Organometallic complexes for non-linear optics V: Syntheses and computationally-derived quadratic non-linearities of trans-[Ru(CCC6H4R-4)Cl(dppm) 2] (R = H, NO2, C6H4NO2-4, CHCHC6H4N02-4,( E));

Andrew M. McDonagh; Ian R. Whittall; Mark G. Humphrey; Brian W. Skelton; Allan H. White

doi:10.1016/S0022-328X(96)06197-9

Organometallic complexes for non-linear optics V: Syntheses and computationally-derived quadratic non-linearities of trans-[Ru(CCC₆H₄R-4)Cl(dppm) ₂] (R = H, NO₂, C₆H₄NO₂-4, CHCHC₆H₄N0₂-4,( E));

Andrew M. McDonagh, Ian R. Whittall, Mark G. Humphrey^*, Brian W. Skelton, Allan H. White

^*Corresponding author for this work

The Australian National University

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

61 Citations (Scopus)

Abstract

A series of systematically-varied donor-acceptor octahedral ruthenium σ-acetylide complexes of general formula trans-[Ru(CCC₆H₄R-4)Cl(dppm)₂] (R = H, NO₂, C₆H₄NO₂-4 CHCHC₆H₄NO₂-4,(E)) has been synthesized. An X-ray structural study of trans- [Ru(CCC₆H₄C₆H₄NO ₂-4,4')Cl(dppm)₂] reveals non-planarity of the biphenylene moiety in the solid state. Semi-empirical calculations employing ZINDO were performed on the acetylide complexes and the dichloro species cis- and trans-[RuCl₂(dppm)₂] to evaluate molecular quadratic optical non-linearities, β; the results are consistent with (a) a significant increase in β upon incorporation of a strong acceptor substituent, (b) a substantial increase in β on chain lengthening, and (c) a 50% decrease in non-linearity upon rotation of phenylene-phenylene dihedral angle from coplanarity to orthogonality for the structurally-characterized complex.

Original language	English
Pages (from-to)	229-235
Number of pages	7
Journal	Journal of Organometallic Chemistry
Volume	519
Issue number	1-2
DOIs	https://doi.org/10.1016/S0022-328X(96)06197-9
Publication status	Published - 26 Jul 1996

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McDonagh, A. M., Whittall, I. R., Humphrey, M. G., Skelton, B. W., & White, A. H. (1996). Organometallic complexes for non-linear optics V: Syntheses and computationally-derived quadratic non-linearities of trans-[Ru(CCC₆H₄R-4)Cl(dppm) ₂] (R = H, NO₂, C₆H₄NO₂-4, CHCHC₆H₄N0₂-4,( E)); Journal of Organometallic Chemistry, 519(1-2), 229-235. https://doi.org/10.1016/S0022-328X(96)06197-9

@article{a390ba8bd59246ea98f090ed4e789667,

title = "Organometallic complexes for non-linear optics V: Syntheses and computationally-derived quadratic non-linearities of trans-[Ru(CCC6H4R-4)Cl(dppm) 2] (R = H, NO2, C6H4NO2-4, CHCHC6H4N02-4,( E));",

abstract = "A series of systematically-varied donor-acceptor octahedral ruthenium σ-acetylide complexes of general formula trans-[Ru(CCC6H4R-4)Cl(dppm)2] (R = H, NO2, C6H4NO2-4 CHCHC6H4NO2-4,(E)) has been synthesized. An X-ray structural study of trans- [Ru(CCC6H4C6H4NO 2-4,4')Cl(dppm)2] reveals non-planarity of the biphenylene moiety in the solid state. Semi-empirical calculations employing ZINDO were performed on the acetylide complexes and the dichloro species cis- and trans-[RuCl2(dppm)2] to evaluate molecular quadratic optical non-linearities, β; the results are consistent with (a) a significant increase in β upon incorporation of a strong acceptor substituent, (b) a substantial increase in β on chain lengthening, and (c) a 50% decrease in non-linearity upon rotation of phenylene-phenylene dihedral angle from coplanarity to orthogonality for the structurally-characterized complex.",

keywords = "Acetylide, Alkynyl, Crystal structure, Non-linear optics, Quadratic hyperpolarizabilities, Ruthenium",

author = "McDonagh, {Andrew M.} and Whittall, {Ian R.} and Humphrey, {Mark G.} and Skelton, {Brian W.} and White, {Allan H.}",

