Dataset Information

Enhancing Third-Order Nonlinear Optical Property by Regulating Interaction between Zr₄(embonate)₆ Cage and N, N-Chelated Transition-Metal Cation.

ABSTRACT: Herein, the combination of anionic Zr₄L₆ (L = embonate) cages and N, N-chelated transition-metal cations leads to a series of new cage-based architectures, including ion pair structures (PTC-355 and PTC-356), dimer (PTC-357), and 3D frameworks (PTC-358 and PTC-359). Structural analyses show that PTC-358 exhibits a 2-fold interpenetrating framework with a 3,4-connected topology, and PTC-359 shows a 2-fold interpenetrating framework with a 4-connected dia network. Both PTC-358 and PTC-359 can be stable in air and other common solvents at room temperature. The investigations of third-order nonlinear optical (NLO) properties indicate that these materials show different degrees of optical limiting effects. It is surprising that increasing coordination interactions between anion and cation moieties can effectively enhance their third-order NLO properties, which can be attributed to the formation of coordination bonds that facilitate charge transfer. In addition, the phase purity, UV-vis spectra, and photocurrent properties of these materials were also studied. This work provides new ideas for the construction of third-order NLO materials.

SUBMITTER: Xiang G

PROVIDER: S-EPMC10005618 | biostudies-literature | 2023 Mar

REPOSITORIES: biostudies-literature

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Publications

Enhancing Third-Order Nonlinear Optical Property by Regulating Interaction between Zr4(embonate)6 Cage and N, N-Chelated Transition-Metal Cation.

Xiang Gang G Li Na N Chen Guang-Hui GH Li Qiao-Hong QH Chen Shu-Mei SM He Yan-Ping YP Zhang Jian J

Molecules (Basel, Switzerland) 20230301 5

Herein, the combination of anionic Zr4L6 (L = embonate) cages and N, N-chelated transition-metal cations leads to a series of new cage-based architectures, including ion pair structures (PTC-355 and PTC-356), dimer (PTC-357), and 3D frameworks (PTC-358 and PTC-359). Structural analyses show that PTC-358 exhibits a 2-fold interpenetrating framework with a 3,4-connected topology, and PTC-359 shows a 2-fold interpenetrating fram ...[more]

PMID: 36903547

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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

Enhancing Third-Order Nonlinear Optical Property by Regulating Interaction between Zr₄(embonate)₆ Cage and N, N-Chelated Transition-Metal Cation.

Publications

Enhancing Third-Order Nonlinear Optical Property by Regulating Interaction between Zr<sub>4</sub>(embonate)<sub>6</sub> Cage and N, N-Chelated Transition-Metal Cation.

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