Second-Order NLO Active Heterotrimetallic Schiff Base Metallopolymer

Salvador Celedón; Thierry Roisnel; Isabelle Ledoux-Rak; Jean René Hamon; David Carrillo; Carolina Manzur

doi:10.1007/s10904-017-0524-x

Second-Order NLO Active Heterotrimetallic Schiff Base Metallopolymer

Salvador Celedón, Thierry Roisnel, Isabelle Ledoux-Rak, Jean René Hamon, David Carrillo, Carolina Manzur

INSTITUTE OF CHEMISTRY

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

13 Scopus citations

Abstract

The new ionic heterotrimetallic unsymmetrically-substituted Schiff base complex [Ni{(η⁵-Cp)Fe(η⁵-C₅H₄)-C(=O)CH=C(4-HO-C₆H₄)NCH₂CH₂N=CH-(2-O-(η⁶-C₆H₄)Ru(η⁵-Cp*)}][PF₆] (3; Cp = C₅H₅ and Cp* = C₅(CH₃)₅) was prepared in 86% yield by a one-pot procedure by mixing equimolar amounts of 4-hydroxyphenyl functionalized ferrocenylenaminone 1, the organometallic aldehyde [(η⁵-Cp*)Ru(η⁶-2-HO-C₆H₄CHO)][PF₆] (2) and nickel(II) acetate tetrahydrate in refluxing ethanol for 2 h. Its corresponding side-chain metallopolymer 4 was synthesized by reacting the organometallic-inorganic hybrid 3 with polyacrylic acid (DP = 25) in DMF at 110 °C for 48 h with an equimolar quantity of N,N′-dicyclohexylcarbodiimide and a catalytic amount of 4-dimethylaminopyridine. The new complex 3 was characterized by FT-IR and multidimensional NMR spectroscopy, elemental analysis and mass spectrometry. Single crystal X-ray diffraction analysis of 3 showed that the ferrocenyl and [(η⁵-Cp*)Ru]⁺ units exhibit an anti-conformation and are almost coplanar with the unsymmetrical Schiff base complex fragment, while the 4-HO-C₆H₄ plane is almost perpendicular. The four-coordinate Ni^II metal ion adopts a square planar geometry, with two nitrogen and two oxygen donor atoms that are mutually trans. Size-Exclusion Chromatography established that metallopolymer 4 is formed of approximately three pendant ionic trimetallic units, while Differential Scanning Calorimetry and Thermal Gravimetric Analysis indicated that 3 and 4 are thermally stable with decomposition temperatures that exceed or border to 250 °C. Harmonic Light Scattering measurements at 1.91 µm incident wavelength showed that compounds 3 and 4 exhibit rather high second-order nonlinear responses, with hyperpolarizability β_1.91 values strongly increasing on passing from the monomeric unit 3 to its metallopolymeric counterpart 4.

Original language	English
Pages (from-to)	795-804
Number of pages	10
Journal	Journal of Inorganic and Organometallic Polymers and Materials
Volume	27
Issue number	3
DOIs	https://doi.org/10.1007/s10904-017-0524-x
State	Published - 1 May 2017

Keywords

Metallopolymer
Nickel
Nonlinear optics
Organometallic donor–acceptor
Ruthenium
Sandwich complexes
X-ray crystal structure