year = "1996",

month = jul,

day = "26",

doi = "10.1016/S0022-328X(96)06197-9",

language = "English",

volume = "519",

pages = "229--235",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier B.V.",

number = "1-2",

}

McDonagh, AM, Whittall, IR, Humphrey, MG, Skelton, BW & White, AH 1996, 'Organometallic complexes for non-linear optics V: Syntheses and computationally-derived quadratic non-linearities of trans-[Ru(CCC₆H₄R-4)Cl(dppm) ₂] (R = H, NO₂, C₆H₄NO₂-4, CHCHC₆H₄N0₂-4,( E));', Journal of Organometallic Chemistry, vol. 519, no. 1-2, pp. 229-235. https://doi.org/10.1016/S0022-328X(96)06197-9

Organometallic complexes for non-linear optics V: Syntheses and computationally-derived quadratic non-linearities of trans-[Ru(CCC₆H₄R-4)Cl(dppm) ₂] (R = H, NO₂, C₆H₄NO₂-4, CHCHC₆H₄N0₂-4,( E)); / McDonagh, Andrew M.; Whittall, Ian R.; Humphrey, Mark G. et al.
In: Journal of Organometallic Chemistry, Vol. 519, No. 1-2, 26.07.1996, p. 229-235.

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

TY - JOUR

T1 - Organometallic complexes for non-linear optics V

T2 - Syntheses and computationally-derived quadratic non-linearities of trans-[Ru(CCC6H4R-4)Cl(dppm) 2] (R = H, NO2, C6H4NO2-4, CHCHC6H4N02-4,( E));

AU - McDonagh, Andrew M.

AU - Whittall, Ian R.

AU - Humphrey, Mark G.

AU - Skelton, Brian W.

AU - White, Allan H.

PY - 1996/7/26

Y1 - 1996/7/26

N2 - A series of systematically-varied donor-acceptor octahedral ruthenium σ-acetylide complexes of general formula trans-[Ru(CCC6H4R-4)Cl(dppm)2] (R = H, NO2, C6H4NO2-4 CHCHC6H4NO2-4,(E)) has been synthesized. An X-ray structural study of trans- [Ru(CCC6H4C6H4NO 2-4,4')Cl(dppm)2] reveals non-planarity of the biphenylene moiety in the solid state. Semi-empirical calculations employing ZINDO were performed on the acetylide complexes and the dichloro species cis- and trans-[RuCl2(dppm)2] to evaluate molecular quadratic optical non-linearities, β; the results are consistent with (a) a significant increase in β upon incorporation of a strong acceptor substituent, (b) a substantial increase in β on chain lengthening, and (c) a 50% decrease in non-linearity upon rotation of phenylene-phenylene dihedral angle from coplanarity to orthogonality for the structurally-characterized complex.

AB - A series of systematically-varied donor-acceptor octahedral ruthenium σ-acetylide complexes of general formula trans-[Ru(CCC6H4R-4)Cl(dppm)2] (R = H, NO2, C6H4NO2-4 CHCHC6H4NO2-4,(E)) has been synthesized. An X-ray structural study of trans- [Ru(CCC6H4C6H4NO 2-4,4')Cl(dppm)2] reveals non-planarity of the biphenylene moiety in the solid state. Semi-empirical calculations employing ZINDO were performed on the acetylide complexes and the dichloro species cis- and trans-[RuCl2(dppm)2] to evaluate molecular quadratic optical non-linearities, β; the results are consistent with (a) a significant increase in β upon incorporation of a strong acceptor substituent, (b) a substantial increase in β on chain lengthening, and (c) a 50% decrease in non-linearity upon rotation of phenylene-phenylene dihedral angle from coplanarity to orthogonality for the structurally-characterized complex.

KW - Acetylide

KW - Alkynyl

KW - Crystal structure

KW - Non-linear optics

KW - Quadratic hyperpolarizabilities

KW - Ruthenium

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U2 - 10.1016/S0022-328X(96)06197-9

DO - 10.1016/S0022-328X(96)06197-9

M3 - Article

AN - SCOPUS:0030602660

SN - 0022-328X

VL - 519

SP - 229

EP - 235

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

IS - 1-2

ER -

Organometallic complexes for non-linear optics V: Syntheses and computationally-derived quadratic non-linearities of trans-[Ru(CCC₆H₄R-4)Cl(dppm) ₂] (R = H, NO₂, C₆H₄NO₂-4, CHCHC₆H₄N0₂-4,( E));

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