Macrocyclic Amines as Structure-Directing Agents for the Synthesis of Three-Dimensional Antimony-Sulfide Frameworks

Abstract

A new family of antimony sulfides, incorporating the macrocyclic tetramine 1,4,8,11-tetraazacyclotetradecane (cyclam), has been prepared by a hydrothermal method. [C10N4H26][Sb4S7] (1), [Ni(C10N4H24)][Sb4S7] (2), and [Co(C10N4H24)]x[C10N4H26](1-x)[Sb4S7] (0.08 < or = x < or = 0.74) (3) have been characterized by single-crystal X-ray diffraction, elemental analysis, thermogravimetry, and analytical electron microscopy. All three materials possess the same novel three-dimensional Sb4S7(2-) framework, constructed from layers of parallel arrays of Sb4S8(4-) chains stacked at 90 degrees to one another. In 1, doubly protonated macrocyclic cations reside in the channel structure of the antimony-sulfide framework. In 2 and 3, the cyclam acts as a ligand, chelating the divalent transition-metal cation. Analytical and X-ray diffraction data indicate that the level of metal incorporation in 2 is effectively complete, whereas in 3, both metalated and nonmetalated forms of the macrocycle coexist within the structure.

Solvothermal Synthesis, Crystal Structures, and Photocatalytic Properties of Iodoplumbate Hybrids with Nickel(II) Complex Templates

“…The Ni 2+ ion is in a lightly distorted squared environment, as is evidenced by the trans N–Ni–N angle of 178.8(5)° and the cis N–Ni–N angles in the range of 85.6(7)–93.5(5)° (Table S7). The Ni–N bond lengths vary in the ranges of 1.977(13)–1.988(13) Å (Table S7), which are in accordant with values observed on the compound containing complex cation [Ni(cyclam)] 2+ (cyclam = 1,4,8,11‐tetraazacyclotetradecane) (Ni‐N: 1.947(6), 1.952(6) Å] . Pb(1) and Pb(2) are coordinated to six I – anions forming PbI 6 PBUs.…”

Effect of lanthanide contraction on the Ln/Sb/Se/dien system: solvothermal syntheses and characterizations of lanthanide(III)-selenidoantimonate complexes with diethylenetriamine as a co-ligand

“…The Se-Sb-Se angles of SbSe 3À 4 are 105.56(3)-113.14 (3)°for 3 and 105.39(4)-113.25(4)°for 4 (table 3), indicating that the SbSe 4 tetrahedron is less distorted than those in 1 and 2. Both Sm 3+ and Gd 3+ are eight coordinates involving six nitrogens of two dien and two Se of η 2 -SbSe 4 to form distorted bicapped trigonal prisms, with Se(1), N(1), and N(3) forming a face and Se (2), N(4), and N(5) forming the opposite face in 3. The capping positions are occupied by N(2) and N(6) ( figure 4(b)).…”

“…Ternary chalcogenidometalates have received attention due to their potential applications in optical and electrical materials [1][2][3][4][5][6]. [15], and [Ni(aepa) 2 ] 3 Sb 6 S 12 , [Ni(aepa) 2 ]Sb 4 S 7 (aepa = N-(aminoethyl)-1,3-propandiamine) [16], as recent examples.…”

The Effect of Temperature onto the Crystal Structure of Thioantimonates: Solvothermal Syntheses and Crystal Structures of [Co(dien)2][Co(tren)SbS4]2·0.5H2O and {[Co(tren)]2[CoSb2S6]}·H2O

“…A challenge in the field of thioantimonate chemistry is the integration of transition metal ions into the thioantimonate networks. Using mono-, bi-or tridentate amine molecules like methylamine, ethylenediamine or diethylenetriamine (dien) mainly transition metal complexes are formed which are separated from the anionic network [25][26][27][28][29][30][31][32][33][34][35][36][37][38]. Exceptions are the chalcophilic cations Cu + and Ag + which easily form bonds to the S atoms of thioantimonate anions [39][40][41][42][43][44][45].…”