Heterometallic Pb-Ag iodometallates [Ln(DMF)8]2Pb3Ag10I22 [Ln = Ce(1), Pr(2)] were prepared by the reactions of PbI2, AgNO3 and KI in dimethylformamide (DMF) templated by [Ln(DMF)8](3+) complexes formed in situ by stirring LnCl3 in DMF. The same reactions in the absence of AgNO3 or PbI2 afforded iodoplumbate [Pr(DMF)9]2[Pr(DMF)8]Pb11I31 (3), and iodoargentates [Ln(DMF)8]Ag6I9 [Ln = Ce(4), Pr(5)], respectively. Compounds 1 and 2 contain a ternary one-dimensional polymeric [Pb3Ag10I22](6-) anion self-assembled from five AgI4, one PbI6 and one PbI4 primary units via edge- and face-sharing. Twelve PbI6 octahedra are interlinked via sharing of common faces to generate a 1D zigzag [Pb11I31(9-)]n chain in 3, which represents a new member of iodoplumbate aggregates. In 4 and 5, three AgI4 tetrahedra connect through common edges to form the [Ag6I12](6-) building block. The [Ag6I12](6-) blocks are further interlinked by sharing common edges, resulting in the 1D [Ag6I9(3-)]n chain. Optical absorption spectra showed that the synthesized Ag-iodoplumbate and iodoplumbate have potential for being used as semiconductors. Our results show that heterometallic halometallate properties can be tuned by combining structural units with different symmetries, enabling the synthesis of specific functional materials.

The novel iron selenidostannates [Fe(bipy)₃]Sn₄Se₉·2H₂O (1) and [Fe(bipy)₃]₂[Sn₃Se₇]₂·bipy·2H₂O (2) (bipy = bipyridine) were prepared by the reactions of Sn, Se, FeCl₂·4H₂O, bipy, and dien with/without KSCN under hydrothermal conditions (dien = diethylenetriamine). In 1, four SnSe₅ units condense via edge sharing to form the novel 3-D framework selenidostannate (∞)³[Sn₄Se₉²⁻] containing an interpenetrating channel system. The [Fe(bipy)₃]²⁺ cations are accommodated in the different channels according to the conformation of the [Fe(bipy)₃]²⁺ cation. In 2, three SnSe₅ units share edges to form a 2-D (∞)²[Sn₃Se₇²⁻] layered anion, while two SnSe₅ units and one SnSe₄ unit are connected via edge sharing, forming a 1-D (∞)¹[Sn₃Se₇²⁻] chainlike anion. The (∞)¹[Sn₃Se₇²⁻], [Fe(bipy)₃]²⁺, bipy, and H₂O species are embedded between the (∞)²[Sn₃Se₇²⁻] layers. 2 is the first example of a selenidostannate constructed by both (∞)²[Sn₃Se₇²⁻]and (∞)¹[Sn₃Se₇²⁻] anions. The coexistence of 1-D (∞)¹[Sn₃Se₇²⁻] and 2-D (∞)²[Sn₃Se₇²⁻] anions in 2 might support the possible reaction mechanism that the (∞)²[Sn₃Se₇²⁻] anions are formed by condensation of the (∞)¹[Sn₃Se₇²⁻] chains. 1 and 2 exhibit band gaps at 1.43 and 2.01 eV, respectively.

Novel iodoargentates [Mn(4,4′-bpy)(DMF)3(H2O)] Ag5I7·4,4′-bpy (1), [Mn(4,4′-bpy)(DMSO)4]2Ag11I15 (2), [Mn(4,4′-bpy)2(DMSO)2(H2O)2]Ag10I12·2DMSO·2H2O (3) and [Mn2(4,4′-bpy)2(DMF)5(DMSO)2(H2O)]Ag10I14·2DMF (4) were prepared, templated by solvated [Mn(4,4′-bpy)]2+ cations.

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The selenidostannates [Mn(dien) 2 ]Sn 3 Se 7 ·0.5H 2 O (1), [Fe(tatda)]Sn 3 Se 7 (2), and [Mn(dien) 2 ] 2 Sn 2 Se 6 (3) (dien = diethylenetriamine, tatda = 3,6,9,12-tetraazatetradecane-1,14-diamine) were prepared under solvothermal conditions. In compounds 1 and 2, the six Sn 3 Se 4 semi-cubes are bridged by double μ 2 -Se atoms to form the [Sn 3 Se 72-] n lamellar anion containing a elliptical 24-membered Sn 12 Se 12 ring, which show conformational flexibility of the 2D [Sn 3 Se 7 2-] n anion influenced by the counter cation. The [Mn(dien) 2 ] 2+