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

Two types of novel ordered chalcogenids Cs[Lu(7)Q(11)] (Q = S, Se) and (ClCs6)[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) angstrom, b = 13.357(3)-13.858(6) angstrom, c = 18.777(5)-19.509(8) angstrom, and Z = 8. (ClCs6)[RE(21)Q(34)] crystallize in the monoclinic C2/m (no. 12) with a = 17.127(2)-18.868(2) angstrom, b = 19.489(2)-21.578(9) angstrom, c = 12.988(9)-14.356(2) angstrom, beta = 128.604(2)-128.738(4)degrees, 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 (ClCs6)@Se-32 in the latter. The band change trend of the majority of A/RE/Q compounds are presented.