Long Chain ketimine synthesis in a gold-thallium polymer

The heteropolynuclear complex [Tl{Au(C6Cl5)2}]n reacts with sterically demanding diamines as tetramethylenediamine (TMDA), 2,20-(ethylenedioxy)bis(ethylamine) (NOON), or triethylenetetramine (trien) in 1:1 molar ratio in tetrahydrofuran (THF), leading to products of stoichiometry [Tl{Au(C6Cl5)2}(L)]n (L=TMDA(1),NOON(2), or trien (3)) or [Tl2{Au(C6Cl5)2}2(L)]n (L=trien (4)) when the solvent used is toluene. Addition of acetylacetone to the diamine complexes in 1:1 molar ratio generates [Tl{Au- (C6Cl5)2}{OdC(CH3)CHC(CH3)NH(CH2)4NH2}]n (5) and in 1:2 molar ratio [Tl{Au(C6Cl5)2}(Lx)]n (Lx = {OdC(CH3)CHC(CH3)NHCH2CH2}2 (6), {OdC(CH3)CHC(CH3)NHCH2CH2OCH2}2 (7)). When the molar ratio is 1:2, with the exception of 3, all these complexes display luminescence in the solid state at room temperature and at 77 K. The origin of the luminescence could be assigned to a delocalizated exciton along the heterometallic chain formed by Au3 3 3 Tl interactions. In addition, a red shift is observed when the temperature decreases, which is attributed to the shortening of the Au-Tl distance at lower temperatures.The emissive properties of solutions of 5-7 and [Tl{Au(C6Cl5)2}]n inTHFwere studied after adding increasing amounts of different metal ions (Zn2þ ,Cd2þ ,Hg2þ ,Pb2þ ,Cu2þ ,Al3þ ,Ni2þ ,Ag þ ,Mn2þ , Bi3þ ) and anions (F-, Cl-, Br-, I-, H2PO4 -, ClO4-, Bz-, Ac-, HSO4-, NO3-). Interestingly, an enhancement of the fluorescence emission intensity was observed for the complexes considered only upon addition of Br-, Cl-, and Ac-.