Quantum chemical design for enhanced second-order NLO response of terpyridine-substituted hexamolybdates

Muhammad Ramzan Saeed Ashraf Janjua; Wei Guan; Likai Yan; Zhong Min Su; Abdul Karim; Jamshed Akbar

doi:10.1002/ejic.201000428

Quantum chemical design for enhanced second-order NLO response of terpyridine-substituted hexamolybdates

Muhammad Ramzan Saeed Ashraf Janjua, Wei Guan, Likai Yan, Zhong Min Su^*, Abdul Karim, Jamshed Akbar

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

49 Scopus citations

Abstract

A dramatic increase in the second-order nonlinear optical (NLO) response of terpyridine-substituted hexamolybdates has been observed from 886.55× 10 ^-30 esu (system 1) to 4622.92× 10 ^-30 esu (system 7). The dipole polarizabilities and second-order nonlinear optical (NLO) properties of terpyridine derivatives of hexamolybdates have been investigated by using time-dependent density functional theory (TDDFT). The quantum mechanical design suggests that [Mo ₆O ₁₈(N ₄C ₂₅H ₁₄(CF ₃) ₂ (CN) ₂)] ^2- (system 7) is the best choice among all studied systems to improve nonlinearity. The electron-withdrawing ability of electron-acceptor groups (F, Cl, Br, I, CF ₃, and CN) at the end of the terpyridine ligand directs the charge transfer (CT) from the POM cluster to the terpyridine segment along the z axis, which leads to an efficient second-order NLO molecular design. These small changes in molecular composition by substitution may have disproportionately huge effects on the NLO properties, which can be attributed to the so-called "butterfly effect".

Original language	English
Pages (from-to)	3466-3472
Number of pages	7
Journal	European Journal of Inorganic Chemistry
Issue number	22
DOIs	https://doi.org/10.1002/ejic.201000428
State	Published - Aug 2010
Externally published	Yes

Keywords

Charge transfer
Density functional calculations
Organic-inorganic hybrid composites
Polyoxometalates
Second-order polarizability

ASJC Scopus subject areas

Inorganic Chemistry

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10.1002/ejic.201000428

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title = "Quantum chemical design for enhanced second-order NLO response of terpyridine-substituted hexamolybdates",

abstract = "A dramatic increase in the second-order nonlinear optical (NLO) response of terpyridine-substituted hexamolybdates has been observed from 886.55× 10 -30 esu (system 1) to 4622.92× 10 -30 esu (system 7). The dipole polarizabilities and second-order nonlinear optical (NLO) properties of terpyridine derivatives of hexamolybdates have been investigated by using time-dependent density functional theory (TDDFT). The quantum mechanical design suggests that [Mo 6O 18(N 4C 25H 14(CF 3) 2 (CN) 2)] 2- (system 7) is the best choice among all studied systems to improve nonlinearity. The electron-withdrawing ability of electron-acceptor groups (F, Cl, Br, I, CF 3, and CN) at the end of the terpyridine ligand directs the charge transfer (CT) from the POM cluster to the terpyridine segment along the z axis, which leads to an efficient second-order NLO molecular design. These small changes in molecular composition by substitution may have disproportionately huge effects on the NLO properties, which can be attributed to the so-called {"}butterfly effect{"}.",

keywords = "Charge transfer, Density functional calculations, Organic-inorganic hybrid composites, Polyoxometalates, Second-order polarizability",

author = "Janjua, {Muhammad Ramzan Saeed Ashraf} and Wei Guan and Likai Yan and Su, {Zhong Min} and Abdul Karim and Jamshed Akbar",

year = "2010",

month = aug,

doi = "10.1002/ejic.201000428",

language = "English",

pages = "3466--3472",

journal = "European Journal of Inorganic Chemistry",

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publisher = "Wiley-VCH Verlag",

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AU - Janjua, Muhammad Ramzan Saeed Ashraf

AU - Guan, Wei

AU - Yan, Likai

AU - Su, Zhong Min

AU - Karim, Abdul

AU - Akbar, Jamshed

PY - 2010/8

Y1 - 2010/8

N2 - A dramatic increase in the second-order nonlinear optical (NLO) response of terpyridine-substituted hexamolybdates has been observed from 886.55× 10 -30 esu (system 1) to 4622.92× 10 -30 esu (system 7). The dipole polarizabilities and second-order nonlinear optical (NLO) properties of terpyridine derivatives of hexamolybdates have been investigated by using time-dependent density functional theory (TDDFT). The quantum mechanical design suggests that [Mo 6O 18(N 4C 25H 14(CF 3) 2 (CN) 2)] 2- (system 7) is the best choice among all studied systems to improve nonlinearity. The electron-withdrawing ability of electron-acceptor groups (F, Cl, Br, I, CF 3, and CN) at the end of the terpyridine ligand directs the charge transfer (CT) from the POM cluster to the terpyridine segment along the z axis, which leads to an efficient second-order NLO molecular design. These small changes in molecular composition by substitution may have disproportionately huge effects on the NLO properties, which can be attributed to the so-called "butterfly effect".

AB - A dramatic increase in the second-order nonlinear optical (NLO) response of terpyridine-substituted hexamolybdates has been observed from 886.55× 10 -30 esu (system 1) to 4622.92× 10 -30 esu (system 7). The dipole polarizabilities and second-order nonlinear optical (NLO) properties of terpyridine derivatives of hexamolybdates have been investigated by using time-dependent density functional theory (TDDFT). The quantum mechanical design suggests that [Mo 6O 18(N 4C 25H 14(CF 3) 2 (CN) 2)] 2- (system 7) is the best choice among all studied systems to improve nonlinearity. The electron-withdrawing ability of electron-acceptor groups (F, Cl, Br, I, CF 3, and CN) at the end of the terpyridine ligand directs the charge transfer (CT) from the POM cluster to the terpyridine segment along the z axis, which leads to an efficient second-order NLO molecular design. These small changes in molecular composition by substitution may have disproportionately huge effects on the NLO properties, which can be attributed to the so-called "butterfly effect".

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KW - Density functional calculations

KW - Organic-inorganic hybrid composites

KW - Polyoxometalates

KW - Second-order polarizability

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JF - European Journal of Inorganic Chemistry

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Quantum chemical design for enhanced second-order NLO response of terpyridine-substituted hexamolybdates

Abstract

Keywords

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