Abstract
Abstract Five new thiogermanates, [Ni II (dien) 2 ] 2 (Ge 2 S 6 ) (dien = diethylenetriamine) ( 1 ), [Ni II (dien) 2 ](H 2 pipe)(Ge 2 S 6 ) (pipe = piperazine) ( 2 ), {[Mn II (tren)] 2 ( μ 2 -Ge 2 S 6 )} (tren = N,N,N-tris(2-aminoethyl)amine) ( 3 ) and {[M II (tepa)] 2 ( μ 2 -Ge 2 S 6 )} (M = Mn ( 4a ), Ni ( 4b ); tepa = tetraethylenepentamine), have been obtained solvothermally in the presence of tri-(L 3 ), tetra-(L 4 ) and penta-dentate (L 5 ) chelating amines and transition metal (TM) ions. Single-crystal X-ray diffraction analyses show that compounds 1 – 2 are comprised of discrete (Ge 2 S 6 ) 4− anions and TM complex (TMC) cations, while compounds 3 – 4b are composed of each dimeric (Ge 2 S 6 ) 4− anion bridging two TMC cations via TM–S bonds to form a neutral molecule. Notably, two interesting in situ metal/ligand reactions were observed in the solvothermal syntheses of 2 and 3 . The present compounds exhibit wide optical gap ranging from 2.94 to 3.39 eV and photoluminescence with the emission maxima occurring around 440 ( 1 , 2 , 3 and 4b ) and 489 nm ( 4a ). Magnetic measurements show the presence of weak antiferromagnetic interactions between magnetic centers in the five compounds.
Published Version
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