Organometallic complexes for nonlinear optics. 22.1 quadratic and cubic hyperpolarizabilities of trans-bis(bidentate phosphine)ruthenium σ-arylvinylidene and σ-arylalkynyl complexes

Stephanie K Hurst, Marie P. Cifuentes, Joseph P L Morrall, Nigel T. Lucas, Ian R. Whittall, Mark G. Humphrey, Inge Asselberghs, André Persoons, Marek Samoc, Barry Luther-Davies, Anthony C. Willis

Research output: Contribution to journalArticle

124 Citations (Scopus)

Abstract

The syntheses of trans-[Ru(C=CHR)Cl(pp)2]PF6 (pp = dppm, R = 4-C6H4C≡CPh, 4-C6H4-CHO, 4,4′-C6H4C≡CC6H4 NO2, (E)-4,4′-C6H4 CH=CHC6H4NO2, 4,4′,4″-C≡CC6H4C≡CC6 H4- C≡CC6H4NO2; pp = dppe, R = 4-C6H4CHO, (E)-4,4′-C6H4CH=CHC6H4 NO2) and trans-[Ru-(C≡CR)Cl(pp)2] (pp = dppm, R = 4-C6H4C≡CPh, 4-C6H4CHO, 4,4′-C6H4C≡CC6 H4NO2, (E)-4,4′-C6H4CH=CHC6H4 NO2, 4,4′,4″-C≡ CC6H4C≡CC6H4 C≡CC6H4NO2; pp = dppe, R = 4-C6H4-CHO, (E)-4,4′-C6H4CH=CHC6H4 NO2) are reported, together with X-ray structural studies of trans-[Ru(C≡CR)Cl(pp)2] (pp = dppm, R = 4-C6H4C≡CPh; pp = dppe, R = 4-C6H4CHO, (E)-4,4′-C6H4CH=CHC6H4 NO2). Cyclic voltammetric, linear optical, and quadratic and cubic nonlinear optical response data for these new complexes, together with the corresponding data for the previously reported trans-[Ru(C=CHR)Cl(pp)2]PF6 (pp = dppm, R = Ph, 4-C6H4-NO2; pp = dppe, R = Ph, 4-C6H4NO2) and trans-[Ru(C≡CR)Cl(pp)2] (pp = dppm, R = Ph, 4-C6H4NO2, (E)-4,4′-C6H4CH=CHC6H4 NO2; pp = dppe, R = Ph, 4-C6H4NO2), are reported. Oxidation potentials for the RuII/III couple increase on proceeding from the neutral alkynyl complex to the analogous cationic vinylidene complex and on introduction of an acceptor group (CHO or NO2); the complexes with 4-C≡CC6H4NO2 ligands are the most difficult to oxidize. In some instances, the RuIII/IV and RuI/II processes have been identified together with, where relevant, nitro-centered reduction processes. The oxidized and reduced vinylidene complexes are shown to transform electrochemically into the corresponding alkynyl complexes. Optical absorption maxima undergo a red shift upon increase of acceptor strength, replacement of the coligand dppm with dppe, and replacement of the alkynyl ligand yne linkage with an ene linkage. Proceeding from the vinylidene complex to an analogous alkynyl complex results in a small red shift in absorption maximum and a significant increase in extinction coefficient. Quadratic molecular nonlinearities by hyper-Rayleigh scattering measurements at 1064 nm increase upon introduction of ligated metal (proceeding from precursor alkyne to alkynyl or vinylidene complex), an increase in acceptor strength (introduction of CHO or NO2), alkynyl chain lengthening (in the series [4-C≡CC6H4]n-4-NO2 proceeding from n = 1 and 2 to 3), and replacing the yne linkage with an ene linkage. Significant differences in β value for two vinylidene/alkynyl complex pairs suggest that they could function as precursors to protically switchable quadratic NLO materials at 1064 nm. Cubic molecular nonlinearities by Z-scan measurements at 800 nm are in many cases characterized by negative real and significant imaginary components, indicative of two-photon effects; nevertheless, a substantial increase in |γ| on proceeding to the largest molecule, trans-Ru(4,4′,4″-C≡CC6H4 C≡CC6H4C≡ CC6H4NO2)Cl(dppm)2, is observed. An order of magnitude difference in γimag values (and therefore two-photon absorption (TPA) cross sections σ2) for vinylidene/alkynyl complex pairs suggest that they have potential as protically switchable TPA materials at 800 nm.

