Synthesis, Structure and Bonding, Optical Properties of Ba₄MTrQ₆ (M=Cu, Ag; Tr=Ga, In; Q=S, Se)

Abstract

Four new quaternary chalcogenides, Ba4AgGaS6 (1), Ba4AgGaSe6 (2), Ba4CuInS6 (3), and Ba4AgInS6 (4), were synthesized by solid-state reactions and their structures were characterized through single-crystal X-ray diffraction. In spite of their similar chemical compositions, the flexible arrangement between the transition metals and the triel atoms leads to subtle differences in their polyanion structures. All structures feature similar [MTrQ6](8-) 1D polyanionic chains (M=Cu, Ag; Tr=Ga, In; Q=S, Se), which are constructed from corner-sharing MQ4 or TrQ4 tetrahedra. However, the transition metals and triels are mixed in 1, 2, and 3, but they occupy independent crystallographic sites in 4. As a result, compounds 1-3 belong to the known Ba2CoS3 (Pnma No. 62) or Ba2 MnS3 (Pnma No. 62) class, whereas 4 crystallizes in its own structural type within the monoclinic P2₁/c (No. 14) space group. The structural relationship among these new phases was also studied with the aid of DFT calculations and related optical properties are presented as well.

Solvothermal Syntheses and Characterizations of Four Quaternary Copper Sulfides BaCu3MS4 (M = In, Ga) and BaCu2MS4 (M = Sn, Ge)

“…In the structure, both of Cu(1) and Cu(2) atoms adopt tetrahedral coordination, with a Cu–S bond range of 2.3388(15) to 2.4584(17) Å, and Ga(1) atom takes tetrahedral coordination with a small range Ga–S bond of 2.2920(15) to 2.3016(15) Å. These bond length values are consistent with those in the literature. , …”

“…The changes of their polymerization behaviors greatly increase the opportunities to generate new compounds. , On the other hand, alkaline earth metal ions possess higher charge density and smaller size comparing with alkali metal ions, which endow them to direct dense anionic frameworks with high negative charge density. Therefore, quaternary sulfides containing alkaline earth metal ions have much better stabilities than their analogs of alkali metal ions. , Up to now, alkaline earth metal quaternary sulfides were mainly synthesized under harsh conditions. − Johrendt and his co-worker synthesized BaCu 6 Ge 2 S 8 by the direct reaction of corresponding elements at 750 °C . These quaternary sulfides have exhibited interesting properties, such as thermoelectric, semiconductor, and photovoltaic properties, which have intriguing application prospects. ,, The harsh conditions of the synthetic method reduce the opportunities to obtain new phases, and the number of quaternary sulfides is greatly limited.…”

“…Therefore, quaternary sulfides containing alkaline earth metal ions have much better stabilities than their analogs of alkali metal ions. , Up to now, alkaline earth metal quaternary sulfides were mainly synthesized under harsh conditions. − Johrendt and his co-worker synthesized BaCu 6 Ge 2 S 8 by the direct reaction of corresponding elements at 750 °C . These quaternary sulfides have exhibited interesting properties, such as thermoelectric, semiconductor, and photovoltaic properties, which have intriguing application prospects. ,, The harsh conditions of the synthetic method reduce the opportunities to obtain new phases, and the number of quaternary sulfides is greatly limited. Therefore, it is necessary to develop mild synthetic routes for the syntheses of such materials.…”

LiBa2MIIIQ4 (MIII = Al, Ga, In; Q = S, Se): A Series of Metal Chalcogenides with a Structural Transition

“…In LiBa 4 Ga 5 Se 12 and CuBa 4 Ga 5 Q 12 , their structures exhibit complex 3D networks composed of corner-sharing M III Q 4 tetrahedra (Figure ). − The results show that the M III /Ba atomic ratio plays an important role in determining the dimension of the M III –Q frame in the Ba- and M III -based chalcogenides. On the basis of the statistical analysis in Figure and Table S4, we can see that the compounds with “0D isolated” M III Q 4 tetrahedra show a M III /Ba ratio smaller than 1.…”

An Unusual Metal Chalcogenide Zeolitic Framework Built from the Extended Spiro-5 Units with Supertetrahedral Clusters as Nodes

“… Unfortunately, the diversity of such structures is limited by the types of alkali-metal species. To maintain the various organic amines as templates for the construction of zeolitic networks with the extended 3-ring composed of a big-sized T n cluster, a feasible strategy is to decrease the negative charge of T n clusters by introducing high-valent metal-like Ge 4+ and Sn 4+ . − In this way, the extended 3-ring can be built in organically templated metal chalcogenides by larger-sized T n clusters, such as T3 and T4. Unfortunately, these extended 3-rings still prefer to fuse together into supersupertetrahedral cluster T p , q (four T p supertetrahedral clusters assembled into a self-closed T q cluster), ,, instead of the extended spiro-5 units.…”