Tunability of Open‐Shell Character, Charge Asymmetry, and Third‐Order Nonlinear Optical Properties of Covalently Linked (Hetero)Phenalenyl Dimers

Minamida, Yuka; Kishi, Ryohei; Fukuda, Kotaro; Matsui, Hiroshi; Takamuku, Shota; Yamane, Masaki; Tonami, Takayoshi; Nakano, Masayoshi

doi:10.1002/chem.201704679

Cited by 4 publications

(3 citation statements)

References 89 publications

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“…34 In addition, the relationship between the second hyperpolarizability (g) and biradical characters for the biradical systems was investigated. 35,36 In 2016, Li and co-workers published a fascinating report on NLO switch, indicating that an electride molecule (e À Á Á ÁK(1) + Á Á Ácalix [4]pyrroleÁ Á ÁK(2) + Á Á Áe À ) had shown a significantly large NLO response under a small electric field, this main reason for this was the centrosymmetric breaking of the electron cloud. 37 In 2017, Timurdogan et al investigated electric-field-induced large second-order nonlinear susceptibility in silicon waveguides using complementary metal-oxidesemiconductor (CMOS)-compatible fabrication methods.…”

Section: Introductionmentioning

confidence: 99%

Stimulating intra- and intermolecular charge transfer and nonlinear optical response for biphenalenyl biradicaloid dimer under an external electric field

Gao

Muhammad

et al. 2018

Phys. Chem. Chem. Phys.

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An interesting biphenalenyl biradicaloid (IDPL) dimer consisting of both-middle superimposed phenalenyls and both-end nonsuperimposed phenalenyls has been synthesized, and has attracted intensive research interest due to its intra- and intermolecular interactions and semiconductive characteristics. It is significant that under regulation of the external electric field the directional charge transfer (CT) can produce attractive properties. In the present work, the structure and electronic properties of the IDPL dimer under an external electric field (along the horizontal Fx or the vertical Fz directions) are explored, and the following properties determined: (i) as the horizontal Fx increases, the intramolecular CT becomes larger, which induces the intermolecular CT of the IDPL dimer. (ii) In contrast, as the vertical Fz increases, the large intermolecular CT gives rise to the intramolecular CT of the IDPL dimer. (iii) More importantly, the external electric field effectively regulates and controls the first hyperpolarizability (βtot) of the IDPL dimer. Compared with the vertical Fz, the horizontal Fx induces a larger first hyperpolarizability (βtot = 5.48 × 105 a.u.). Furthermore, the application of a uniform external electric field (Fx,y,z) to the IDPL dimer was investigated to define the external electric field direction of the material application. The βtot values were increased with increasing of the uniform Fx,y,z. Our study provides an effective strategy for developing high-performance NLO materials by tuning the external electric field, and could be of significance for application in switch devices.

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Section: Introductionmentioning

confidence: 99%

Stimulating intra- and intermolecular charge transfer and nonlinear optical response for biphenalenyl biradicaloid dimer under an external electric field

Gao

Muhammad

et al. 2018

Phys. Chem. Chem. Phys.

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“…The introduction of B/N atoms can effectively regulate the charge redistribution. At present, there have been reported on the nonlinear optical (NLO) based on PLY and CPP. – However, there is still a lack of research on the NLO of the supramolecular complexes based on PLY and CPP. The study aims to employ supramolecular complexes as a versatile platform for the control of inter- and intramolecular charge transfer (CT) processes in order to achieve the modulation of second-order NLO responses.…”

Section: Introductionmentioning

confidence: 99%

Density Functional Theory Studies of B/N-Doped Phenalenyl Nanorings with C₆₀ for Tuning Second-Order Nonlinear Optical Properties

Huang,

Gan,

Liu

et al. 2023

ACS Appl. Nano Mater.

