Linear and Third-Order Nonlinear Optical Properties of Fe(η5-C5Me5)(κ2-dppe)- and trans-Ru(κ2-dppe)2-Alkynyl Complexes Containing 2-Fluorenyl End Groups

Amedee Triadon; Guillaume Grelaud; Nicolas Richy; Olivier Mongin; Graeme J. Moxey; Isabelle M. Dixon; Xinwei Yang; Genmiao Wang; Adam Barlow; Joelle Rauh-Berthelot; Marie P. Cifuentes; Mark G. Humphrey; Frederic Paul

doi:10.1021/acs.organomet.8b00229

Linear and Third-Order Nonlinear Optical Properties of Fe(η5-C5Me5)(κ2-dppe)- and trans-Ru(κ2-dppe)2-Alkynyl Complexes Containing 2-Fluorenyl End Groups

Amedee Triadon, Guillaume Grelaud, Nicolas Richy, Olivier Mongin, Graeme J. Moxey, Isabelle M. Dixon, Xinwei Yang, Genmiao Wang, Adam Barlow, Joelle Rauh-Berthelot, Marie P. Cifuentes, Mark G. Humphrey, Frederic Paul

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

Abstract

The synthesis and characterization of a set of redox-active iron and ruthenium alkynyl complexes of general formula [[M]Cl(1-p){C equivalent to CC6H5-m(C equivalent to CFlu)(m)}((1+p))][PF6](n) are reported (n = 01; m = 12; [M] = [Fe(eta(5)-C5Me5)(kappa(2)-dppe)] and p = 1 or [M] = [trans-Ru(kappa(2)-dppe)(2)] and p = 01). The linear and third-order nonlinear optical properties of these new organometallic complexes featuring phenylalkynyl ligands functionalized by 2-fluorenyl (Flu) groups were studied in their stable redox states. Their first electronic transitions are assigned with the help of DFT calculations. We show here that these compounds possess significant third-order NLO responses in the near-IR range for molecules of their size. In particular, the remarkably large 2PA activities of the new Ru(II) compounds in the 600-800 nm range (Z-scan) make them attractive nonlinear chromophores. Structure-property studies emphasize the importance of para- versus meta-connection of the 2-fluorenylethynyl units on the phenylalkynyl core and reveal that upon progressing from mono- to bis-alkynyl complexes a further increase of the 2PA cross section can be obtained while maintaining linear transparency in the visible range.

Original language	English
Pages (from-to)	2245-2262
Number of pages	18
Journal	Organometallics
Volume	37
Issue number	14
DOIs	https://doi.org/10.1021/acs.organomet.8b00229
Publication status	Published - 23 Jul 2018

Access to Document

10.1021/acs.organomet.8b00229

Fingerprint

Dive into the research topics of 'Linear and Third-Order Nonlinear Optical Properties of Fe(η5-C5Me5)(κ2-dppe)- and trans-Ru(κ2-dppe)2-Alkynyl Complexes Containing 2-Fluorenyl End Groups'. Together they form a unique fingerprint.

Cite this

Triadon, A., Grelaud, G., Richy, N., Mongin, O., Moxey, G. J., Dixon, I. M., Yang, X., Wang, G., Barlow, A., Rauh-Berthelot, J., Cifuentes, M. P., Humphrey, M. G., & Paul, F. (2018). Linear and Third-Order Nonlinear Optical Properties of Fe(η5-C5Me5)(κ2-dppe)- and trans-Ru(κ2-dppe)2-Alkynyl Complexes Containing 2-Fluorenyl End Groups. Organometallics, 37(14), 2245-2262. https://doi.org/10.1021/acs.organomet.8b00229

