Third order NLO properties of corannulene and its Li-doped dimers: effect of concave–convex and convex–convex structures

Wang, Li; Wang, Wenyong; Fang, Xin-Yan; Zhu, Changli; Qiu, Yong‐Qing

doi:10.1039/c5ra09864e

Cited by 26 publications

(8 citation statements)

References 61 publications

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“…To the best of our knowledge, the ⟨ R 2 ⟩ is used to characterize the electron density volume around the molecule as a physical property. The more diffuse electron cloud may lead to a larger ⟨ R 2 ⟩ value, resulting in a larger α value. , …”

Section: Resultsmentioning

confidence: 99%

Regulation of the Molecular Architectures on Second-Order Nonlinear Optical Response and Thermally Activated Delayed Fluorescence Property: Homoconjugation and Twisted Donor–Acceptor

Wang

Zhang

et al. 2019

J. Phys. Chem. C

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The nonlinear optical (NLO) and thermally activated delayed fluorescence (TADF) properties of organic push–pull materials consisting of π-conjugated electron-donating (D) and electron-accepting (A) subunits are dominated by the interaction of D and A moieties via intramolecular charge transfer (ICT). Understanding the structure–property relationship, at the microscopic level, is the prerequisite for further performance optimization or improvement. In this work, we theoretically investigated the geometric and electronic structures, CT properties, polarizabilities (α), first hyperpolarizabilities (βtot), and singlet–triplet energy gap (ΔE ST) of the homoconjugation (as type I) and the conventional conjugation D–A (as type II) compounds. A noteworthy finding was that the type II molecule was suggested to promote the performance in NLO due to the lower excited energy and larger dipole moment variations for the crucial excited state, as well as the larger separate distributions of first hyperpolarizability density. In addition, the electron transition properties, second-order NLO responses, and ΔE ST values strongly depend on the nature of different electron acceptors (pyrazine → dicyanopyrazine → dicyanoquinoxaline). Further, based on the polarizable continuum model analysis, the increment in the βtot of all studied compounds is preferable for NLO applications. Moreover, the ΔE ST values of the molecules in which the acceptor are replaced by dicyanopyrazine/dicyanoquinoxaline (2, 3, and 6) in vacuum are reduced by an order of magnitude when embedded in a polarizable environment, indicating they are potentially efficient TADF materials. Overall, we envision that the various architectures and the polarization effect introduced in the present work will offer a route toward the rational design of such kind of D–A system for novel functional second-order NLO and TADF materials.

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Section: Resultsmentioning

confidence: 99%

Regulation of the Molecular Architectures on Second-Order Nonlinear Optical Response and Thermally Activated Delayed Fluorescence Property: Homoconjugation and Twisted Donor–Acceptor

Wang

Zhang

et al. 2019

J. Phys. Chem. C

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“…Previous studies of our group have shown that substitution of the central CC of TTF by Ni has a large effect on the L and NLO properties. , The resulting bis(ethylene-1,2-dithiolato)nickel (NiBDT) has many interesting properties (e.g., photochemical and thermal stability, tunable properties), due to which it is considered to be a very promising material. − Several theoretical studies have also shown that lithiation may lead to a significant increase of the second hyperpolarizability. − …”

Section: Introductionmentioning

confidence: 99%

A Series of Novel Derivatives with Giant Second Hyperpolarizabilities, Based on Radiaannulenes, Tetrathiafulvalene, Nickel Dithiolene, and Their Lithiated Analogues

