Nonlinear optical studies on transition metal complexes of o-aminobenzenethiol

Kafafi, Zakya H.; Lindle, J. R.; Weisbecker, Carl S.; Bartoli, F. J.; Shirk, James S.; Yoon, Tae Hoon; Kim, O.-K.

doi:10.1016/0009-2614(91)90295-k

Cited by 16 publications

(3 citation statements)

References 17 publications

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“…On the other hand, transition-metal compounds are known to display diradical character. , In particular, recent theoretical and experimental studies have shown that square planar nickel complexes involving two bidentate ligands [Ni( o -C 6 H 4 XY) 2 ] [where X = Y = O, NH, and S as well as (X, Y) = (NH, S) and (NH, O)] give different singlet diradical characters and that the amount of the diradical character is related to the stability of the semiquinone forms of the ligands depending on the strength of the double bond between the donor atom (X, Y) and the ring carbon . Several experimental studies employing the degenerate four wave mixing (DFWM) technique have also shown that some of these complexes exhibit large γ values . However, the latter systems have been considered to be closed-shell and have not so far been investigated from the viewpoint of their possible open-shell character.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Study on Second Hyperpolarizabilities of Singlet Diradical Square Planar Nickel Complexes Involving o-Semiquinonato Type Ligands

et al. 2008

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Hybrid density functional theory method is applied for investigating the diradical character dependence of the second hyperpolarizability (gamma) of square planar nickel complexes involving several types of bidentate ligands [o-C6H4XY, where X = Y = O, NH, S, Se, and PH as well as (X, Y) = (NH, NH2) and (S, NH2)]. It is found that, as a function of the donor atoms, the diradical character of these complexes varies from 0.0 to 0.884 and is associated with substantial variations of gamma ranging from 14 x 10(3) to 819 x 10(3) au. In particular, the largest gamma values are associated with intermediate diradical characters in good agreement with the structure-property relationship obtained for pure hydrocarbon systems. Increasing the electronegativity of the X and Y donor groups of the ligands leads to larger diradical characters as a result of the enhancement of the double bond nature of the C=X(Y) bonds, which further stabilizes the diradicals on both-end benzene rings. This demonstrates that the electronegativities of the donor atoms of the ligands become a tuning parameter of the diradical character and then of the gamma values of these complexes.

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Section: Introductionmentioning

confidence: 99%

Theoretical Study on Second Hyperpolarizabilities of Singlet Diradical Square Planar Nickel Complexes Involving o-Semiquinonato Type Ligands

et al. 2008

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“…In the last decade there has been an increasing focus on organometallic compounds in the search for materials exhibiting nonlinear optical properties suitable for photonic applications. , Studies of square-planar transition metal bis(dithiolene) complexes and their derivatives have revealed large third-order optical nonlinearities (γ ≈ 10 -31 −10 -29 esu) when measured by the degenerate four-wave mixing technique (DFWM) of the complexes in solutions − and with the Z-scan technique applied to the complexes in the form of guest−host polymer films. , This class of complexes possesses an intense near-infrared (NIR) absorption band that has been assigned to a mainly ligand-based π−π* transition with some degree of metal−ligand mixing . The position of the NIR band has been tuned over the range from 630 to 1500 nm by either varying the substituents on the ligand, changing the central metal atom, or changing the charge on the metal complex. , This wavelength tuneability of the absorption band has been proposed to be an effective way of obtaining near resonance enhancement and at the same time giving rise to only moderate absorption losses in nonlinear optical devices .…”

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Spectral Dispersion of Third-Harmonic Generation in Thin Films Containing Transition Metal Complexes

Geisler¹,

Pedersen²,

Underhill³

et al. 1997

J. Phys. Chem. B

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The optical third-harmonic generation technique has been used in a study of several transition metal complexes having different near-infrared (NIR) absorption features. The complexes were dispersed in polymer matrices, and the molecular second hyperpolarizabilities γ(3ω;ω,ω,ω) were derived from thin film Maker fringe measurements at 1064 and 1907 nm. Dispersion measurements of the complexes TBA[Ni(dmit)2] and TBA[Pd(dmit)2], both having strong NIR transitions, were performed in the region from 1065 to 1480 nm, revealing resonances in the NIR. For the TBA[Ni(dmit)2] complex a maximum γ-value of 20 × 10-33 esu was observed at approximately 1325 nm, red-shifted by 172 nm (0.14 eV) compared with the position of the NIR absorption peak at 1153 nm. For the TBA[Pd(dmit)2] complex the exact location of the resonance could not be determined definitively but was shifted to or even beyond 1480 nm. The maximum γ-value of the Pd-complex was more than 2.5 times that of the Ni-complex. The γ-values were strongly influenced by a number of resonances (one-, two-, and three-photon resonances); however, no clear correlation with the near-infrared transition was observed.

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A theoretical study of the hyperpolarisabilities of nickel dithiolene molecules

Craig

Williams

1992

Adv Material for Optics Elec

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The hyperpolarisabilities y of nickel dithiolene complexes have been calculated by the finite field method in combination with the CNDO/S molecular orbital method. This computational technique, which has been developed for calculating the polarisation of large organic molecules by a perturbing electric field, is discussed. The changes in y that occur as a result of different selections of substituent groups in the dithiolene ligand are described. The results are compared with recent experiments investigating these types of molecules. Large values for y are found to arise from the interaction of the nickel 3d electrons with the conjugated *-electrons of the metal-ligand complex.

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Nonlinear optical studies on transition metal complexes of o-aminobenzenethiol

Cited by 16 publications

References 17 publications

Theoretical Study on Second Hyperpolarizabilities of Singlet Diradical Square Planar Nickel Complexes Involving o-Semiquinonato Type Ligands

Theoretical Study on Second Hyperpolarizabilities of Singlet Diradical Square Planar Nickel Complexes Involving o-Semiquinonato Type Ligands

Spectral Dispersion of Third-Harmonic Generation in Thin Films Containing Transition Metal Complexes

A theoretical study of the hyperpolarisabilities of nickel dithiolene molecules

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