Synthesis, Optical, Electrochemical, and Theoretical Studies of Dipolar Ruthenium Alkynyl Complexes with Oligo(phenylenevinylene) Bridges

Huihua Zhang; Mahbod Morshedi; Mahesh S. Kodikara; Graeme J. Moxey; Genmiao Wang; Huan Wang; Cristóbal Quintana; Rob Stranger; Chi Zhang; Marie P. Cifuentes; Mark G. Humphrey

doi:10.1002/cplu.201600203

Synthesis, Optical, Electrochemical, and Theoretical Studies of Dipolar Ruthenium Alkynyl Complexes with Oligo(phenylenevinylene) Bridges

Huihua Zhang, Mahbod Morshedi, Mahesh S. Kodikara, Graeme J. Moxey, Genmiao Wang, Huan Wang, Cristóbal Quintana, Rob Stranger, Chi Zhang, Marie P. Cifuentes, Mark G. Humphrey^*

^*Corresponding author for this work

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

6 Citations (Scopus)

Abstract

The syntheses of oligo(p-phenylenevinylene)s (OPVs) end-functionalized with a ligated ruthenium alkynyl unit as a donor and a nitro as acceptor, namely trans-[Ru{C≡C-1-C₆H₄-4-(E)-CH=CH-1-C₆H₂-2,5-Et₂-4-(E)-CH=CH-1-C₆H₂-2,5-Et₂-4-(E)-CH=CH-1-C₆H₄-4-NO₂}Cl(dppe)₂] (Ru4), trans-[Ru{C≡C-1-C₆H₄-4-(E)-CH=CH-1-C₆H₂-2,5-Et₂-4-(E)-CH=CH-1-C₆H₂-2,5-Et₂-4-(E)-CH=CH-1-C₆H₂-2,5-(n-hexyl)₂-4-(E)-CH=CH-1-C₆H₂-2,5-(n-hexyl)₂-4-(E)-CH=CH-1-C₆H₄-4-NO₂}Cl(dppe)₂] (Ru6), and trans-[Ru{C≡C-1-C₆H₄-4-(E)-CH=CH-1-C₆H₂-2,5-Et₂-4-(E)-CH=CH-1-C₆H₂-2,5-Et₂-4-(E)-CH=CH-1-C₆H₂-2,5-(n-hexyl)₂-4-(E)-CH=CH-1-C₆H₂-2,5-(n-hexyl)₂-4-(E)-CH=CH-1-C₆H₂-2,5-(2-ethyl-n-hexyl)₂-4-(E)-CH=CH-1-C₆H₂-2,5-(2-ethyl-n-hexyl)₂-4-(E)-CH=CH-1-C₆H₄-4-NO₂}Cl(dppe)₂] (Ru8), are reported, together with those of precursor alkynes. Their electrochemical properties were assessed by cyclic voltammetry (CV), their linear optical and quadratic nonlinear optical (NLO) properties assayed by UV/Vis-NIR spectroscopy and hyper-Rayleigh scattering studies at 1064 nm, respectively, and their linear optical properties in the formally Ru^III state examined by UV/Vis-NIR spectroelectrochemistry. Computational studies employing time-dependent density functional theory were undertaken on model complexes to rationalize the optical observations.

Original language	English
Pages (from-to)	613-620
Number of pages	8
Journal	ChemPlusChem
Volume	81
Issue number	7
DOIs	https://doi.org/10.1002/cplu.201600203
Publication status	Published - 1 Jul 2016