et al. 2016

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The main goal of this study was the design/ recognition of a series of derivatives with exceptionally large hyperpolarizabilities, the understanding of the mechanism through which these properties are derived, and the generalization of the resulting findings. Thus, we have studied the structure, a series of properties involving the excitation energies and the diradical character, but mainly the (hyper)polarizabilities of some oligomers of radiaannulene-tetrathiafulvalene (RA-TTF), radiaannulene-bis(ethylene-1,2dithiolato)nickel (RA-NiBDT), and their lithiated analogues. The employed methodology involves MP2 and DFT techniques, approaches for the computation of static and frequency-dependent properties, and techniques for the calculation of electronic and vibrational contributions. The polarizability has been partitioned be employing the fractional occupational Hirshfeld iterative method. Indices for the calculation of the diradical character of the NiBDT oligomers have been employed. We have found that (i) oligomerization increases γ zzzz (second hyperpolarizability), (ii) substitution of TTF with NiBDT leads to a very large increase of γ zzzz , and (iii) lithiation leads to extremely large nonlinearities. The importance of NiBDT and lithium as building blocks for the production of NLO materials is highlighted.

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“…In addition, the orbital overlap for HOMO reflects π–π stacking interaction between superimposed B/N-PLYs, which is conducive to intra- and intermolecular CT transitions from B-PLY to N-PLY. Further, the transition density matrix (TDM) , and the charge density difference maps (CDDMs) of dominant electron transitions are investigated for systems 2 , 3 , and 2 2 (Figures S3 and S4), providing valuable evidence for the above discussions.…”

Section: Resultsmentioning

confidence: 99%

Intra- and Intermolecular Charge Transfer in a Novel Dimer: Cooperatively Enhancing Second-Order Optical Nonlinearity

Gao

Zhong

et al. 2017

J. Phys. Chem. C

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Based on s-indaceno [1,2,3-cd;5,6,7-c′d′]diphenalene (1) consisting of two phenalenyl moieties, the monomer 2 and its dimer 2 2 are designed by boron and nitrogen atoms substituting the central carbon atoms of phenalenyl moieties. Calculated energy decompose analysis (EDA) shows that the orbital interaction for 2 2 possesses a large attractive contribution of −18.31 kcal mol −1 , which is dominated by the π−π stacking interaction between the upper and the lower π-conjugated units. Interestingly, the natural population analysis (NPA) charge and the transition density matrix (TDM) show that both intramolecular charge transfer and intermolecular charge transfer (CT) exist in 2 2 . Further, the first hyperpolarizability (β tot = 4.56 × 10 4 au) of 2 with intramolecular CT is greatly larger than that of reported molecule 3 (5.45 × 10 3 au) with intermolecular CT. Significantly, 2 2 exhibits the largest β tot value to be 1.42 × 10 5 au, which is caused by combining the intra-and intermolecular CT transitions (β x = 1.40 × 10 5 au and β z = 2.27 × 10 4 au). Correspondingly, highest occupied molecular orbital (HOMO) → lowest unoccupied molecular orbital (LUMO) (intramolecular CT) in the low-energy electronic transition of 2 2 is 68%, while HOMO → LUMO + 1 (intermolecular CT) is 18%, which demonstrates that the intramolecular CT effect on the β tot value is stronger than the case of the intermolecular CT effect. The present work might provide rich insight into designing and developing potential second-order optical nonlinearity materials with inter-and intramolecular CT characters.

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Third order NLO properties of corannulene and its Li-doped dimers: effect of concave–convex and convex–convex structures

Abstract: The convex–convex stacking motif of corannulene dimers enhances the third-order NLO response due to obvious interlayer charge transfer.

Cited by 26 publications

References 61 publications

Regulation of the Molecular Architectures on Second-Order Nonlinear Optical Response and Thermally Activated Delayed Fluorescence Property: Homoconjugation and Twisted Donor–Acceptor

Regulation of the Molecular Architectures on Second-Order Nonlinear Optical Response and Thermally Activated Delayed Fluorescence Property: Homoconjugation and Twisted Donor–Acceptor

A Series of Novel Derivatives with Giant Second Hyperpolarizabilities, Based on Radiaannulenes, Tetrathiafulvalene, Nickel Dithiolene, and Their Lithiated Analogues

Intra- and Intermolecular Charge Transfer in a Novel Dimer: Cooperatively Enhancing Second-Order Optical Nonlinearity

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