Ferrocene Thio Single Formic Acid Complex Synthesis, Crystal Structure And Performance

In this paper, using FcCOSNa ( Fc= (η⁵-C₅H₄)Fe(η⁵-C₅H₅)) and some subsidiary organic ligands as starting material, we obtained several metal-organic coordination compounds containing ferrocenethiocarboxylate components. Furthermore, we also investigated their crystal structures, electrochemical properties, fluorescent properties and third-order nonlinear optical (NLO) properties.Treatment of FcCOSNa with Cd(Ac)₂·2H₂O in the presence of bbp (bbp = 4,4'-trimethylene-dipyridine) or 4,4'-bpy afforded two one-dimensional chain polymers [Cd(SOCFc)₂(bbp)]_n (1) and [Cd₂(η²-SOCFc)₂(η¹-μ₂-SOCFc)₂(4,4'-bpy)]_n (4), respectively. in polymer 1, FcCOS^- units just as monodentate ligands coordinate with metal ions, but in polymer 4, FcCOS^- units exist as bridging monodentate (η¹-μ₂-SOCFc ) and bidentate (η²-SOCFc) modes coordinating with Cd(II) ions. The differences in structure between 1 and 4 are probably caused by the differences of the subsidiary ligands: bbp is longer than 4,4'-bpy, and bbp has more flexibility than 4,4'-bpy.Additionally, under the same condition, the reaction of FcCOSNa with Ni(OAc)₂·4H₂O and CoCl₂·6H₂O afforded two similar one-dimensional chain srtuctural polymers [Ni(η²-SOCFc)₂(btx)]_n (2) and [Co(η²-SOCFc)₂(btx)]_n (3) in the presence of btx (btx = 1,4-bis(triazol-1-ylmethyl)benzene). In the two polymers, the btx ligand connects metal ions leading to the one-dimensional chain with FcCOS^- units acting as chelate ligands in the side chain. By comparing polymers 1⁴, we can conclude that the organic bridging ligands play an important role in the formation of coordination compounds, and the difference of organic subsidiary ligands would lead to the difference of coordinate modes of the FcCOSNa ligand.To the mixture solution of FcCOSNa and metal ions, adding chelating ligands 2,2'-bpy or phen, we obtained three mononuclear complexs {[Ni(η²-SOCFc)₂(2,2'-bpy)] (CH₃OH)} (5), [Zn(SOCFc)₂(2,2'-bpy)] (6) and {[Hg(SOCFc)₂(phen)](0.5CH₃OH)}(7). In 6 and 7, the FcCOS^- units coordinate with metal ions as monodentate mode, while the FcCOS^- units in 5 bind to Ni(II) ions as chelating bidentate ligands (η²-SOCFc).The electrochemical properties of complexes 1⁷ and the free ferrocenethiocarboxylic...