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@article{8d455c055662410caa49481c437c36ff,

title = "Synthesis, Optical, Electrochemical, and Theoretical Studies of Dipolar Ruthenium Alkynyl Complexes with Oligo(phenylenevinylene) Bridges",

abstract = "The syntheses of oligo(p-phenylenevinylene)s (OPVs) end-functionalized with a ligated ruthenium alkynyl unit as a donor and a nitro as acceptor, namely trans-[Ru{C≡C-1-C6H4-4-(E)-CH=CH-1-C6H2-2,5-Et2-4-(E)-CH=CH-1-C6H2-2,5-Et2-4-(E)-CH=CH-1-C6H4-4-NO2}Cl(dppe)2] (Ru4), trans-[Ru{C≡C-1-C6H4-4-(E)-CH=CH-1-C6H2-2,5-Et2-4-(E)-CH=CH-1-C6H2-2,5-Et2-4-(E)-CH=CH-1-C6H2-2,5-(n-hexyl)2-4-(E)-CH=CH-1-C6H2-2,5-(n-hexyl)2-4-(E)-CH=CH-1-C6H4-4-NO2}Cl(dppe)2] (Ru6), and trans-[Ru{C≡C-1-C6H4-4-(E)-CH=CH-1-C6H2-2,5-Et2-4-(E)-CH=CH-1-C6H2-2,5-Et2-4-(E)-CH=CH-1-C6H2-2,5-(n-hexyl)2-4-(E)-CH=CH-1-C6H2-2,5-(n-hexyl)2-4-(E)-CH=CH-1-C6H2-2,5-(2-ethyl-n-hexyl)2-4-(E)-CH=CH-1-C6H2-2,5-(2-ethyl-n-hexyl)2-4-(E)-CH=CH-1-C6H4-4-NO2}Cl(dppe)2] (Ru8), are reported, together with those of precursor alkynes. Their electrochemical properties were assessed by cyclic voltammetry (CV), their linear optical and quadratic nonlinear optical (NLO) properties assayed by UV/Vis-NIR spectroscopy and hyper-Rayleigh scattering studies at 1064 nm, respectively, and their linear optical properties in the formally RuIII state examined by UV/Vis-NIR spectroelectrochemistry. Computational studies employing time-dependent density functional theory were undertaken on model complexes to rationalize the optical observations.",

keywords = "computational chemistry, electrochemistry, nonlinear optics, organometallic chemistry, transition metals",

author = "Huihua Zhang and Mahbod Morshedi and Kodikara, {Mahesh S.} and Moxey, {Graeme J.} and Genmiao Wang and Huan Wang and Crist{\'o}bal Quintana and Rob Stranger and Chi Zhang and Cifuentes, {Marie P.} and Humphrey, {Mark G.}",

note = "Publisher Copyright: {\textcopyright} 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim",

year = "2016",

month = jul,

day = "1",

doi = "10.1002/cplu.201600203",

language = "English",

volume = "81",

pages = "613--620",

journal = "ChemPlusChem",

issn = "2192-6506",

publisher = "Wiley-VCH Verlag GmbH",

number = "7",

}

TY - JOUR

T1 - Synthesis, Optical, Electrochemical, and Theoretical Studies of Dipolar Ruthenium Alkynyl Complexes with Oligo(phenylenevinylene) Bridges

AU - Zhang, Huihua

AU - Morshedi, Mahbod

AU - Kodikara, Mahesh S.

AU - Moxey, Graeme J.

AU - Wang, Genmiao

AU - Wang, Huan

AU - Quintana, Cristóbal

AU - Stranger, Rob

AU - Zhang, Chi

AU - Cifuentes, Marie P.

AU - Humphrey, Mark G.

