A series of new lanthanoid thioantimonates: a rare example of organic-decorated cationic lanthanoid thioantimonate chains based on asymmetric dinuclear lanthanide complexes

作者：Zhou, Jian^*; An, Litao; Hu, Feilong; Liu, Xing; Zhao, Rongqing; Lin, Jianwu

来源：CrystEngComm, 2012, 14(17): 5544-5551.

DOI：10.1039/c2ce25680k

• TRANSITION-METAL-COMPLEXES
• STRUCTURE-DIRECTING AGENTS
• SOLVOTHERMAL SYNTHESIS
• CRYSTAL-STRUCTURES
• THERMAL-STABILITY
• 1ST EXAMPLE
• ANTIMONY SULFIDES
• LAYERED THIOANTIMONATE(III)
• HYDROTHERMAL SYNTHESIS
• CHELATING LIGAND

A series of new lanthanoid thioantimonates [Ln(teta)(2)]SbS4 [teta = triethylenetetramine; Ln = Eu (1), Gd (2), Er (3)], {[Ln(tepa)](2)[mu(2)-(SbS3)-S-III](mu(2)-OH)}(2){[Ln(tepa)](2)(mu(2)-OH)(2)((SbS4)-S-V)(2)}Cl-2 [tepa = tetraethylene-pentamine; Ln = Y(4), Eu(5), Er(6)], and [Gd-2(tepa)(2)(mu(2)-OH)(2)(mu(2)-SbS4)]Cl center dot 0.25H(2)O (7) were synthesized via reactions of Sb, S and LnCl(3) in teta or tepa under solvothermal conditions and were structurally characterized. Compounds 1-3 consist of isolated [Ln(teta)(4)](3+) cations and tetrahedral [SbS4](3-) anions. Compounds 4-6 contain heterometallic mixed amino-thiocluster cations {[Ln(tepa)](2)[mu(2)-SbS3](mu(2)-OH)}(2+), heterometallic anions {[Ln(2)(tepa)(2)(mu(2)-OH)(2)](SbS4)(2)}(2-) and free Cl- ions, which provide a rare example of the coexistence of noncondensed pyramidal [(SbS3)-S-III](3-) and tetrahedral [(SbS4)-S-V](3-) anions in a single thioantimonate. 7 consists of a 1-D polymeric cation [Gd-2(tepa)(2)(mu(2)-OH)(2)(mu(2)-SbS4)](+), constructed through the linkage of asymmetric dinuclear gadolinium complex [Gd-2(tepa)(2)(mu(2)-OH)(2)](4+) cations, tetrahedral [(SbS4)-S-V](3-) anions and a Cl- ion and water molecule, which represents a rare example of organic-decorated cationic lanthanoid thioantimonate chains based on asymmetric dinuclear lanthanide complexes. The present compounds exhibit semiconducting properties with absorption band edges between 2.00 and 3.03 eV.

• 出版日期2012
• 单位重庆师范大学; 玉林师范学院; 淮阴师范学院