Organometallic complexes for nonlinear optics. Part 36. Quadratic and cubic optical nonlinearities of 4-fluorophenylethynyl- and 4-nitro-(E)- stilbenylethynylruthenium complexes

Joseph P.L. Morrall; Marie P. Cifuentes; Mark G. Humphrey; Ruben Kellens; Elke Robijns; Inge Asselberghs; Koen Clays; André Persoons; Marek Samoc; Anthony C. Willis

doi:10.1016/j.ica.2005.09.012

Organometallic complexes for nonlinear optics. Part 36. Quadratic and cubic optical nonlinearities of 4-fluorophenylethynyl- and 4-nitro-(E)- stilbenylethynylruthenium complexes

Joseph P.L. Morrall, Marie P. Cifuentes, Mark G. Humphrey^*, Ruben Kellens, Elke Robijns, Inge Asselberghs, Koen Clays, André Persoons, Marek Samoc, Anthony C. Willis

^*Corresponding author for this work

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

26 Citations (Scopus)

Abstract

The complexes trans-[Ru(CC-4-C₆H₄F)X(dppe) ₂] [X = Cl (1), CCPh (2), CC-4-C₆H₄NO ₂ (3)], trans-[Ru{CC-4-C₆H₄-(E)-CHCH-4-C ₆H₄NO₂}X(dppe)₂] [X = CCPh (4), CC-4-C₆H₄CCPh (5)], and [C₆H ₃-1,3-{CC-trans-[RuCl(dppe)₂]}₂-5-(CC-4-C ₆H₄F)] (6) have been synthesized and the identity of 1 confirmed by a single-crystal X-ray diffraction study. Cyclic voltammetry reveals a metal-centered oxidation, the potential of which is largely invariant on alkynyl ligand replacement across the series 1-5; the diruthenium complex 6 shows two oxidation processes, consistent with weakly interacting metal centers. Hyper-Rayleigh scattering (HRS) studies at 1064 nm using ns pulses suggest quadratic nonlinearities for 3-5 that are amongst the largest thus far for organometallic complexes, a trend maintained with the two-level-corrected data. HRS studies at 800 nm using fs pulses and amplitude modulation to remove multi-photon fluorescence contributions reveal significant fluorescence-free nonlinearities for 3-5; the frequency-independent nonlinearities calculated from the 800 nm results are suggestive of fluorescence contributions to the 1064 nm data. Z-scan studies at 820 nm reveal cubic nonlinearities that increase with the size of the π-system, although error margins are significant.

Original language	English
Pages (from-to)	998-1005
Number of pages	8
Journal	Inorganica Chimica Acta
Volume	359
Issue number	3
DOIs	https://doi.org/10.1016/j.ica.2005.09.012
Publication status	Published - 1 Feb 2006

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Morrall, J. P. L., Cifuentes, M. P., Humphrey, M. G., Kellens, R., Robijns, E., Asselberghs, I., Clays, K., Persoons, A., Samoc, M., & Willis, A. C. (2006). Organometallic complexes for nonlinear optics. Part 36. Quadratic and cubic optical nonlinearities of 4-fluorophenylethynyl- and 4-nitro-(E)- stilbenylethynylruthenium complexes. Inorganica Chimica Acta, 359(3), 998-1005. https://doi.org/10.1016/j.ica.2005.09.012

@article{62efca65d2604c84ad6cc381b287d16c,

title = "Organometallic complexes for nonlinear optics. Part 36. Quadratic and cubic optical nonlinearities of 4-fluorophenylethynyl- and 4-nitro-(E)- stilbenylethynylruthenium complexes",

abstract = "The complexes trans-[Ru(CC-4-C6H4F)X(dppe) 2] [X = Cl (1), CCPh (2), CC-4-C6H4NO 2 (3)], trans-[Ru{CC-4-C6H4-(E)-CHCH-4-C 6H4NO2}X(dppe)2] [X = CCPh (4), CC-4-C6H4CCPh (5)], and [C6H 3-1,3-{CC-trans-[RuCl(dppe)2]}2-5-(CC-4-C 6H4F)] (6) have been synthesized and the identity of 1 confirmed by a single-crystal X-ray diffraction study. Cyclic voltammetry reveals a metal-centered oxidation, the potential of which is largely invariant on alkynyl ligand replacement across the series 1-5; the diruthenium complex 6 shows two oxidation processes, consistent with weakly interacting metal centers. Hyper-Rayleigh scattering (HRS) studies at 1064 nm using ns pulses suggest quadratic nonlinearities for 3-5 that are amongst the largest thus far for organometallic complexes, a trend maintained with the two-level-corrected data. HRS studies at 800 nm using fs pulses and amplitude modulation to remove multi-photon fluorescence contributions reveal significant fluorescence-free nonlinearities for 3-5; the frequency-independent nonlinearities calculated from the 800 nm results are suggestive of fluorescence contributions to the 1064 nm data. Z-scan studies at 820 nm reveal cubic nonlinearities that increase with the size of the π-system, although error margins are significant.",

keywords = "Alkynyl, Crystal structure, Cyclic voltammetry, Non-linear optics, Ruthenium",

author = "Morrall, {Joseph P.L.} and Cifuentes, {Marie P.} and Humphrey, {Mark G.} and Ruben Kellens and Elke Robijns and Inge Asselberghs and Koen Clays and Andr{\'e} Persoons and Marek Samoc and Willis, {Anthony C.}",

year = "2006",

month = feb,

day = "1",

doi = "10.1016/j.ica.2005.09.012",

language = "English",

volume = "359",

pages = "998--1005",

journal = "Inorganica Chimica Acta",

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Morrall, JPL, Cifuentes, MP, Humphrey, MG, Kellens, R, Robijns, E, Asselberghs, I, Clays, K, Persoons, A, Samoc, M & Willis, AC 2006, 'Organometallic complexes for nonlinear optics. Part 36. Quadratic and cubic optical nonlinearities of 4-fluorophenylethynyl- and 4-nitro-(E)- stilbenylethynylruthenium complexes', Inorganica Chimica Acta, vol. 359, no. 3, pp. 998-1005. https://doi.org/10.1016/j.ica.2005.09.012

