Syntheses, Electrochemical, Linear Optical, And Cubic Nonlinear Optical Properties Of Ruthenium Alkynyl-Functionalized Oligo(Styrenes)

The nonlinear optical(NLO) properties of materials have come under increasing scrutiny. This is because when light interacts with materials possessing NLO properties, the incident light can be changed and new electromagnetic field components produced(e.g., with differing phase, frequency, amplitude, polarization, path, etc). As a result, NLO materials have potential applications in optical signal processing, switching and frequency generation(making use of processes such as harmonic generation, frequency mixing, and optical parametric oscillation), and may also contribute to optical data storage, optical communication, and image processing.Aryl acetylynes 3,5-RC6H3Et2(C≡CH 2c, C≡CC6H4-4-C≡CSi Me3 a2, C≡CC6H4-4-C≡CH a3) were prepared through sequentional Sonogashira coupling and desilylation reactions from the diethyliodoaryl compound 3,5-IC6H3Et2(2b). trans-Ru(C≡CC6H4-4-CHO)(C≡CC6H4-4-R)(dppe)2(R = H b5, NO2 b6, C≡CC6H4-3,5-Et2 b7,(E)-CH=CHC6H4-4-But b8, trans-Ru(C≡CC6H4-4-R)Cl(R = C≡CC6H4-3,5-Et2 b3,(E)-CH=CHC6H4-4-But b4), 1,2,4,5-{trans-Ru(RC6H4C≡C)(C≡CC6H4-4-(E)-CH=CH)(dppe)2}4C6H2)(R = Ph b9, C≡CC6H4-3,5-Et2 b11,(E)-CH=CHC6H4-4-But b12) were prepared. All of the structures of complexes were characterized by NMR, x-ray single crystal diffusion, MS, IR and element analysis.The cyclic voltammetry of each of the metal-containing species, and the low temperature UV-vis-NIR spectroelectrochemistry of the cruciform series 1,2,4,5-{trans-Ru(RC6H4C≡C)(C≡CC6H4-4-(E)-CH=CH)(dppe)2}4C6H2)(R = Ph b9, C≡CC6H4-3,5-Et2 b11,(E)-CH=CHC6H4-4-But b12) are studied. What’s more, third-order nonlinearities and two-photon absorption cross-section parameters were measured for the bisalkynyl complexes b7 and b8 and the cruciform complexes b9, b11, b12, using the Z-scan technique.