Theoretical study on second hyperpolarizabilities of singlet diradical square planar nickel complexes involving o-semiquinonato type ligands

Hitoshi Fukui, Ryohei Kishi, Takuya Minami, Hiroshi Nagai, Hideaki Takahashi, Takashi Kubo, Kenji Kamada, Koji Ohta, Benoît Champagne, Edith Botek, Masayoshi Nakano

Résultats de recherche: Contribution à un journal/une revueArticle

Résumé

Hybrid density functional theory method is applied for investigating the diradical character dependence of the second hyperpolarizability (γ) 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 γ ranging from 14 × 103 to 819 × 103 au. In particular, the largest γ 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 γ values of these complexes.

langue originaleAnglais
Pages (de - à)8423-8429
Nombre de pages7
journalJournal of physical chemistry A
Volume112
Numéro de publication36
Les DOIs
étatPublié - 11 sept. 2008

Empreinte digitale

Nickel
Electronegativity
nickel
Ligands
ligands
Atoms
Hydrocarbons
Benzene
Density functional theory
atoms
Tuning
hydrocarbons
tuning
benzene
density functional theory
augmentation
rings

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Fukui, Hitoshi ; Kishi, Ryohei ; Minami, Takuya ; Nagai, Hiroshi ; Takahashi, Hideaki ; Kubo, Takashi ; Kamada, Kenji ; Ohta, Koji ; Champagne, Benoît ; Botek, Edith ; Nakano, Masayoshi. / Theoretical study on second hyperpolarizabilities of singlet diradical square planar nickel complexes involving o-semiquinonato type ligands. Dans: Journal of physical chemistry A. 2008 ; Vol 112, Numéro 36. p. 8423-8429.
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title = "Theoretical study on second hyperpolarizabilities of singlet diradical square planar nickel complexes involving o-semiquinonato type ligands",
abstract = "Hybrid density functional theory method is applied for investigating the diradical character dependence of the second hyperpolarizability (γ) 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 γ ranging from 14 × 103 to 819 × 103 au. In particular, the largest γ 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 γ values of these complexes.",
author = "Hitoshi Fukui and Ryohei Kishi and Takuya Minami and Hiroshi Nagai and Hideaki Takahashi and Takashi Kubo and Kenji Kamada and Koji Ohta and Beno{\^i}t Champagne and Edith Botek and Masayoshi Nakano",
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Theoretical study on second hyperpolarizabilities of singlet diradical square planar nickel complexes involving o-semiquinonato type ligands. / Fukui, Hitoshi; Kishi, Ryohei; Minami, Takuya; Nagai, Hiroshi; Takahashi, Hideaki; Kubo, Takashi; Kamada, Kenji; Ohta, Koji; Champagne, Benoît; Botek, Edith; Nakano, Masayoshi.

Dans: Journal of physical chemistry A, Vol 112, Numéro 36, 11.09.2008, p. 8423-8429.

Résultats de recherche: Contribution à un journal/une revueArticle

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T1 - Theoretical study on second hyperpolarizabilities of singlet diradical square planar nickel complexes involving o-semiquinonato type ligands

AU - Fukui, Hitoshi

AU - Kishi, Ryohei

AU - Minami, Takuya

AU - Nagai, Hiroshi

AU - Takahashi, Hideaki

AU - Kubo, Takashi

AU - Kamada, Kenji

AU - Ohta, Koji

AU - Champagne, Benoît

AU - Botek, Edith

AU - Nakano, Masayoshi

PY - 2008/9/11

Y1 - 2008/9/11

N2 - Hybrid density functional theory method is applied for investigating the diradical character dependence of the second hyperpolarizability (γ) 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 γ ranging from 14 × 103 to 819 × 103 au. In particular, the largest γ 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 γ values of these complexes.

AB - Hybrid density functional theory method is applied for investigating the diradical character dependence of the second hyperpolarizability (γ) 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 γ ranging from 14 × 103 to 819 × 103 au. In particular, the largest γ 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 γ values of these complexes.

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