Organometallic complexes for nonlinear optics. Part 36. Quadratic and cubic optical nonlinearities of 4-fluorophenylethynyl- and 4-nitro-(E)- stilbenylethynylruthenium complexes. / Morrall, Joseph P.L.; Cifuentes, Marie P.; Humphrey, Mark G. et al.
In: Inorganica Chimica Acta, Vol. 359, No. 3, 01.02.2006, p. 998-1005.

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

TY - JOUR

T1 - Organometallic complexes for nonlinear optics. Part 36. Quadratic and cubic optical nonlinearities of 4-fluorophenylethynyl- and 4-nitro-(E)- stilbenylethynylruthenium complexes

AU - Morrall, Joseph P.L.

AU - Cifuentes, Marie P.

AU - Humphrey, Mark G.

AU - Kellens, Ruben

AU - Robijns, Elke

AU - Asselberghs, Inge

AU - Clays, Koen

AU - Persoons, André

AU - Samoc, Marek

AU - Willis, Anthony C.

PY - 2006/2/1

Y1 - 2006/2/1

N2 - The complexes trans-[Ru(CC-4-C6H4F)X(dppe) 2] [X = Cl (1), CCPh (2), CC-4-C6H4NO 2 (3)], trans-[Ru{CC-4-C6H4-(E)-CHCH-4-C 6H4NO2}X(dppe)2] [X = CCPh (4), CC-4-C6H4CCPh (5)], and [C6H 3-1,3-{CC-trans-[RuCl(dppe)2]}2-5-(CC-4-C 6H4F)] (6) have been synthesized and the identity of 1 confirmed by a single-crystal X-ray diffraction study. Cyclic voltammetry reveals a metal-centered oxidation, the potential of which is largely invariant on alkynyl ligand replacement across the series 1-5; the diruthenium complex 6 shows two oxidation processes, consistent with weakly interacting metal centers. Hyper-Rayleigh scattering (HRS) studies at 1064 nm using ns pulses suggest quadratic nonlinearities for 3-5 that are amongst the largest thus far for organometallic complexes, a trend maintained with the two-level-corrected data. HRS studies at 800 nm using fs pulses and amplitude modulation to remove multi-photon fluorescence contributions reveal significant fluorescence-free nonlinearities for 3-5; the frequency-independent nonlinearities calculated from the 800 nm results are suggestive of fluorescence contributions to the 1064 nm data. Z-scan studies at 820 nm reveal cubic nonlinearities that increase with the size of the π-system, although error margins are significant.

AB - The complexes trans-[Ru(CC-4-C6H4F)X(dppe) 2] [X = Cl (1), CCPh (2), CC-4-C6H4NO 2 (3)], trans-[Ru{CC-4-C6H4-(E)-CHCH-4-C 6H4NO2}X(dppe)2] [X = CCPh (4), CC-4-C6H4CCPh (5)], and [C6H 3-1,3-{CC-trans-[RuCl(dppe)2]}2-5-(CC-4-C 6H4F)] (6) have been synthesized and the identity of 1 confirmed by a single-crystal X-ray diffraction study. Cyclic voltammetry reveals a metal-centered oxidation, the potential of which is largely invariant on alkynyl ligand replacement across the series 1-5; the diruthenium complex 6 shows two oxidation processes, consistent with weakly interacting metal centers. Hyper-Rayleigh scattering (HRS) studies at 1064 nm using ns pulses suggest quadratic nonlinearities for 3-5 that are amongst the largest thus far for organometallic complexes, a trend maintained with the two-level-corrected data. HRS studies at 800 nm using fs pulses and amplitude modulation to remove multi-photon fluorescence contributions reveal significant fluorescence-free nonlinearities for 3-5; the frequency-independent nonlinearities calculated from the 800 nm results are suggestive of fluorescence contributions to the 1064 nm data. Z-scan studies at 820 nm reveal cubic nonlinearities that increase with the size of the π-system, although error margins are significant.

KW - Alkynyl

KW - Crystal structure

KW - Cyclic voltammetry

KW - Non-linear optics

KW - Ruthenium

UR - http://www.scopus.com/inward/record.url?scp=30944455472&partnerID=8YFLogxK

U2 - 10.1016/j.ica.2005.09.012

DO - 10.1016/j.ica.2005.09.012

M3 - Article

SN - 0020-1693

VL - 359

SP - 998

EP - 1005

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

IS - 3

ER -

Organometallic complexes for nonlinear optics. Part 36. Quadratic and cubic optical nonlinearities of 4-fluorophenylethynyl- and 4-nitro-(E)- stilbenylethynylruthenium complexes

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