A DFT study of the second-order nonlinear optical properties of Ru(<scp>ii</scp>) polypyridine complexes

Chen, Yu; Zhang, Yuan; Shen, Yonghang; Zhao, Yuanyuan; Qiu, Yong‐Qing

doi:10.1039/d2cp00941b

Cited by 7 publications

(5 citation statements)

References 48 publications

(65 reference statements)

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“…Usually, the more diffuse electron may lead to larger <R 2 > and then a larger α value. 50,51 The <R 2 > value follows the descending order: trans-Rh (8.1 × 10 4 a.u.) > cis-Rh (7.2 × 10 4 a.u.…”

Section: Resultsmentioning

confidence: 99%

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Theoretical Perspective on Two-State “ON–OFF” NLO Switch of Rh(III)-Azobenzene Complex with Considerable First Hyperpolarizability

Wang

Chen

2023

J. Phys. Chem. A

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In this paper, a light-induced Rh(III)-azobenzene (azo) complex in its two conformations (cis- and trans-form) is analyzed via density functional theory methods, focusing on the geometrical and electronic structure, linear and second-order nonlinear optical (NLO) properties, as well as UV–vis absorption spectra. The results show that trans-Rh exhibits more obvious charge separation and more extensive π-conjugation than cis-Rh. The energy gaps (E gap) between the highest occupied molecular orbital and lowest unoccupied molecular orbital of cis-Rh and trans-Rh are as small as 0.28 and 0.36 eV, respectively. The unusual small E gap facilitates electronic transition and accompanies large NLO responses. In particular, cis-Rh and trans-Rh possess considerably large second-order NLO responses with the first hyperpolarizability (βtot) up to 7.0 × 104 a.u. (“OFF” state) and 8.5 × 104 a.u. (“ON” state), respectively. trans-Rh shows good π-conjugation and obvious electric delocalization relative to cis-Rh and thus a considerable βtot value. The switchable ratio of βtot ( trans-Rh)/βtot ( cis-Rh) is equal to 1.2, showing switch characteristics. UV–vis analyses indicate that the ON and OFF states can finely tune the absorption range due to the strongest absorption peaks of cis-Rh (301 nm) and trans-Rh (446 nm) lying in the UV and vis region, respectively. It is expected that the studied Rh(III)-azo complexes may be applied in the field of optoelectronics.

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Section: Resultsmentioning

confidence: 99%

“…The electronic spatial extent < R 2 > is often used to characterize the electron density volume around the molecule. Usually, the more diffuse electron may lead to larger < R 2 > and then a larger α value. , The < R 2 > value follows the descending order: trans -Rh (8.1 × 10 4 a.u.) > cis -Rh (7.2 × 10 4 a.u.…”

Section: Resultsmentioning

confidence: 99%

Theoretical Perspective on Two-State “ON–OFF” NLO Switch of Rh(III)-Azobenzene Complex with Considerable First Hyperpolarizability

Wang

Chen

2023

J. Phys. Chem. A

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“…The CAM-B3LYP function adds a longrange-corrected version of B3LYP using the Coulomb-attenuating method, which has been proven to be an appropriate approach for calculating hyperpolarizabilities [39]. This function was proven to be reliable for calculating the (hyper)polarizabilities for metal complexes [40]. In addition, the polarizable continuum model (PCM) was taken into account and the (hyper)polarizabilities were calculated in dichloromethane (DCM) solution for the studied complexes [41,42].…”

Section: Computational Detailsmentioning

confidence: 99%

Multinuclear Pd(II) oligomeric nanohoop complexes with 2,2′‐bipyridyl‐embedded cycloparaphenylenes ligands exhibiting ultrahigh third‐order nonlinear optical performance

Zhang,

Qiu,

Zhao

et al. 2023

Int J of Quantum Chemistry

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Unlike traditionally available linear frameworks, cyclic transition‐metal architectures with cycloparaphenylenes (CPPs) ligands provide new access to develop modern nonlinear optical (NLO) materials. In this work, a sequence of “staircase” Pd(II) oligomeric nanohoop complexes with the 2,2′‐bipyridyl‐embedded CPPs ligand unit through “series connection” mode and “Ω‐type” Pd(II) trimeric isomer have been systematically designed and investigated via density functional theory. Herein, we first report the dependence of third‐order NLO responses on the number of bipyridine CPP building ligands in a quantitative way. Impressively, the Pd(II) trimeric complexes possess ultrahigh third‐order NLO responses, which are ascribed to the large orbital delocalization and decreased energy gap. To our delight, the enlargement of the nanohoop size is beneficial to improving third‐order NLO responses for Pd(II) oligomeric nanohoop complexes, and the maximum absorption spikes show the blue shift tendency. The effect of size on the third‐order NLO responses becomes much larger with the addition of bipyridine CPPs ligand. Overall, we hope the current work will deliver a new quantitative structure–property relationship toward the design and synthesis of Pd(II) oligomeric nanohoop complexes with high third‐order NLO responses.