@article{e4f75be578c64df3b762f32269d09ce5,

title = "Linear and Third-Order Nonlinear Optical Properties of Fe(η5-C5Me5)(κ2-dppe)- and trans-Ru(κ2-dppe)2-Alkynyl Complexes Containing 2-Fluorenyl End Groups",

abstract = "The synthesis and characterization of a set of redox-active iron and ruthenium alkynyl complexes of general formula [[M]Cl(1-p){C equivalent to CC6H5-m(C equivalent to CFlu)(m)}((1+p))][PF6](n) are reported (n = 01; m = 12; [M] = [Fe(eta(5)-C5Me5)(kappa(2)-dppe)] and p = 1 or [M] = [trans-Ru(kappa(2)-dppe)(2)] and p = 01). The linear and third-order nonlinear optical properties of these new organometallic complexes featuring phenylalkynyl ligands functionalized by 2-fluorenyl (Flu) groups were studied in their stable redox states. Their first electronic transitions are assigned with the help of DFT calculations. We show here that these compounds possess significant third-order NLO responses in the near-IR range for molecules of their size. In particular, the remarkably large 2PA activities of the new Ru(II) compounds in the 600-800 nm range (Z-scan) make them attractive nonlinear chromophores. Structure-property studies emphasize the importance of para- versus meta-connection of the 2-fluorenylethynyl units on the phenylalkynyl core and reveal that upon progressing from mono- to bis-alkynyl complexes a further increase of the 2PA cross section can be obtained while maintaining linear transparency in the visible range.",

keywords = "Enhanced 2-photon absorption, Excited-state absorption, Iron sigma-acetylides, X-ray crystal, Organometallic complexes, Molecular wires, Chiroptical properties, Diacetylide complexes, Electronic-structures, Fluorene derivatives",

author = "Amedee Triadon and Guillaume Grelaud and Nicolas Richy and Olivier Mongin and Moxey, {Graeme J.} and Dixon, {Isabelle M.} and Xinwei Yang and Genmiao Wang and Adam Barlow and Joelle Rauh-Berthelot and Cifuentes, {Marie P.} and Humphrey, {Mark G.} and Frederic Paul",

year = "2018",

month = jul,

day = "23",

doi = "10.1021/acs.organomet.8b00229",

language = "English",

volume = "37",

pages = "2245--2262",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "14",

}

Triadon, A, Grelaud, G, Richy, N, Mongin, O, Moxey, GJ, Dixon, IM, Yang, X, Wang, G, Barlow, A, Rauh-Berthelot, J, Cifuentes, MP, Humphrey, MG & Paul, F 2018, 'Linear and Third-Order Nonlinear Optical Properties of Fe(η5-C5Me5)(κ2-dppe)- and trans-Ru(κ2-dppe)2-Alkynyl Complexes Containing 2-Fluorenyl End Groups', Organometallics, vol. 37, no. 14, pp. 2245-2262. https://doi.org/10.1021/acs.organomet.8b00229

Linear and Third-Order Nonlinear Optical Properties of Fe(η5-C5Me5)(κ2-dppe)- and trans-Ru(κ2-dppe)2-Alkynyl Complexes Containing 2-Fluorenyl End Groups. / Triadon, Amedee; Grelaud, Guillaume; Richy, Nicolas et al.
In: Organometallics, Vol. 37, No. 14, 23.07.2018, p. 2245-2262.

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

TY - JOUR

T1 - Linear and Third-Order Nonlinear Optical Properties of Fe(η5-C5Me5)(κ2-dppe)- and trans-Ru(κ2-dppe)2-Alkynyl Complexes Containing 2-Fluorenyl End Groups

AU - Triadon, Amedee

AU - Grelaud, Guillaume

AU - Richy, Nicolas

AU - Mongin, Olivier

AU - Moxey, Graeme J.

AU - Dixon, Isabelle M.

AU - Yang, Xinwei

AU - Wang, Genmiao

AU - Barlow, Adam

AU - Rauh-Berthelot, Joelle

AU - Cifuentes, Marie P.

AU - Humphrey, Mark G.