Original languageEnglish (US)
Pages (from-to)4664-4675
Number of pages12
JournalOrganometallics
Volume20
Issue number22
DOIs
StatePublished - Oct 29 2001
Externally publishedYes

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phosphine
Nonlinear optics
Ruthenium
nonlinear optics
Organometallics
vinylidene
phosphines
ruthenium
linkages
Photons
red shift
photons
nonlinearity
material absorption
Ligands
Rayleigh scattering
ligands
Alkynes
alkynes
absorption cross sections

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Organometallic complexes for nonlinear optics. 22.1 quadratic and cubic hyperpolarizabilities of trans-bis(bidentate phosphine)ruthenium σ-arylvinylidene and σ-arylalkynyl complexes. / Hurst, Stephanie K; Cifuentes, Marie P.; Morrall, Joseph P L; Lucas, Nigel T.; Whittall, Ian R.; Humphrey, Mark G.; Asselberghs, Inge; Persoons, André; Samoc, Marek; Luther-Davies, Barry; Willis, Anthony C.

In: Organometallics, Vol. 20, No. 22, 29.10.2001, p. 4664-4675.

Research output: Contribution to journalArticle

Hurst, SK, Cifuentes, MP, Morrall, JPL, Lucas, NT, Whittall, IR, Humphrey, MG, Asselberghs, I, Persoons, A, Samoc, M, Luther-Davies, B & Willis, AC 2001, 'Organometallic complexes for nonlinear optics. 22.1 quadratic and cubic hyperpolarizabilities of trans-bis(bidentate phosphine)ruthenium σ-arylvinylidene and σ-arylalkynyl complexes', Organometallics, vol. 20, no. 22, pp. 4664-4675. https://doi.org/10.1021/om0101700
Hurst, Stephanie K ; Cifuentes, Marie P. ; Morrall, Joseph P L ; Lucas, Nigel T. ; Whittall, Ian R. ; Humphrey, Mark G. ; Asselberghs, Inge ; Persoons, André ; Samoc, Marek ; Luther-Davies, Barry ; Willis, Anthony C. / Organometallic complexes for nonlinear optics. 22.1 quadratic and cubic hyperpolarizabilities of trans-bis(bidentate phosphine)ruthenium σ-arylvinylidene and σ-arylalkynyl complexes. In: Organometallics. 2001 ; Vol. 20, No. 22. pp. 4664-4675.
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title = "Organometallic complexes for nonlinear optics. 22.1 quadratic and cubic hyperpolarizabilities of trans-bis(bidentate phosphine)ruthenium σ-arylvinylidene and σ-arylalkynyl complexes",
abstract = "The syntheses of trans-[Ru(C=CHR)Cl(pp)2]PF6 (pp = dppm, R = 4-C6H4C≡CPh, 4-C6H4-CHO, 4,4′-C6H4C≡CC6H4 NO2, (E)-4,4′-C6H4 CH=CHC6H4NO2, 4,4′,4″-C≡CC6H4C≡CC6 H4- C≡CC6H4NO2; pp = dppe, R = 4-C6H4CHO, (E)-4,4′-C6H4CH=CHC6H4 NO2) and trans-[Ru-(C≡CR)Cl(pp)2] (pp = dppm, R = 4-C6H4C≡CPh, 4-C6H4CHO, 4,4′-C6H4C≡CC6 H4NO2, (E)-4,4′-C6H4CH=CHC6H4 NO2, 4,4′,4″-C≡ CC6H4C≡CC6H4 C≡CC6H4NO2; pp = dppe, R = 4-C6H4-CHO, (E)-4,4′-C6H4CH=CHC6H4 NO2) are reported, together with X-ray structural studies of trans-[Ru(C≡CR)Cl(pp)2] (pp = dppm, R = 4-C6H4C≡CPh; pp = dppe, R = 4-C6H4CHO, (E)-4,4′-C6H4CH=CHC6H4 NO2). Cyclic voltammetric, linear optical, and quadratic and cubic nonlinear optical response data for these new complexes, together with the corresponding data for the previously reported trans-[Ru(C=CHR)Cl(pp)2]PF6 (pp = dppm, R = Ph, 4-C6H4-NO2; pp = dppe, R = Ph, 4-C6H4NO2) and trans-[Ru(C≡CR)Cl(pp)2] (pp = dppm, R = Ph, 4-C6H4NO2, (E)-4,4′-C6H4CH=CHC6H4 NO2; pp = dppe, R = Ph, 4-C6H4NO2), are reported. Oxidation potentials for the RuII/III couple increase on proceeding from the neutral alkynyl complex to the analogous cationic vinylidene complex and on introduction of an acceptor group (CHO or NO2); the complexes with 4-C≡CC6H4NO2 ligands are the most difficult to oxidize. In some instances, the RuIII/IV and RuI/II processes have been identified together with, where relevant, nitro-centered reduction processes. The oxidized and reduced vinylidene complexes are shown to transform electrochemically into the corresponding alkynyl complexes. Optical absorption maxima undergo a red shift upon increase of acceptor strength, replacement of the coligand dppm with dppe, and replacement of the alkynyl ligand yne linkage with an ene linkage. Proceeding from the vinylidene complex to an analogous alkynyl complex results in a small red shift in absorption maximum and a significant increase in extinction coefficient. Quadratic molecular nonlinearities by hyper-Rayleigh scattering measurements at 1064 nm increase upon introduction of ligated metal (proceeding from precursor alkyne to alkynyl or vinylidene complex), an increase in acceptor strength (introduction of CHO or NO2), alkynyl chain lengthening (in the series [4-C≡CC6H4]n-4-NO2 proceeding from n = 1 and 2 to 3), and replacing the yne linkage with an ene linkage. Significant differences in β value for two vinylidene/alkynyl complex pairs suggest that they could function as precursors to protically switchable quadratic NLO materials at 1064 nm. Cubic molecular nonlinearities by Z-scan measurements at 800 nm are in many cases characterized by negative real and significant imaginary components, indicative of two-photon effects; nevertheless, a substantial increase in |γ| on proceeding to the largest molecule, trans-Ru(4,4′,4″-C≡CC6H4 C≡CC6H4C≡ CC6H4NO2)Cl(dppm)2, is observed. An order of magnitude difference in γimag values (and therefore two-photon absorption (TPA) cross sections σ2) for vinylidene/alkynyl complex pairs suggest that they have potential as protically switchable TPA materials at 800 nm.",
author = "Hurst, {Stephanie K} and Cifuentes, {Marie P.} and Morrall, {Joseph P L} and Lucas, {Nigel T.} and Whittall, {Ian R.} and Humphrey, {Mark G.} and Inge Asselberghs and Andr{\'e} Persoons and Marek Samoc and Barry Luther-Davies and Willis, {Anthony C.}",
year = "2001",
month = "10",
day = "29",
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TY - JOUR

T1 - Organometallic complexes for nonlinear optics. 22.1 quadratic and cubic hyperpolarizabilities of trans-bis(bidentate phosphine)ruthenium σ-arylvinylidene and σ-arylalkynyl complexes

AU - Hurst, Stephanie K

AU - Cifuentes, Marie P.

AU - Morrall, Joseph P L

AU - Lucas, Nigel T.

AU - Whittall, Ian R.

AU - Humphrey, Mark G.