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“…[18][19][20][21] The DFT studies done on nonlinear optical properties established its accuracy in the calculation of non-optical parameters. [22][23][24][25] The endohedral doping of alkali Li and superhalogen PF 6 with C60 enhances its optical behavior. [26] This paper investigates whether CNT's doping of speralkali Na2F (inside), superhalogen BF4, and AlF4 (outside) improves its electro-optical properties.…”

Section: Introductionmentioning

confidence: 99%

A Quantum Chemical Study on the Enormously Large Nonlinear Optical Response of Doped Endohedral Superalkali Na₂F and Superhalogens MF₄ (M = B, Al) with CNT (C56H16) Cage

Singh,

Masanja,

Dwivedi

et al. 2024

Macromolecular Symposia

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In the present communication, the interaction of single‐wall carbon nanotubes (SWCNTs) CNT (C56H16) with endohedral doped superhalogens (MF4:M = B, Al) placed outside of CNT cage and superalkali (Na2F) placed inside the cage has been studied by using a combination of DFT/B3LYP method and 6–311G(d, p) basis set. The geometry and stability of MF4@CNT‐Li2F have been studied using optimization parameters, highest occupied molecular orbit (HOMO), lowest unoccupied molecular orbital (LUMO), vibration frequencies, and thermodynamic parameters of absorption reactions. The quantum theory in atoms in molecules (QTAIM) analysis is used to analyze the nature of interactions between MF4 (M = B, Al) and Na2F@CNT. Several electronic parameters are computed by using HOMO–LUMO energy. The dipole moment, polarizability, hyperpolarizability, order parameters, anisotropic polarizability, and molar refractivity of MF4@CNT‐Li2F (M = Al, B) are used to calculate the nonlinear optical parameters (MR). The NBO analysis is used to calculate the transfer of charge to stabilized system. The calculated hyperpolarizability of Na2F@CNT‐BF4/Na2F@CNT‐AlF4 is nearly 81 times that of reference material urea (40 a.u.). The intramolecular charge transfer (ICT) moment of π electron cloud is responsible for the nonlinear optical behavior of the system.

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A DFT study of the second-order nonlinear optical properties of Ru(ii) polypyridine complexes

Abstract: It is an important task to search for efficient nonlinear optical (NLO) materials due to their potential application in electrooptic devices. Theoretical investigations on the second-order NLO response of ten...

Cited by 7 publications

References 48 publications

Theoretical Perspective on Two-State “ON–OFF” NLO Switch of Rh(III)-Azobenzene Complex with Considerable First Hyperpolarizability

Theoretical Perspective on Two-State “ON–OFF” NLO Switch of Rh(III)-Azobenzene Complex with Considerable First Hyperpolarizability

Multinuclear Pd(II) oligomeric nanohoop complexes with 2,2′‐bipyridyl‐embedded cycloparaphenylenes ligands exhibiting ultrahigh third‐order nonlinear optical performance

A Quantum Chemical Study on the Enormously Large Nonlinear Optical Response of Doped Endohedral Superalkali Na₂F and Superhalogens MF₄ (M = B, Al) with CNT (C56H16) Cage

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A DFT study of the second-order nonlinear optical properties of Ru(ii) polypyridine complexes

Abstract: It is an important task to search for efficient nonlinear optical (NLO) materials due to their potential application in electrooptic devices. Theoretical investigations on the second-order NLO response of ten...

Cited by 7 publications

References 48 publications

Theoretical Perspective on Two-State “ON–OFF” NLO Switch of Rh(III)-Azobenzene Complex with Considerable First Hyperpolarizability

Theoretical Perspective on Two-State “ON–OFF” NLO Switch of Rh(III)-Azobenzene Complex with Considerable First Hyperpolarizability

Multinuclear Pd(II) oligomeric nanohoop complexes with 2,2′‐bipyridyl‐embedded cycloparaphenylenes ligands exhibiting ultrahigh third‐order nonlinear optical performance

A Quantum Chemical Study on the Enormously Large Nonlinear Optical Response of Doped Endohedral Superalkali Na2F and Superhalogens MF4 (M = B, Al) with CNT (C56H16) Cage

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A Quantum Chemical Study on the Enormously Large Nonlinear Optical Response of Doped Endohedral Superalkali Na₂F and Superhalogens MF₄ (M = B, Al) with CNT (C56H16) Cage