Organometallic complexes for nonlinear optics: Part 19. Syntheses and molecular quadratic hyperpolarizabilities of indoanilino-alkynyl-ruthenium complexes

Andrew M. McDonagh; Marie P. Cifuentes; Nigel T. Lucas; Mark G. Humphrey; Stephan Houbrechts; André Persoons

doi:10.1016/S0022-328X(00)00311-9

Organometallic complexes for nonlinear optics: Part 19. Syntheses and molecular quadratic hyperpolarizabilities of indoanilino-alkynyl-ruthenium complexes

Andrew M. McDonagh^*, Marie P. Cifuentes, Nigel T. Lucas, Mark G. Humphrey, Stephan Houbrechts, André Persoons

^*Corresponding author for this work

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

43 Citations (Scopus)

Abstract

The terminal alkyne 4-HCCC₆H₄N=CCH=C^tBuC(O)C^tBu=CH (1) and ruthenium complex derivatives trans-[Ru(CC-4-C₆H₄N=CCH=C^tBuC(O)C ^tBu=CH}Cl(dppm)₂] (2) and [Ru{CC-4-C₆H₄N=CCH=C^tBuC(O)C ^tBu=CH}(PPh₃)₂(η-C₅H ₅)] (3) have been synthesized. An X-ray structural study of 3 reveals the expected equivalent C-C bond lengths of the phenyl and alternating C-C and C=C bond lengths of the quinonal ring in the indoanilino-alkynyl ligand; there is a dihedral angle of 47.59° between the phenyl and quinonal rings, probably a result of ortho-hydrogen repulsion. Metal-centred oxidation potentials of 2 and 3 are similar to those of 'extended chain' 4-nitroaryl-alkynyl complex analogues. Irreversible quinonal ring-centred reductions occur at significantly more negative potentials than the quasi-reversible reductions in their nitro-containing analogues. Quadratic optical nonlinearities by hyper-Rayleigh scattering at 1064 nm for 2 (417×10^-30 esu) and 3 (658×10^-30 esu) are both large, but resonance enhanced. Two-level-corrected nonlinearities for these complexes (124×10^-30, 159×10^-30 esu, respectively) are also large, despite the presence of electron-donating tert-butyl groups reducing the efficiency of the (formally) electron-accepting quinonal ring in these donor-bridge-acceptor complexes.

Original language	English
Pages (from-to)	193-201
Number of pages	9
Journal	Journal of Organometallic Chemistry
Volume	605
Issue number	2
DOIs	https://doi.org/10.1016/S0022-328X(00)00311-9
Publication status	Published - 7 Jul 2000

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@article{2ee5013b07ed44b194b273b210e1af7a,

title = "Organometallic complexes for nonlinear optics: Part 19. Syntheses and molecular quadratic hyperpolarizabilities of indoanilino-alkynyl-ruthenium complexes",

abstract = "The terminal alkyne 4-HCCC6H4N=CCH=CtBuC(O)CtBu=CH (1) and ruthenium complex derivatives trans-[Ru(CC-4-C6H4N=CCH=CtBuC(O)C tBu=CH}Cl(dppm)2] (2) and [Ru{CC-4-C6H4N=CCH=CtBuC(O)C tBu=CH}(PPh3)2(η-C5H 5)] (3) have been synthesized. An X-ray structural study of 3 reveals the expected equivalent C-C bond lengths of the phenyl and alternating C-C and C=C bond lengths of the quinonal ring in the indoanilino-alkynyl ligand; there is a dihedral angle of 47.59° between the phenyl and quinonal rings, probably a result of ortho-hydrogen repulsion. Metal-centred oxidation potentials of 2 and 3 are similar to those of 'extended chain' 4-nitroaryl-alkynyl complex analogues. Irreversible quinonal ring-centred reductions occur at significantly more negative potentials than the quasi-reversible reductions in their nitro-containing analogues. Quadratic optical nonlinearities by hyper-Rayleigh scattering at 1064 nm for 2 (417×10-30 esu) and 3 (658×10-30 esu) are both large, but resonance enhanced. Two-level-corrected nonlinearities for these complexes (124×10-30, 159×10-30 esu, respectively) are also large, despite the presence of electron-donating tert-butyl groups reducing the efficiency of the (formally) electron-accepting quinonal ring in these donor-bridge-acceptor complexes.",

keywords = "Alkynyl, Electrochemistry, Nonlinear optics, Quadratic hyperpolarizabilities, Ruthenium, X-ray structure",

author = "McDonagh, {Andrew M.} and Cifuentes, {Marie P.} and Lucas, {Nigel T.} and Humphrey, {Mark G.} and Stephan Houbrechts and Andr{\'e} Persoons",

year = "2000",

month = jul,

day = "7",

doi = "10.1016/S0022-328X(00)00311-9",

language = "English",

volume = "605",

pages = "193--201",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier B.V.",

number = "2",

}

Organometallic complexes for nonlinear optics: Part 19. Syntheses and molecular quadratic hyperpolarizabilities of indoanilino-alkynyl-ruthenium complexes. / McDonagh, Andrew M.; Cifuentes, Marie P.; Lucas, Nigel T. et al.
In: Journal of Organometallic Chemistry, Vol. 605, No. 2, 07.07.2000, p. 193-201.