Access to Document

10.1007/s10904-017-0524-x

Cite this

@article{031a2beb59a84049aba92cba4d83a244,

title = "Second-Order NLO Active Heterotrimetallic Schiff Base Metallopolymer",

abstract = "The new ionic heterotrimetallic unsymmetrically-substituted Schiff base complex [Ni{(η5-Cp)Fe(η5-C5H4)-C(=O)CH=C(4-HO-C6H4)NCH2CH2N=CH-(2-O-(η6-C6H4)Ru(η5-Cp*)}][PF6] (3; Cp = C5H5 and Cp* = C5(CH3)5) was prepared in 86% yield by a one-pot procedure by mixing equimolar amounts of 4-hydroxyphenyl functionalized ferrocenylenaminone 1, the organometallic aldehyde [(η5-Cp*)Ru(η6-2-HO-C6H4CHO)][PF6] (2) and nickel(II) acetate tetrahydrate in refluxing ethanol for 2 h. Its corresponding side-chain metallopolymer 4 was synthesized by reacting the organometallic-inorganic hybrid 3 with polyacrylic acid (DP = 25) in DMF at 110 °C for 48 h with an equimolar quantity of N,N′-dicyclohexylcarbodiimide and a catalytic amount of 4-dimethylaminopyridine. The new complex 3 was characterized by FT-IR and multidimensional NMR spectroscopy, elemental analysis and mass spectrometry. Single crystal X-ray diffraction analysis of 3 showed that the ferrocenyl and [(η5-Cp*)Ru]+ units exhibit an anti-conformation and are almost coplanar with the unsymmetrical Schiff base complex fragment, while the 4-HO-C6H4 plane is almost perpendicular. The four-coordinate NiII metal ion adopts a square planar geometry, with two nitrogen and two oxygen donor atoms that are mutually trans. Size-Exclusion Chromatography established that metallopolymer 4 is formed of approximately three pendant ionic trimetallic units, while Differential Scanning Calorimetry and Thermal Gravimetric Analysis indicated that 3 and 4 are thermally stable with decomposition temperatures that exceed or border to 250 °C. Harmonic Light Scattering measurements at 1.91 µm incident wavelength showed that compounds 3 and 4 exhibit rather high second-order nonlinear responses, with hyperpolarizability β1.91 values strongly increasing on passing from the monomeric unit 3 to its metallopolymeric counterpart 4.",

keywords = "Metallopolymer, Nickel, Nonlinear optics, Organometallic donor–acceptor, Ruthenium, Sandwich complexes, X-ray crystal structure",

author = "Salvador Celed{\'o}n and Thierry Roisnel and Isabelle Ledoux-Rak and Hamon, {Jean Ren{\'e}} and David Carrillo and Carolina Manzur",

note = "Publisher Copyright: {\textcopyright} 2017, Springer Science+Business Media New York.",

year = "2017",

month = may,

day = "1",

doi = "10.1007/s10904-017-0524-x",

language = "English",

volume = "27",

pages = "795--804",

journal = "Journal of Inorganic and Organometallic Polymers and Materials",

issn = "1574-1443",

publisher = "Springer New York",

number = "3",

}

TY - JOUR

T1 - Second-Order NLO Active Heterotrimetallic Schiff Base Metallopolymer

AU - Celedón, Salvador

AU - Roisnel, Thierry

AU - Ledoux-Rak, Isabelle

AU - Hamon, Jean René

AU - Carrillo, David

AU - Manzur, Carolina

PY - 2017/5/1

Y1 - 2017/5/1

N2 - The new ionic heterotrimetallic unsymmetrically-substituted Schiff base complex [Ni{(η5-Cp)Fe(η5-C5H4)-C(=O)CH=C(4-HO-C6H4)NCH2CH2N=CH-(2-O-(η6-C6H4)Ru(η5-Cp*)}][PF6] (3; Cp = C5H5 and Cp* = C5(CH3)5) was prepared in 86% yield by a one-pot procedure by mixing equimolar amounts of 4-hydroxyphenyl functionalized ferrocenylenaminone 1, the organometallic aldehyde [(η5-Cp*)Ru(η6-2-HO-C6H4CHO)][PF6] (2) and nickel(II) acetate tetrahydrate in refluxing ethanol for 2 h. Its corresponding side-chain metallopolymer 4 was synthesized by reacting the organometallic-inorganic hybrid 3 with polyacrylic acid (DP = 25) in DMF at 110 °C for 48 h with an equimolar quantity of N,N′-dicyclohexylcarbodiimide and a catalytic amount of 4-dimethylaminopyridine. The new complex 3 was characterized by FT-IR and multidimensional NMR spectroscopy, elemental analysis and mass spectrometry. Single crystal X-ray diffraction analysis of 3 showed that the ferrocenyl and [(η5-Cp*)Ru]+ units exhibit an anti-conformation and are almost coplanar with the unsymmetrical Schiff base complex fragment, while the 4-HO-C6H4 plane is almost perpendicular. The four-coordinate NiII metal ion adopts a square planar geometry, with two nitrogen and two oxygen donor atoms that are mutually trans. Size-Exclusion Chromatography established that metallopolymer 4 is formed of approximately three pendant ionic trimetallic units, while Differential Scanning Calorimetry and Thermal Gravimetric Analysis indicated that 3 and 4 are thermally stable with decomposition temperatures that exceed or border to 250 °C. Harmonic Light Scattering measurements at 1.91 µm incident wavelength showed that compounds 3 and 4 exhibit rather high second-order nonlinear responses, with hyperpolarizability β1.91 values strongly increasing on passing from the monomeric unit 3 to its metallopolymeric counterpart 4.

