With
assistance of reactive and coordinative hydrazine, transition-metal
telluromercurates [Mn(trien)(N2H4)2]2[Hg2Te4]2 (A), [Zn(trien)(N2H4)2]Hg2Te4 (B), [Mn(tepa)(N2H4)]2Hg4Te12 (C), [TM(trien)(Hg2Te4)] (TM = Mn (D), Zn (E)), and [Zn(atep)]2Hg5Te12 (atep = 4-(2-aminoethyl)triethylenetetramine)
(F) were solvothermally prepared in triethylenetetramine
(trien) or tetraethylenepentamine (tepa) solvents using elemental
Te as precursor in lower temperature range. Compounds A and B consist of mixed coordination cations [TM(trien)(N2H4)2]2+ (TM = Mn, Zn) and
one-dimensional polyanion [Hg2Te4]2– with the five-membered Hg2Te3 rings being
coplanar. Compound C is composed of two [Mn(tepa)(N2H4)]2+ cations and a [Hg4Te12]4– cluster with a centrosymmetric
structure. Compounds D and E consist of
coordination polymer [TM(trien) (Hg2Te4)] containing
novel doubled [Hg2Te4]n chain with tetrahedrally coordinated Hg(II) centers, which
is quite different from the common single chain with the same composition
of [Hg2Te4]n. D and E are the first examples of telluromercurates
incorporated with TM complex units via TM–Te bonds. Compound F contains fivefold coordinated [Zn(atep)]2+ cations
and zigzag [Hg5Te124–]n polymeric anion. The [Hg5Te124–]n anion
is a new species of the binary telluromercurates. It is built from
[Hg4Te6] and [HgTe2(Te4)] subunits via interconnectivity, which generates Hg3Te3 and Hg4Te4 rings in the structure.
Compounds A–F are potential semiconductors
with narrow band gaps in the range of 0.96–1.09 eV. Photocatalytic
investigation of Mn(II) complexes show that they are photocatalytically
active in the degradation of CV under visible-light irradiation with
the highest catalytic effective of cluster compound C.