Syntheses and Optical Properties of Azo-Functionalized Ruthenium Alkynyl Complexes

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

doi:10.1002/cplu.201600222

Syntheses and Optical Properties of Azo-Functionalized Ruthenium Alkynyl Complexes

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

^*Corresponding author for this work

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

10 Citations (Scopus)

Abstract

The syntheses of trans-[Ru(C≡C-1-C₆H₄-4-N=N-1-C₆H₄-4-C≡C-1-C₆H₄-4-NO₂)Cl(L₂)₂] (L₂=dppm (Ru1), dppe) (Ru2)), trans-[Ru(C≡C-1-C₆H₄-4-N=N-1-C₆H₄-4-(E)-CH=CH-1-C₆H₄-4-NO₂)Cl(dppe)₂] (Ru3), and trans-[Ru(C≡C-1-C₆H₄-4-(E)-CH=CH-1-C₆H₂-2,6-Et₂-4-N=N-1-C₆H₄-4-NO₂)Cl(dppe)₂] (Ru4) are reported, together with those of precursor alkynes. Their electrochemical properties were assessed by cyclic voltammetry (CV), 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. These data were compared to those of analogues with E-ene and yne linkages in place of the azo groups. Computational studies using time-dependent density functional theory were undertaken on model compounds (Ru2′–Ru4′) to rationalize the optical behaviour of the experimental complexes.

Original language	English
Pages (from-to)	621-628
Number of pages	8
Journal	ChemPlusChem
Volume	81
Issue number	7
DOIs	https://doi.org/10.1002/cplu.201600222
Publication status	Published - 1 Jul 2016

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@article{d87c40367a0a4687b6c876e0380bacef,

title = "Syntheses and Optical Properties of Azo-Functionalized Ruthenium Alkynyl Complexes",

abstract = "The syntheses of trans-[Ru(C≡C-1-C6H4-4-N=N-1-C6H4-4-C≡C-1-C6H4-4-NO2)Cl(L2)2] (L2=dppm (Ru1), dppe) (Ru2)), trans-[Ru(C≡C-1-C6H4-4-N=N-1-C6H4-4-(E)-CH=CH-1-C6H4-4-NO2)Cl(dppe)2] (Ru3), and trans-[Ru(C≡C-1-C6H4-4-(E)-CH=CH-1-C6H2-2,6-Et2-4-N=N-1-C6H4-4-NO2)Cl(dppe)2] (Ru4) are reported, together with those of precursor alkynes. Their electrochemical properties were assessed by cyclic voltammetry (CV), 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. These data were compared to those of analogues with E-ene and yne linkages in place of the azo groups. Computational studies using time-dependent density functional theory were undertaken on model compounds (Ru2′–Ru4′) to rationalize the optical behaviour of the experimental complexes.",

keywords = "alkene ligands, alkyne ligands, electrochemistry, nonlinear optics, transition metals",

author = "Dilan Wei and Kodikara, {Mahesh S.} and Mahbod Morshedi and Moxey, {Graeme J.} and Huan Wang and Genmiao Wang and Crist{\'o}bal Quintana and Chi Zhang and Rob Stranger 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.201600222",

language = "English",

volume = "81",

pages = "621--628",

journal = "ChemPlusChem",

issn = "2192-6506",

publisher = "Wiley-VCH Verlag GmbH",

number = "7",

}

TY - JOUR

T1 - Syntheses and Optical Properties of Azo-Functionalized Ruthenium Alkynyl Complexes

AU - Wei, Dilan

AU - Kodikara, Mahesh S.

AU - Morshedi, Mahbod

AU - Moxey, Graeme J.

AU - Wang, Huan

AU - Wang, Genmiao

AU - Quintana, Cristóbal

AU - Zhang, Chi

AU - Stranger, Rob

AU - Cifuentes, Marie P.

AU - Humphrey, Mark G.

PY - 2016/7/1

Y1 - 2016/7/1

N2 - The syntheses of trans-[Ru(C≡C-1-C6H4-4-N=N-1-C6H4-4-C≡C-1-C6H4-4-NO2)Cl(L2)2] (L2=dppm (Ru1), dppe) (Ru2)), trans-[Ru(C≡C-1-C6H4-4-N=N-1-C6H4-4-(E)-CH=CH-1-C6H4-4-NO2)Cl(dppe)2] (Ru3), and trans-[Ru(C≡C-1-C6H4-4-(E)-CH=CH-1-C6H2-2,6-Et2-4-N=N-1-C6H4-4-NO2)Cl(dppe)2] (Ru4) are reported, together with those of precursor alkynes. Their electrochemical properties were assessed by cyclic voltammetry (CV), 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. These data were compared to those of analogues with E-ene and yne linkages in place of the azo groups. Computational studies using time-dependent density functional theory were undertaken on model compounds (Ru2′–Ru4′) to rationalize the optical behaviour of the experimental complexes.

AB - The syntheses of trans-[Ru(C≡C-1-C6H4-4-N=N-1-C6H4-4-C≡C-1-C6H4-4-NO2)Cl(L2)2] (L2=dppm (Ru1), dppe) (Ru2)), trans-[Ru(C≡C-1-C6H4-4-N=N-1-C6H4-4-(E)-CH=CH-1-C6H4-4-NO2)Cl(dppe)2] (Ru3), and trans-[Ru(C≡C-1-C6H4-4-(E)-CH=CH-1-C6H2-2,6-Et2-4-N=N-1-C6H4-4-NO2)Cl(dppe)2] (Ru4) are reported, together with those of precursor alkynes. Their electrochemical properties were assessed by cyclic voltammetry (CV), 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. These data were compared to those of analogues with E-ene and yne linkages in place of the azo groups. Computational studies using time-dependent density functional theory were undertaken on model compounds (Ru2′–Ru4′) to rationalize the optical behaviour of the experimental complexes.

KW - alkene ligands

KW - alkyne ligands

KW - electrochemistry

KW - nonlinear optics

KW - transition metals

UR - http://www.scopus.com/inward/record.url?scp=84978110468&partnerID=8YFLogxK

U2 - 10.1002/cplu.201600222

DO - 10.1002/cplu.201600222

M3 - Article

SN - 2192-6506

VL - 81

SP - 621

EP - 628

JO - ChemPlusChem

JF - ChemPlusChem

IS - 7

ER -

Syntheses and Optical Properties of Azo-Functionalized Ruthenium Alkynyl Complexes

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