In situ amination and side group effect of multifunctional heterocyclic thione ligand toward discrete and polymeric cluster constructionsElectronic supplementary information (ESI) available: Fig. S1S5, PXRD pattern for 13 (Fig. S6S8), 1H NMR spectra of 1 and 2 (Fig. S9 and S10) and UV-Vis spectra of reaction medium in the formation of 1. CCDC 919307919309 for 13. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c3dt50165e

• Main Authors: Hu, Sheng, Yu, Fang-Yong, Zhang, Peng, Lin, Dian-Rong
• Format: Article
• Language: English
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/c3dt50165e

Three metal complexes [Cu I 6 (atdm) 6 ] ( 1 ), [Cu I (Hatd)(H 2 atd)] ( 2 ) and [H 3 O][Co II 4 Co III 2 Cl 3 (atd) 6 ]H 2 O ( 3 ) [atdm = 4-dimethylamino-6-anilino-1,3,5-triazine-2-thiolate, H 2 atd = 6-anilino-1,3,5-triazine-2,4-dithiol, atdH 2 = 6-anilino-1,3,5-triazine-2,4(1 H ,3 H )-dithione] have been solvothermally synthesized. The luminescent complexes 1 and 2 provide remarkable structural diversity depending on different reaction solutions. Complex 1 consists of a discrete pseudohexagonal prismatic [Cu 6 S 6 ] core that can be described as two stacked, chair-shaped [Cu 3 S 3 ] rings bound together by the CN bridges of the atdm ligands, in which the atdm ligand was generated via in situ amination of H 2 atd in the presence of DMF solution. Whereas complex 2 is a 2D (4,4) net based on single node Cu I ions crystallized in acetonitrile, in which H 2 atd ligands exist in the thione form atdH 2 and the partially deprotonated form atdH. Complex 3 has a two-fold interpenetrated (10,3)- a topological network based on unprecedented cobalt-centered trigonal-bipyramidal [Co 6 (atd) 6 ] building blocks, linked by Cl double-bridges and showing oriented effects of aniline side groups. IR spectra, elemental analyses and XRD analyses confirmed the phase-purities of the as-synthesized complexes. The photoluminescence properties of 1 and 2 in the solid state and the magnetic properties of 3 are investigated. A discussion of the crystal structures, as well as the coordination properties of the multifunctional sulfur-containing ligands upon different geometries of the central units, is also provided. The unexpectedly in situ aminated ligand reaction and side group effect of a multifunctional heterocyclic thione ligand lead to two luminescent copper and one cobalt complexes with special cluster SBUs.