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

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

Amédée Triadon, Guillaume Grelaud, Nicolas Richy, Olivier Mongin, Graeme J. Moxey, Isabelle M. Dixon, Xinwei Yang, Genmiao Wang, Adam Barlow, Joelle Rault-Berthelot, Marie P. Cifuentes, Mark G. Humphrey^*, Frédéric Paul

^*Corresponding author for this work

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

17 Citations (Scopus)

Abstract

The synthesis and characterization of a set of redox-active iron and ruthenium alkynyl complexes of general formula [[M]Cl_(1-p){C≡CC₆H_5-m(C≡CFlu)_m}_(1+p)][PF₆]_n are reported (n = 0-1; m = 1-2; [M] = [Fe(η⁵-C₅Me₅)(κ²-dppe)] and p = 1 or [M] = [trans-Ru(κ²-dppe)₂] and p = 0-1). 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

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Triadon, A., Grelaud, G., Richy, N., Mongin, O., Moxey, G. J., Dixon, I. M., Yang, X., Wang, G., Barlow, A., Rault-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{f59cbfb47daa452a8054b31bfa6585c1,

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≡CC6H5-m(C≡CFlu)m}(1+p)][PF6]n are reported (n = 0-1; m = 1-2; [M] = [Fe(η5-C5Me5)(κ2-dppe)] and p = 1 or [M] = [trans-Ru(κ2-dppe)2] and p = 0-1). 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.",

author = "Am{\'e}d{\'e}e 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 Rault-Berthelot and Cifuentes, {Marie P.} and Humphrey, {Mark G.} and Fr{\'e}d{\'e}ric Paul",

note = "Publisher Copyright: {\textcopyright} 2018 American Chemical Society.",

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",

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Triadon, A, Grelaud, G, Richy, N, Mongin, O, Moxey, GJ, Dixon, IM, Yang, X, Wang, G, Barlow, A, Rault-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

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, Amédée

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 - Rault-Berthelot, Joelle

AU - Cifuentes, Marie P.

AU - Humphrey, Mark G.

AU - Paul, Frédéric

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≡CC6H5-m(C≡CFlu)m}(1+p)][PF6]n are reported (n = 0-1; m = 1-2; [M] = [Fe(η5-C5Me5)(κ2-dppe)] and p = 1 or [M] = [trans-Ru(κ2-dppe)2] and p = 0-1). 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≡CC6H5-m(C≡CFlu)m}(1+p)][PF6]n are reported (n = 0-1; m = 1-2; [M] = [Fe(η5-C5Me5)(κ2-dppe)] and p = 1 or [M] = [trans-Ru(κ2-dppe)2] and p = 0-1). 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.

UR - http://www.scopus.com/inward/record.url?scp=85050457046&partnerID=8YFLogxK

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 -

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

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