AB - The new ionic heterotrimetallic unsymmetrically-substituted Schiff base complex [Ni{(η5-Cp)Fe(η5-C5H4)-C(=O)CH=C(4-HO-C6H4)NCH2CH2N=CH-(2-O-(η6-C6H4)Ru(η5-Cp*)}][PF6] (3; Cp = C5H5 and Cp* = C5(CH3)5) was prepared in 86% yield by a one-pot procedure by mixing equimolar amounts of 4-hydroxyphenyl functionalized ferrocenylenaminone 1, the organometallic aldehyde [(η5-Cp*)Ru(η6-2-HO-C6H4CHO)][PF6] (2) and nickel(II) acetate tetrahydrate in refluxing ethanol for 2 h. Its corresponding side-chain metallopolymer 4 was synthesized by reacting the organometallic-inorganic hybrid 3 with polyacrylic acid (DP = 25) in DMF at 110 °C for 48 h with an equimolar quantity of N,N′-dicyclohexylcarbodiimide and a catalytic amount of 4-dimethylaminopyridine. The new complex 3 was characterized by FT-IR and multidimensional NMR spectroscopy, elemental analysis and mass spectrometry. Single crystal X-ray diffraction analysis of 3 showed that the ferrocenyl and [(η5-Cp*)Ru]+ units exhibit an anti-conformation and are almost coplanar with the unsymmetrical Schiff base complex fragment, while the 4-HO-C6H4 plane is almost perpendicular. The four-coordinate NiII metal ion adopts a square planar geometry, with two nitrogen and two oxygen donor atoms that are mutually trans. Size-Exclusion Chromatography established that metallopolymer 4 is formed of approximately three pendant ionic trimetallic units, while Differential Scanning Calorimetry and Thermal Gravimetric Analysis indicated that 3 and 4 are thermally stable with decomposition temperatures that exceed or border to 250 °C. Harmonic Light Scattering measurements at 1.91 µm incident wavelength showed that compounds 3 and 4 exhibit rather high second-order nonlinear responses, with hyperpolarizability β1.91 values strongly increasing on passing from the monomeric unit 3 to its metallopolymeric counterpart 4.

KW - Metallopolymer

KW - Nickel

KW - Nonlinear optics

KW - Organometallic donor–acceptor

KW - Ruthenium

KW - Sandwich complexes

KW - X-ray crystal structure

UR - http://www.scopus.com/inward/record.url?scp=85015658716&partnerID=8YFLogxK

U2 - 10.1007/s10904-017-0524-x

DO - 10.1007/s10904-017-0524-x

M3 - Article

AN - SCOPUS:85015658716

SN - 1574-1443

VL - 27

SP - 795

EP - 804

JO - Journal of Inorganic and Organometallic Polymers and Materials

JF - Journal of Inorganic and Organometallic Polymers and Materials

IS - 3

ER -

Second-Order NLO Active Heterotrimetallic Schiff Base Metallopolymer

Abstract

Keywords

Access to Document

Other files and links

Fingerprint

Cite this