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

TY - JOUR

T1 - Organometallic complexes for nonlinear optics

T2 - Part 19. Syntheses and molecular quadratic hyperpolarizabilities of indoanilino-alkynyl-ruthenium complexes

AU - McDonagh, Andrew M.

AU - Cifuentes, Marie P.

AU - Lucas, Nigel T.

AU - Humphrey, Mark G.

AU - Houbrechts, Stephan

AU - Persoons, André

PY - 2000/7/7

Y1 - 2000/7/7

N2 - The terminal alkyne 4-HCCC6H4N=CCH=CtBuC(O)CtBu=CH (1) and ruthenium complex derivatives trans-[Ru(CC-4-C6H4N=CCH=CtBuC(O)C tBu=CH}Cl(dppm)2] (2) and [Ru{CC-4-C6H4N=CCH=CtBuC(O)C tBu=CH}(PPh3)2(η-C5H 5)] (3) have been synthesized. An X-ray structural study of 3 reveals the expected equivalent C-C bond lengths of the phenyl and alternating C-C and C=C bond lengths of the quinonal ring in the indoanilino-alkynyl ligand; there is a dihedral angle of 47.59° between the phenyl and quinonal rings, probably a result of ortho-hydrogen repulsion. Metal-centred oxidation potentials of 2 and 3 are similar to those of 'extended chain' 4-nitroaryl-alkynyl complex analogues. Irreversible quinonal ring-centred reductions occur at significantly more negative potentials than the quasi-reversible reductions in their nitro-containing analogues. Quadratic optical nonlinearities by hyper-Rayleigh scattering at 1064 nm for 2 (417×10-30 esu) and 3 (658×10-30 esu) are both large, but resonance enhanced. Two-level-corrected nonlinearities for these complexes (124×10-30, 159×10-30 esu, respectively) are also large, despite the presence of electron-donating tert-butyl groups reducing the efficiency of the (formally) electron-accepting quinonal ring in these donor-bridge-acceptor complexes.

AB - The terminal alkyne 4-HCCC6H4N=CCH=CtBuC(O)CtBu=CH (1) and ruthenium complex derivatives trans-[Ru(CC-4-C6H4N=CCH=CtBuC(O)C tBu=CH}Cl(dppm)2] (2) and [Ru{CC-4-C6H4N=CCH=CtBuC(O)C tBu=CH}(PPh3)2(η-C5H 5)] (3) have been synthesized. An X-ray structural study of 3 reveals the expected equivalent C-C bond lengths of the phenyl and alternating C-C and C=C bond lengths of the quinonal ring in the indoanilino-alkynyl ligand; there is a dihedral angle of 47.59° between the phenyl and quinonal rings, probably a result of ortho-hydrogen repulsion. Metal-centred oxidation potentials of 2 and 3 are similar to those of 'extended chain' 4-nitroaryl-alkynyl complex analogues. Irreversible quinonal ring-centred reductions occur at significantly more negative potentials than the quasi-reversible reductions in their nitro-containing analogues. Quadratic optical nonlinearities by hyper-Rayleigh scattering at 1064 nm for 2 (417×10-30 esu) and 3 (658×10-30 esu) are both large, but resonance enhanced. Two-level-corrected nonlinearities for these complexes (124×10-30, 159×10-30 esu, respectively) are also large, despite the presence of electron-donating tert-butyl groups reducing the efficiency of the (formally) electron-accepting quinonal ring in these donor-bridge-acceptor complexes.

KW - Alkynyl

KW - Electrochemistry

KW - Nonlinear optics

KW - Quadratic hyperpolarizabilities

KW - Ruthenium

KW - X-ray structure

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U2 - 10.1016/S0022-328X(00)00311-9

DO - 10.1016/S0022-328X(00)00311-9

M3 - Article

SN - 0022-328X

VL - 605

SP - 193

EP - 201

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

IS - 2

ER -

Organometallic complexes for nonlinear optics: Part 19. Syntheses and molecular quadratic hyperpolarizabilities of indoanilino-alkynyl-ruthenium complexes

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