obtained through the inspection of Frontier molecular orbitals, the density of states (TDOS and PDOS), and molecular electrostatic potential diagrams including the transition density matrix. Hence, the current examination will not just feature the NLO capability of entitled compounds yet additionally incite the interest of experimentalists to adequately modify the structure of these oligothiophenes for efficient optical and NLO applications.

Dataset Information

Third-Order Nonlinear Optical Properties of One-Dimensional Quinoidal Oligothiophene Derivatives Involving Phenoxyl Groups.

Publications

Third-Order Nonlinear Optical Properties of One-Dimensional Quinoidal Oligothiophene Derivatives Involving Phenoxyl Groups.

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