AU - Asselberghs, Inge

AU - Persoons, André

AU - Samoc, Marek

AU - Luther-Davies, Barry

AU - Willis, Anthony C.

PY - 2001/10/29

Y1 - 2001/10/29

N2 - The syntheses of trans-[Ru(C=CHR)Cl(pp)2]PF6 (pp = dppm, R = 4-C6H4C≡CPh, 4-C6H4-CHO, 4,4′-C6H4C≡CC6H4 NO2, (E)-4,4′-C6H4 CH=CHC6H4NO2, 4,4′,4″-C≡CC6H4C≡CC6 H4- C≡CC6H4NO2; pp = dppe, R = 4-C6H4CHO, (E)-4,4′-C6H4CH=CHC6H4 NO2) and trans-[Ru-(C≡CR)Cl(pp)2] (pp = dppm, R = 4-C6H4C≡CPh, 4-C6H4CHO, 4,4′-C6H4C≡CC6 H4NO2, (E)-4,4′-C6H4CH=CHC6H4 NO2, 4,4′,4″-C≡ CC6H4C≡CC6H4 C≡CC6H4NO2; pp = dppe, R = 4-C6H4-CHO, (E)-4,4′-C6H4CH=CHC6H4 NO2) are reported, together with X-ray structural studies of trans-[Ru(C≡CR)Cl(pp)2] (pp = dppm, R = 4-C6H4C≡CPh; pp = dppe, R = 4-C6H4CHO, (E)-4,4′-C6H4CH=CHC6H4 NO2). Cyclic voltammetric, linear optical, and quadratic and cubic nonlinear optical response data for these new complexes, together with the corresponding data for the previously reported trans-[Ru(C=CHR)Cl(pp)2]PF6 (pp = dppm, R = Ph, 4-C6H4-NO2; pp = dppe, R = Ph, 4-C6H4NO2) and trans-[Ru(C≡CR)Cl(pp)2] (pp = dppm, R = Ph, 4-C6H4NO2, (E)-4,4′-C6H4CH=CHC6H4 NO2; pp = dppe, R = Ph, 4-C6H4NO2), are reported. Oxidation potentials for the RuII/III couple increase on proceeding from the neutral alkynyl complex to the analogous cationic vinylidene complex and on introduction of an acceptor group (CHO or NO2); the complexes with 4-C≡CC6H4NO2 ligands are the most difficult to oxidize. In some instances, the RuIII/IV and RuI/II processes have been identified together with, where relevant, nitro-centered reduction processes. The oxidized and reduced vinylidene complexes are shown to transform electrochemically into the corresponding alkynyl complexes. Optical absorption maxima undergo a red shift upon increase of acceptor strength, replacement of the coligand dppm with dppe, and replacement of the alkynyl ligand yne linkage with an ene linkage. Proceeding from the vinylidene complex to an analogous alkynyl complex results in a small red shift in absorption maximum and a significant increase in extinction coefficient. Quadratic molecular nonlinearities by hyper-Rayleigh scattering measurements at 1064 nm increase upon introduction of ligated metal (proceeding from precursor alkyne to alkynyl or vinylidene complex), an increase in acceptor strength (introduction of CHO or NO2), alkynyl chain lengthening (in the series [4-C≡CC6H4]n-4-NO2 proceeding from n = 1 and 2 to 3), and replacing the yne linkage with an ene linkage. Significant differences in β value for two vinylidene/alkynyl complex pairs suggest that they could function as precursors to protically switchable quadratic NLO materials at 1064 nm. Cubic molecular nonlinearities by Z-scan measurements at 800 nm are in many cases characterized by negative real and significant imaginary components, indicative of two-photon effects; nevertheless, a substantial increase in |γ| on proceeding to the largest molecule, trans-Ru(4,4′,4″-C≡CC6H4 C≡CC6H4C≡ CC6H4NO2)Cl(dppm)2, is observed. An order of magnitude difference in γimag values (and therefore two-photon absorption (TPA) cross sections σ2) for vinylidene/alkynyl complex pairs suggest that they have potential as protically switchable TPA materials at 800 nm.

