Syntheses and Optical Properties of Azo‐Functionalized Ruthenium Alkynyl Complexes1. Issue 7 (22nd June 2016)

• Record Type: Journal Article
• Authors: 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.
• Is Part Of: ChemPlusChem. Volume 81:Issue 7(2016)
• Page Start: 621
• Page End: 628
• Publication Date: 2016-06-22
• Subjects: alkene ligands -- alkyne ligands -- electrochemistry -- nonlinear optics -- transition metals; Chemistry -- Periodicals; 540.5
• DOI: 10.1002/cplu.201600222
• Languages: English
• ISSNs: 2192-6506

Abstract

Abstract: The syntheses of trans ‐[Ru(C≡C‐1‐C6 H4 ‐4‐N=N‐1‐C6 H4 ‐4‐C≡C‐1‐C6 H4 ‐4‐NO2 )Cl(L2 )2 ] (L2 =dppm (Ru1 ), dppe) (Ru2 )), trans ‐[Ru(C≡C‐1‐C6 H4 ‐4‐N=N‐1‐C6 H4 ‐4‐( E )‐CH=CH‐1‐C6 H4 ‐4‐NO2 )Cl(dppe)2 ] (Ru3 ), and trans ‐[Ru(C≡C‐1‐C6 H4 ‐4‐( E )‐CH=CH‐1‐C6 H2 ‐2, 6‐Et2 ‐4‐N=N‐1‐C6 H4 ‐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. Abstract : It takes alkynes : Dipolar organometallic complexes with a ligated ruthenium donor, nitro acceptor, and a π‐delocalizable bridge incorporating an azo group exhibit large quadratic optical nonlinearities (see figure). The potentials of their reversible oxidation processes and the wavelengths of their absorption maxima in both the resting and oxidized forms are tuned by systematic structural modification.