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Syntheses and Optical Properties of Azo‐Functionalized Ruthenium Alkynyl Complexes
Author(s) -
Wei Dilan,
Kodikara Mahesh S.,
Morshedi Mahbod,
Moxey Graeme J.,
Wang Huan,
Wang Genmiao,
Quintana Cristóbal,
Zhang Chi,
Stranger Rob,
Cifuentes Marie P.,
Humphrey Mark G.
Publication year - 2016
Publication title -
chempluschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.801
H-Index - 61
ISSN - 2192-6506
DOI - 10.1002/cplu.201600222
Subject(s) - ruthenium , cyclic voltammetry , chemistry , spectroscopy , nonlinear optical , density functional theory , electrochemistry , ultraviolet visible spectroscopy , photochemistry , medicinal chemistry , stereochemistry , computational chemistry , organic chemistry , catalysis , physics , electrode , nonlinear system , quantum mechanics
Abstract The syntheses of trans ‐[Ru(C≡C‐1‐C 6 H 4 ‐4‐N=N‐1‐C 6 H 4 ‐4‐C≡C‐1‐C 6 H 4 ‐4‐NO 2 )Cl(L 2 ) 2 ] (L 2 =dppm ( Ru1 ), dppe) ( Ru2 )), trans ‐[Ru(C≡C‐1‐C 6 H 4 ‐4‐N=N‐1‐C 6 H 4 ‐4‐( E )‐CH=CH‐1‐C 6 H 4 ‐4‐NO 2 )Cl(dppe) 2 ] ( Ru3 ), and trans ‐[Ru(C≡C‐1‐C 6 H 4 ‐4‐( E )‐CH=CH‐1‐C 6 H 2 ‐2,6‐Et 2 ‐4‐N=N‐1‐C 6 H 4 ‐4‐NO 2 )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.