PY - 2016/7/1

Y1 - 2016/7/1

N2 - The syntheses of oligo(p-phenylenevinylene)s (OPVs) end-functionalized with a ligated ruthenium alkynyl unit as a donor and a nitro as acceptor, namely trans-[Ru{C≡C-1-C6H4-4-(E)-CH=CH-1-C6H2-2,5-Et2-4-(E)-CH=CH-1-C6H2-2,5-Et2-4-(E)-CH=CH-1-C6H4-4-NO2}Cl(dppe)2] (Ru4), trans-[Ru{C≡C-1-C6H4-4-(E)-CH=CH-1-C6H2-2,5-Et2-4-(E)-CH=CH-1-C6H2-2,5-Et2-4-(E)-CH=CH-1-C6H2-2,5-(n-hexyl)2-4-(E)-CH=CH-1-C6H2-2,5-(n-hexyl)2-4-(E)-CH=CH-1-C6H4-4-NO2}Cl(dppe)2] (Ru6), and trans-[Ru{C≡C-1-C6H4-4-(E)-CH=CH-1-C6H2-2,5-Et2-4-(E)-CH=CH-1-C6H2-2,5-Et2-4-(E)-CH=CH-1-C6H2-2,5-(n-hexyl)2-4-(E)-CH=CH-1-C6H2-2,5-(n-hexyl)2-4-(E)-CH=CH-1-C6H2-2,5-(2-ethyl-n-hexyl)2-4-(E)-CH=CH-1-C6H2-2,5-(2-ethyl-n-hexyl)2-4-(E)-CH=CH-1-C6H4-4-NO2}Cl(dppe)2] (Ru8), are reported, together with those of precursor alkynes. Their electrochemical properties were assessed by cyclic voltammetry (CV), their linear optical and quadratic nonlinear optical (NLO) properties assayed by UV/Vis-NIR spectroscopy and hyper-Rayleigh scattering studies at 1064 nm, respectively, and their linear optical properties in the formally RuIII state examined by UV/Vis-NIR spectroelectrochemistry. Computational studies employing time-dependent density functional theory were undertaken on model complexes to rationalize the optical observations.

AB - The syntheses of oligo(p-phenylenevinylene)s (OPVs) end-functionalized with a ligated ruthenium alkynyl unit as a donor and a nitro as acceptor, namely trans-[Ru{C≡C-1-C6H4-4-(E)-CH=CH-1-C6H2-2,5-Et2-4-(E)-CH=CH-1-C6H2-2,5-Et2-4-(E)-CH=CH-1-C6H4-4-NO2}Cl(dppe)2] (Ru4), trans-[Ru{C≡C-1-C6H4-4-(E)-CH=CH-1-C6H2-2,5-Et2-4-(E)-CH=CH-1-C6H2-2,5-Et2-4-(E)-CH=CH-1-C6H2-2,5-(n-hexyl)2-4-(E)-CH=CH-1-C6H2-2,5-(n-hexyl)2-4-(E)-CH=CH-1-C6H4-4-NO2}Cl(dppe)2] (Ru6), and trans-[Ru{C≡C-1-C6H4-4-(E)-CH=CH-1-C6H2-2,5-Et2-4-(E)-CH=CH-1-C6H2-2,5-Et2-4-(E)-CH=CH-1-C6H2-2,5-(n-hexyl)2-4-(E)-CH=CH-1-C6H2-2,5-(n-hexyl)2-4-(E)-CH=CH-1-C6H2-2,5-(2-ethyl-n-hexyl)2-4-(E)-CH=CH-1-C6H2-2,5-(2-ethyl-n-hexyl)2-4-(E)-CH=CH-1-C6H4-4-NO2}Cl(dppe)2] (Ru8), are reported, together with those of precursor alkynes. Their electrochemical properties were assessed by cyclic voltammetry (CV), their linear optical and quadratic nonlinear optical (NLO) properties assayed by UV/Vis-NIR spectroscopy and hyper-Rayleigh scattering studies at 1064 nm, respectively, and their linear optical properties in the formally RuIII state examined by UV/Vis-NIR spectroelectrochemistry. Computational studies employing time-dependent density functional theory were undertaken on model complexes to rationalize the optical observations.

KW - computational chemistry

KW - electrochemistry

KW - nonlinear optics

KW - organometallic chemistry

KW - transition metals

UR - http://www.scopus.com/inward/record.url?scp=84978805168&partnerID=8YFLogxK

U2 - 10.1002/cplu.201600203

DO - 10.1002/cplu.201600203

M3 - Article

SN - 2192-6506

VL - 81

SP - 613

EP - 620

JO - ChemPlusChem

JF - ChemPlusChem

IS - 7

ER -

Synthesis, Optical, Electrochemical, and Theoretical Studies of Dipolar Ruthenium Alkynyl Complexes with Oligo(phenylenevinylene) Bridges

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