AU - Paul, Frederic

PY - 2018/7/23

Y1 - 2018/7/23

N2 - The synthesis and characterization of a set of redox-active iron and ruthenium alkynyl complexes of general formula [[M]Cl(1-p){C equivalent to CC6H5-m(C equivalent to CFlu)(m)}((1+p))][PF6](n) are reported (n = 01; m = 12; [M] = [Fe(eta(5)-C5Me5)(kappa(2)-dppe)] and p = 1 or [M] = [trans-Ru(kappa(2)-dppe)(2)] and p = 01). The linear and third-order nonlinear optical properties of these new organometallic complexes featuring phenylalkynyl ligands functionalized by 2-fluorenyl (Flu) groups were studied in their stable redox states. Their first electronic transitions are assigned with the help of DFT calculations. We show here that these compounds possess significant third-order NLO responses in the near-IR range for molecules of their size. In particular, the remarkably large 2PA activities of the new Ru(II) compounds in the 600-800 nm range (Z-scan) make them attractive nonlinear chromophores. Structure-property studies emphasize the importance of para- versus meta-connection of the 2-fluorenylethynyl units on the phenylalkynyl core and reveal that upon progressing from mono- to bis-alkynyl complexes a further increase of the 2PA cross section can be obtained while maintaining linear transparency in the visible range.

AB - The synthesis and characterization of a set of redox-active iron and ruthenium alkynyl complexes of general formula [[M]Cl(1-p){C equivalent to CC6H5-m(C equivalent to CFlu)(m)}((1+p))][PF6](n) are reported (n = 01; m = 12; [M] = [Fe(eta(5)-C5Me5)(kappa(2)-dppe)] and p = 1 or [M] = [trans-Ru(kappa(2)-dppe)(2)] and p = 01). The linear and third-order nonlinear optical properties of these new organometallic complexes featuring phenylalkynyl ligands functionalized by 2-fluorenyl (Flu) groups were studied in their stable redox states. Their first electronic transitions are assigned with the help of DFT calculations. We show here that these compounds possess significant third-order NLO responses in the near-IR range for molecules of their size. In particular, the remarkably large 2PA activities of the new Ru(II) compounds in the 600-800 nm range (Z-scan) make them attractive nonlinear chromophores. Structure-property studies emphasize the importance of para- versus meta-connection of the 2-fluorenylethynyl units on the phenylalkynyl core and reveal that upon progressing from mono- to bis-alkynyl complexes a further increase of the 2PA cross section can be obtained while maintaining linear transparency in the visible range.

KW - Enhanced 2-photon absorption

KW - Excited-state absorption

KW - Iron sigma-acetylides

KW - X-ray crystal

KW - Organometallic complexes

KW - Molecular wires

KW - Chiroptical properties

KW - Diacetylide complexes

KW - Electronic-structures

KW - Fluorene derivatives

UR - https://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=anu_research_portal_plus2&SrcAuth=WosAPI&KeyUT=WOS:000439955400007&DestLinkType=FullRecord&DestApp=WOS_CPL

U2 - 10.1021/acs.organomet.8b00229

DO - 10.1021/acs.organomet.8b00229

M3 - Article

SN - 0276-7333

VL - 37

SP - 2245

EP - 2262

JO - Organometallics

JF - Organometallics

IS - 14

ER -

Triadon A, Grelaud G, Richy N, Mongin O, Moxey GJ, Dixon IM et al. Linear and Third-Order Nonlinear Optical Properties of Fe(η5-C5Me5)(κ2-dppe)- and trans-Ru(κ2-dppe)2-Alkynyl Complexes Containing 2-Fluorenyl End Groups. Organometallics. 2018 Jul 23;37(14):2245-2262. doi: 10.1021/acs.organomet.8b00229

Linear and Third-Order Nonlinear Optical Properties of Fe(η<SUP>5</SUP>-C<sub>5</sub>Me<sub>5</sub>)(κ<SUP>2</SUP>-dppe)- and <i>trans</i>-Ru(κ<SUP>2</SUP>-dppe)<sub>2</sub>-Alkynyl Complexes Containing 2-Fluorenyl End Groups

Abstract

Access to Document

Other files and links

Fingerprint

Cite this