Nonlinear optical properties of rhenium(I) complexes: Influence of the extended π-conjugated connectors and proton abstraction

Yu, Hao; Hong, Bo; Yang, Ning; Zhao, Hongyan

doi:10.1016/j.jmgm.2015.07.008

Cited by 7 publications

(4 citation statements)

References 46 publications

(41 reference statements)

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“…32 The Re(I) complexes ([Re( phen)(CO) 3 ( py-phOH)] + ) can exhibit molecular second-order NLO switching, which originates from reversible deprotonation-protonation processes. 29 During the reversible photoisomerization process, the second-order NLO response value of Re(I) dithienylethene complexes can increase about 5-fold and achieve excellent NLO switches. 33 Recently, a chiral bis-chelating ligand (−)-2,5-bis(4,5pinene-2-pyridyl) pyrazine named L R (ligand 1) was synthesized as shown in Fig.…”

Section: Introductionmentioning

confidence: 98%

“…Thus, rhenium(I) complexes have attracted great interest from NLO researchers. [29][30][31] For example, the second-order NLO response of fac-ClRe (CO) 3 L 3 is about 1.2 times larger than that of 2-methyl-4nitroaniline. 32 The Re(I) complexes ([Re( phen)(CO) 3 ( py-phOH)] + ) can exhibit molecular second-order NLO switching, which originates from reversible deprotonation-protonation processes.…”

Section: Introductionmentioning

confidence: 99%

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Understanding the photophysical properties of chiral dinuclear Re(i) complexes and the role of Re(i) in their complexes

Liu

Shi

et al. 2016

Dalton Trans.

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Chiral transition metal complexes not only have large nonlinear optical (NLO) response but also meet the non-centrosymmetric requirement of second-order NLO materials. Therefore, chiral transition metal complexes become very active in the NLO area. Recently, the second-order NLO response of chiral dinuclear Re(i) complex 2 has been found to be 1.5 times larger than that of KH2PO4 (KDP) based on experimental measurement. However, its NLO origin has not been determined and a structure-property relationship has not been established at the microscopic level, which are very important to further improve the performance. It is found that charge transfer from metal to ligand is mainly responsible for its NLO origin. Based on complex 2, the designed complexes have remarkably large second-order NLO activity. For instance, the designed complex 9 has a very large second-order NLO response value (115.81 × 10(-30) esu), which is about 668 times larger than the organic molecule urea. Moreover, time-dependent density functional theory (TDDFT) calculations have been used to investigate their UV-Vis/CD spectra. The simulated circular dichroism (CD) spectra of the complex 2 are in good agreement with the experimental ones, which can be used to assign the absolute configurations (ACs) of chiral dinuclear Re(i) complexes with high confidence. The electronic absorption wavelengths, electron transition properties, and the second-order NLO responses strongly depend on the nature of substituent, different ligands (pyridine and isoquinoline) and their combinations. Based on NBO analysis, the interactions between [Re(CO)3Cl] fragments and ligands are of n →σ* character.

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Section: Introductionmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

Understanding the photophysical properties of chiral dinuclear Re(i) complexes and the role of Re(i) in their complexes

Liu

Shi

et al. 2016

Dalton Trans.

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“…They can be stimulated by the outside world to convert between two or more chemical forms (including structures) to show significant differences in NLO properties. To our knowledge, the types of stimulus used to trigger the commutation of NLO molecular switches studied mainly include light irradiation (photoisomerization), − redox reaction, ,− pH variation, , temperature, ion recognition, ,,− and induction of external electric field (EEF). − Interestingly, Li et al have exhibited that a high EEF can make a centrosymmetric benzene molecule without NLO response generates a large first hyperpolarizability (β 0 ) because of a centrosymmetry breaking of the electron cloud . The electride NLO switch induced by EEF can exhibit large β 0 values of 3.15 × 10 6 au for e@K(1)@calyx[4]pyrrole@K(2)@e, 2.2 × 10 6 au for e – + Ca 2+ (Ni@Pb 12 ) 2– Ca 2+ + e – , and 5.0 × 10 6 au for Be 6 Li 14 …”

Section: Introductionmentioning

confidence: 99%

Long-Range Charge Transfer Driven by External Electric Field in Alkalides M–LCaL–M (M = Li or Na, L = All-cis 1,2,3,4,5,6-Hexafluorocyclohexane): Facially Polarized Janus-Type Second Order Nonlinear Molecular Optical Switches

