Synthesis, Characterization And Properties Of Ruthenium Complexes With Linear Hydrocarbon Chains

The studies on molecular-scale electronic devices have been developed very rapidly. Linear conjugated metallic complexes are one of the models for the study of molecular wires and molecular switches. A study on the synthesis, structures and properties of ruthenium complexes with linear conjugated hydrocarbon chains was systematically carried out. The main results are as follows:1 A total of 32 new compounds were synthesized. Five new polyene bridged heterobimetallic ferrocene-ruthenium complexes, two (CH)14-bridged bimetallic ruthenium complexes, three linear conjugated bridged bi-Au complexes and thirteen mono-ruthenium complexes with linear conjugated hydrocarbon chains were successfully synthesized. The structures for all these new compounds were fully characterized by elemental analysis, 1H NMR (HHCOSY), 13C NMR, 31P NMR, UV-vis spectroscopies, as well as for five new complexes being determined by X-ray diffraction techniques.2 The insertion reaction of RuHCl(CO)(PPh3)3 and ROCH have been studied further. The result shows that for different compounds RC=CH, the reaction goes well, and that only with CH2Cl2 as the solvent, the reaction works well. In this way, five ruthenium complexes Fc(CH=CH)3RuCl(CO)(PPh3)2, [RuCl(CO)(PPh3)2]2-(μ-(CH=CH)7) and RuCl(CO)(PPh3)2(μ-CH=CHCH=CHPh-R) (R = p-NO2, p-N(CH3)2, p-OCH3) were synthesized, which were very sensitive to oxygen, after treated with other ligands they could be changed to six coordinated complexes respectively with good stability.3 Hetero-bimetallic complexes Fc(CH=CH)3[Ru] have been successfully prepared. The structures of FcCH=CH-CH=CH-OCH and FcCH=CH-CH=CH-CH=CH-RuCl(CO)(PMe3)3 have been confirmed by X-ray diffraction. Electrochemical studies have shown that the metals linked through the CH=CH-CH=CH-CH=CH bridge interact with each other.4 The longest polyene-bridged bimetallic complexes to date, [Ru]-(CH)14-[Ru], have been successfully prepared. The structure of complex RuCl(CO)(PMe3)3(CH)14RuCl(CO)(PMe3)3 has been confirmed by X-ray diffraction. Electrochemical study shows that the metals linked through the (CH)14-bridge interact with each other. Through the investigation of UV-Visible spectra, λmax for RuCl(CO)(PMe3)3(CH)∞ RuCl(CO)(PMe3)3 can be estimated at 533 nm from the plot of λmax versus 1/n.5 Conjugated bridged bi-Au complexes Cy3PAu-C = C-(CH=CH)n-C = C-AuPCy3 (n=1,2,3) have been successfully synthesized. The structure of Cy3PAu-C=C-CH=CH-C=C-AuPCy3 has been confirmed by X-ray diffraction. Fluorescence study shows that complexes Cy3PAu-C = C-(CH=CH)n-C = C-AuPCy3(n=1,2,3) all have fluorescence properties, and the emmition spectrums exhibit progressively red-shifted with the increasing of the length of the bridge between the two Au.6 Complexes [Ru](μ-CH=CHCH=CHPhR) (R = p-NO2, p-N(CH3)2, p-OCH3) have been synthesized. The structure of RuTp(CO)(PPh3)-(μ-CH=CHCH=CHPh-N(CH3)2) have been confirmed by X-ray diffraction. HRS studies have shown that when R=NO2 the complexes have good NLO properties (large β value).