Syntheses And Cubic Nolinear Optical Properities Of Oligo(Phenylene)vinylene(OPV) Ruthenium Alkynyl Complexes

The incorporation of electron-rich metal centers into an oligo（phenylenevinylene）（O PV） structure to form a metal alkynyl complexes with a centrosymmetric structure is of considerable interest for the third-order nonlinear optical（NLO） materials. This thes is aims at preparing a series of metal alkynyl complexes with different lengths of the OPV π-bridge. These linear complexes had solubility problems that increased with in creasing chain length, necessitating the use of phenylene groups bearing solubilizing al hoxy substituents to ensure that linear optical data and particularly nonlinear optical da ta for the complexes were accessible.Aryl acetylynes（b1-b4） were prepared through reactions. Four organometallic mat erials have been synthesized in this thesis, trans-[RuCl（dppe）₂]{C≡C-1-C₆H₄-4-（E）-CH=CH-1-C₆H₂-{2,5-O（CH₂）₅CH₃}₂-4-（E）-CH=CH-1-C₆H₄-4-C≡C}-trans-[RuCl（dppe）₂]（c1）, trans-[RuCl（dppe）₂]{C≡C-1-C₆H₄-4-（E）-CH=CH-1-C₆H₂-{2,5-O（CH₂）₅CH₃}2-4-（E）-CH=CH-1-C₆H₂-{2,5-O（CH₂）₅CH₃}2-4-（E）-CH=CH-1-C₆H₂-{2,5-O（CH₂）₅CH₃}₂-4-（E）-CH=CH-1-C₆H₄-4-C≡C}-trans-[RuCl（dppe）₂]（c2）, trans-[RuCl（dppe）₂]{C≡C-1-C₆H₄-4-（E）-CH=CH-1-C₆H₂-{2,5-O（CH₂）₅CH₃}2-4-（E）-CH=CH-1-C₆H₂-{2,5-O（CH₂）₅CH₃}2-4-（E）-CH=CH-1-C₆H₂-{2,5-O（CH₂）₅CH₃}2-4-（E）-CH=CH-1-C₆H₂-{2,5-O（CH₂）₅CH₃}2-4-（E）-CH=CH-1-C₆H₂-{2,5-O（CH₂）₅CH₃}2-4-（E）-CH=CH-1-C₆H₄-4-C≡C}-trans-[RuCl（dppe）₂]（c3）, trans-[RuCl（dppe）₂]{C≡C-1-C₆H₄-4-（E）-CH=CH-1-C₆H₄-4-（E）-CH=CH-1-C₆H₂-{2,5-O（CH₂）₅CH₃}2-4-（E）-CH=CH-1-C₆H₂-{2,5-O（CH₂）₅CH₃}2-4-（E）-CH=CH-1-C₆H₂-{2,5-O（CH₂）₅CH₃}2-4-（E）-CH=CH-1-C₆H₂-{2,5-O（CH₂）₅CH₃}₂-4-（E）-CH=CH-1-C₆H₂-{2,5-O（CH₂）₅CH₃}₂-4-（E）-CH=CH-1-C₆H₄-4-（E）-CH=CH-1-C₆H₄-4-C≡C}-trans-[RuCl（dppe）₂]（c4）. All complexes have run NM R, ESI-MS, FT-IR, EA and the accurancy of the compounds also be confirmed by th ose tests. The cyclic voltammetry of each of the metal-containing species, and the low temperature UV-vis-NIR spectroelectrochemistry of organometallic materials are studied,and the third-order nonlinearities, two-photon absorption and three-photon absorption cr oss-section parameters were measured for the organometallic materials c1-c4, using the Z-scan technique. Exceptionally large two-photon absorption and three-photon absorptio n cross sections are found for the 8PV-containing example, highlighting the potential of an "organometalation" approach to NLO-efficient organic materials. The results are suggestive an approach to saturation, and that further increase in OPV size is unlikely to significantly increase the maximal value.