AB - The syntheses of trans-[Ru(C=CHR)Cl(pp)2]PF6 (pp = dppm, R = 4-C6H4C≡CPh, 4-C6H4-CHO, 4,4′-C6H4C≡CC6H4 NO2, (E)-4,4′-C6H4 CH=CHC6H4NO2, 4,4′,4″-C≡CC6H4C≡CC6 H4- C≡CC6H4NO2; pp = dppe, R = 4-C6H4CHO, (E)-4,4′-C6H4CH=CHC6H4 NO2) and trans-[Ru-(C≡CR)Cl(pp)2] (pp = dppm, R = 4-C6H4C≡CPh, 4-C6H4CHO, 4,4′-C6H4C≡CC6 H4NO2, (E)-4,4′-C6H4CH=CHC6H4 NO2, 4,4′,4″-C≡ CC6H4C≡CC6H4 C≡CC6H4NO2; pp = dppe, R = 4-C6H4-CHO, (E)-4,4′-C6H4CH=CHC6H4 NO2) are reported, together with X-ray structural studies of trans-[Ru(C≡CR)Cl(pp)2] (pp = dppm, R = 4-C6H4C≡CPh; pp = dppe, R = 4-C6H4CHO, (E)-4,4′-C6H4CH=CHC6H4 NO2). Cyclic voltammetric, linear optical, and quadratic and cubic nonlinear optical response data for these new complexes, together with the corresponding data for the previously reported trans-[Ru(C=CHR)Cl(pp)2]PF6 (pp = dppm, R = Ph, 4-C6H4-NO2; pp = dppe, R = Ph, 4-C6H4NO2) and trans-[Ru(C≡CR)Cl(pp)2] (pp = dppm, R = Ph, 4-C6H4NO2, (E)-4,4′-C6H4CH=CHC6H4 NO2; pp = dppe, R = Ph, 4-C6H4NO2), are reported. Oxidation potentials for the RuII/III couple increase on proceeding from the neutral alkynyl complex to the analogous cationic vinylidene complex and on introduction of an acceptor group (CHO or NO2); the complexes with 4-C≡CC6H4NO2 ligands are the most difficult to oxidize. In some instances, the RuIII/IV and RuI/II processes have been identified together with, where relevant, nitro-centered reduction processes. The oxidized and reduced vinylidene complexes are shown to transform electrochemically into the corresponding alkynyl complexes. Optical absorption maxima undergo a red shift upon increase of acceptor strength, replacement of the coligand dppm with dppe, and replacement of the alkynyl ligand yne linkage with an ene linkage. Proceeding from the vinylidene complex to an analogous alkynyl complex results in a small red shift in absorption maximum and a significant increase in extinction coefficient. Quadratic molecular nonlinearities by hyper-Rayleigh scattering measurements at 1064 nm increase upon introduction of ligated metal (proceeding from precursor alkyne to alkynyl or vinylidene complex), an increase in acceptor strength (introduction of CHO or NO2), alkynyl chain lengthening (in the series [4-C≡CC6H4]n-4-NO2 proceeding from n = 1 and 2 to 3), and replacing the yne linkage with an ene linkage. Significant differences in β value for two vinylidene/alkynyl complex pairs suggest that they could function as precursors to protically switchable quadratic NLO materials at 1064 nm. Cubic molecular nonlinearities by Z-scan measurements at 800 nm are in many cases characterized by negative real and significant imaginary components, indicative of two-photon effects; nevertheless, a substantial increase in |γ| on proceeding to the largest molecule, trans-Ru(4,4′,4″-C≡CC6H4 C≡CC6H4C≡ CC6H4NO2)Cl(dppm)2, is observed. An order of magnitude difference in γimag values (and therefore two-photon absorption (TPA) cross sections σ2) for vinylidene/alkynyl complex pairs suggest that they have potential as protically switchable TPA materials at 800 nm.

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