Wang

Huang

et al. 2019

J. Phys. Chem. C

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Alkalides with large nonlinear optical (NLO) responses exhibit broad applications in the electro-optical device field. In the present work, based on alkali (Li and Na) in conjunction with alkaline-earth (Ca) atoms doped into facially polarized all-cis 1,2,3,4,5,6-hexafluorocyclohexane (C6F6H6), we first reported two facially polarized Janus-type alkalides as an external electric field (EEF)-induced second order NLO switches M–LCaL–M (M = Li or Na, L = C6F6H6). The two 4s electrons of the Ca atom are, respectively, pushed out by the negative fluorocarbon face of one L and each of them concentrate on one alkali atom and combine with the s electron of the later to form excess electron pair. Owing to the two excess electron pairs [highest occupied molecular orbital (HOMO) and HOMO – 1], the novel alkalides M––LCa2+L–M– is formed. Interestingly, with continuous increasing of EEF magnitude, the centrosymmetric M––LCa2+L–M– bearing two excess electron pairs is obviously broken and a long-range charge transfer is exhibited gradually from one end of the alkali atom through the middle LCaL to the other end of it. Meanwhile, the influence of EEF brings a large static electronic first hyperpolarizability from 0 (EEF = 0, off form) to 59 826 (M = Li, EEF = 19 × 10–4 au, on form) or 64 231 au (M = Na, EEF = 12 × 10–4 au, on form). They also have the largest vibrational first hyperpolarizabilities (on form). These results show that alkalides M––LCa2+L–M– have potential application for NLO materials as well as exhibit advantages such as high sensitivity, being fast, and having reversible switching.

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“…[25][26][27][28][29] However, presently, only a few reports describe NLO studies on the crown ethers, let alone investigate their use in the NLO-based detection of cations. 30,31 Inspired by our previous papers [32][33][34][35][36][37][38] on the NLO switching and the strong complex formation ability of crown compounds, the crown ether compounds formed by N15C5 with group I alkali metal cations (Li + , Na + , K + ), group II alkali metal cations (Be 2+ , Mg 2+ , Ca 2+ ) and transition metal cations (Co 2+ , Ni 2+ , Cu 2+ ) (Fig. 1) were investigated by using density functional theory (DFT).…”

Section: Introductionmentioning

confidence: 99%

Variational first hyperpolarizabilities of 2,3-naphtho-15-crown-5 ether derivatives with cation-complexing: a potential and selective cation detector

Wang

Hong

et al. 2016

Phys. Chem. Chem. Phys.

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Crown ethers, as a kind of heterocycle, have been the subject of great interest over recent decades due to their selective capability to bind to metal cations. The use of a constant crown ether, such as naphtho-15-crown-5 (N15C5), and varied metal cations (Li, Na, K, Be, Mg, Ca, Co, Ni, Cu) makes it possible to determine the contributions of the metal cations to nonlinear optical (NLO) responses and to design an appropriate NLO-based cation detector. N15C5 and its metal cation derivatives have been systematically investigated by density functional theory. It is found that the dependency of the first hyperpolarizability relies on the metal cation, especially for transition metals. The decrease of the first hyperpolarizabilities for alkali metal cation derivatives is due to their relatively low oscillator strengths, whereas the significant increase of the first hyperpolarizabilities for transition metal cation derivatives can be further illustrated by their low transition energies, large amplitudes and separate distributions of first hyperpolarizability density. Thus, the alkali metal and transition metal cations are distinguishable and the transition metal cations are easier to detect by utilizing the variations in NLO responses.

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Nonlinear optical properties of rhenium(I) complexes: Influence of the extended π-conjugated connectors and proton abstraction

Cited by 7 publications

References 46 publications

Understanding the photophysical properties of chiral dinuclear Re(i) complexes and the role of Re(i) in their complexes

Understanding the photophysical properties of chiral dinuclear Re(i) complexes and the role of Re(i) in their complexes

Long-Range Charge Transfer Driven by External Electric Field in Alkalides M–LCaL–M (M = Li or Na, L = All-cis 1,2,3,4,5,6-Hexafluorocyclohexane): Facially Polarized Janus-Type Second Order Nonlinear Molecular Optical Switches

Variational first hyperpolarizabilities of 2,3-naphtho-15-crown-5 ether derivatives with cation-complexing: a potential and selective cation detector

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