Diverse Closed Cavities in Condensed Rare Earth Metal–Chalcogenide Matrixes: Cs[Lu₇Q₁₁] and (ClCs₆)[RE₂₁Q₃₄] (RE = Dy, Ho; Q = S, Se, Te)

Abstract

Two types of novel ordered chalcogenids Cs[Lu 7 Q 11 ] (Q = S, Se) and (ClCs 6 )[RE 21 Q 34 ] (RE = Dy, Ho; Q = S, Se, Te) were discovered by high-temperature solid state reactions. The structures were characterized by single-crystal X-ray diffraction data. Cs[Lu 7 Q 11 ] crystallize in the orthorhombic Cmca (no. 64) with a = 15.228(4)−15.849(7) Å, b = 13.357(3)−13.858(6) Å, c = 18.777(5)−19.509(8) Å, and Z = 8. (ClCs 6 )[RE 21 Q 34 ] crystallize in the monoclinic C2/m (no. 12) with a = 17.127(2)−18.868(2) Å, b = 19.489(2)− 21.578(9) Å, c = 12.988(9)−14.356(2) Å, β = 128.604(2)−128.738( 4)°, and Z = 2. Both types of compounds feature 3D RE−Q network structures that embed with dual tricapped cubes Cs 2 @Se 18 in the former or unprecedented matryoshka nesting doll structure cavities of (ClCs 6 )@Se 32 in the latter. The band gap, band structure, as well as a structure change trend of the majority of A/RE/Q compounds are presented.

[Cs6Cl][Fe24Se26]: A Host–Guest Compound with Unique Fe–Se Topology

“…Here the corresponding separation is 3.26 o na verage ( Figure 2d). This is almosti dentical to the CsÀCl separation in the host-guest compound [Cs 6 Cl][RE 21 Ch 34 ] (RE = Dy,H o, Ch = S, Se, Te )o f3 .27 , [22] in whicht he charges add up properly with only RE + 3 .M oreover,C lw as identified in fitting relative amounts, as estimated from EDX data. Thus, am inor iron deficiency in the title compound is the most probablee xplanation,b ut cannotb eu nambiguously resolved with the diffraction data at hand.…”

Supercubooctahedron (Cs6Cl)2Cs5[Ga15Ge9Se48] Exhibiting Both Cation and Anion Exchange

“…The CsÀ Cl distances ranging from 3.399(3) to 3.474(3) c oincide with the normal ionic CsÀld istance. [24] The Cs···Se distances, which lie in the range of 3.608(1) to 4.140 (1) , are similart ot hose in related selenides:3 .571(3)-4.130(3) i nC s 3 AsGeSe 5…”

“…Compound 1 crystallizes in tetragonal space group I4/m andf eatures unprecedented discrete supercubooctahedra [M 24 Se 48 ] 15À (M = Ga/Ge), which are well separated by (Cs 6 Cl) 5 + complex cations and isolated Cs + cations. (Figure 1a) The supercubooctahedral [M 24 Se 48 ] 15À (M = Ga/Ge) cluster consists of 72 atoms, has an edge length of about 10.8 (Figure 1b), and contains 17 atoms more than the T4-[M 20 Q 35 ]c luster.…”

“…Compound 1 crystallizes in tetragonal space group I4/m andf eatures unprecedented discrete supercubooctahedra [M 24 Se 48 ] 15À (M = Ga/Ge), which are well separated by (Cs 6 Cl) 5 + complex cations and isolated Cs + cations. (Figure 1a) The supercubooctahedral [M 24 Se 48 ] 15À (M = Ga/Ge) cluster consists of 72 atoms, has an edge length of about 10.8 (Figure 1b), and contains 17 atoms more than the T4-[M 20 Q 35 ]c luster. [8] Each of the eight vertices is in fact an M 3 Se 9 SBU, which is linked to the neighboring vertex through sharing SeÀSe edges,a nd such an M 3 Se 9 unit is commonly regarded as aT 2 cluster without ac orner,a so bserved in Na 2Àx Ga 2Àx Sn 1 + x Se, [19] NaBa 4 Ge 3 S 10 Cl, [20] and( BMMIm) 24 [Sn 36 Ge 24 Se 132 ].…”

“…(Figure 1a) The supercubooctahedral [M 24 Se 48 ] 15À (M = Ga/Ge) cluster consists of 72 atoms, has an edge length of about 10.8 (Figure 1b), and contains 17 atoms more than the T4-[M 20 Q 35 ]c luster. [8] Each of the eight vertices is in fact an M 3 Se 9 SBU, which is linked to the neighboring vertex through sharing SeÀSe edges,a nd such an M 3 Se 9 unit is commonly regarded as aT 2 cluster without ac orner,a so bserved in Na 2Àx Ga 2Àx Sn 1 + x Se, [19] NaBa 4 Ge 3 S 10 Cl, [20] and( BMMIm) 24 [Sn 36 Ge 24 Se 132 ]. [21] In complete contrastt ot he normalT n ,P n ,o rC nclusters, [8] such as upercu- Figure S5) are comparable to the GaÀSe bond length in K 2 CuGa 3 Se 6 (2.374(1)-2.432(1) ) [22] and GeÀSe bond length in K 2 EuGeSe 5 (2.339(2)-2.408(1) ).…”