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A series of triangular nanorings, denoted B n N 3−n -CPLY 3 (n = 0, 1, 2, and 3), are designed by incorporating boron-/nitrogen-doped phenalenyl (B/N-PLY) units into cycloparaphenylene. These nanorings exhibit appropriate cavity size and shape complementarity to encapsulate fullerene (C 60 ), resulting in the formation of supramolecular complexes termed B n N 3−n -CPLY 3 @C 60 (n = 0, 1, 2, 3). The geometric and electronic structures of nanorings and supramolecular complexes are investigated by density functional theory. Importantly, the self-assembly strategy effectively enhances the second-order nonlinear optical (NLO) response of the supramolecular complexes. The findings demonstrate that the first hyperpolarizabilities of B n N 3−n -CPLY 3 @C 60 (n = 0, 1, 2) are higher compared to that of B 3 -CPLY 3 @C 60 , which is attributed to the intra-and intermolecular charge transfer (CT) regulated by adjusting the amount of the B/N-PLY unit. By absorption spectrum analysis, the absorption peaks of B n N 3−n -CPLY 3 @C 60 (n = 0, 1, 2) are attributed to the host−guest interaction between B n N 3−n -CPLY 3 and C 60 . Furthermore, CT spectroscopy, main electron transition, and CT properties are studied to gain insights into the optical properties of B n N 3−n -CPLY 3 @C 60 . This work not only emphasizes the importance of the B/N-PLY unit in supramolecular complexes to improve NLO properties but also shows that the B n N 3−n -CPLY 3 @C 60 complexes are important materials for optoelectronic applications.

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“…In this sense, we design and synthesize six chalcone compounds ( L1 – L6 ) combining nonlinear functional building blocks (anthracene) and an electron-deficient group (nitrogenous heterocyclic) , shown in Scheme . Hence, L1 – L6 can not only show ideal NLO properties , but also provide a possibility for the NLO regulation of metal ions because of the existence of nitrogen atoms.…”

Section: Introductionmentioning

confidence: 99%

Investigation of Regulating Third-Order Nonlinear Optical Property by Coordination Interaction

Zhao

Shao

et al. 2019

Inorg. Chem.

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In this paper, a series of organic compounds (L1–L6) with a D-π-A conjugation system were prepared. The investigations of third-order nonlinear optical (NLO) properties indicate that L1–L6 show different degrees of third-order NLO responses. It is surprising that introducing metal ions can effectively regulate their third-order NLO properties and even change the type of nonlinear absorption signal from reverse saturable absorption to saturable absorption, which can be attributed to the formation of coordination bonds between metal ions and L1–L6. It has aroused our tremendous interests in regulating third-order NLO performance. The regulation mechanisms were also discussed through the pump–probe measurements and the density functional theory. The enhancement of electron transfer efficiency is considered to be the key to improving NLO performance. Furthermore, we also obtained two coordination complexes [Cu(L1)2(NO3)2] (1) and [Cd(L1)2I2] (2) based on L1, which further proved the coordination between metal ions and L1–L6. Ligand-to-metal or metal-to-ligand charge transfer makes more electronic delocalization, leading to better third-order NLO properties. This work provides new ideas and explorations for the excogitation of third-order NLO materials.

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Tunability of Open‐Shell Character, Charge Asymmetry, and Third‐Order Nonlinear Optical Properties of Covalently Linked (Hetero)Phenalenyl Dimers

Cited by 4 publications

References 89 publications

Stimulating intra- and intermolecular charge transfer and nonlinear optical response for biphenalenyl biradicaloid dimer under an external electric field

Stimulating intra- and intermolecular charge transfer and nonlinear optical response for biphenalenyl biradicaloid dimer under an external electric field

Density Functional Theory Studies of B/N-Doped Phenalenyl Nanorings with C₆₀ for Tuning Second-Order Nonlinear Optical Properties

Investigation of Regulating Third-Order Nonlinear Optical Property by Coordination Interaction

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Tunability of Open‐Shell Character, Charge Asymmetry, and Third‐Order Nonlinear Optical Properties of Covalently Linked (Hetero)Phenalenyl Dimers

Cited by 4 publications

References 89 publications

Stimulating intra- and intermolecular charge transfer and nonlinear optical response for biphenalenyl biradicaloid dimer under an external electric field

Stimulating intra- and intermolecular charge transfer and nonlinear optical response for biphenalenyl biradicaloid dimer under an external electric field

Density Functional Theory Studies of B/N-Doped Phenalenyl Nanorings with C60 for Tuning Second-Order Nonlinear Optical Properties

Investigation of Regulating Third-Order Nonlinear Optical Property by Coordination Interaction

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Density Functional Theory Studies of B/N-Doped Phenalenyl Nanorings with C₆₀ for Tuning Second-Order Nonlinear Optical Properties