In situ hydrothermal synthesis of a twofold entangled coordination network based on tetranuclear zinc(II) clusters: An experimental and theoretical study

• Published in: Inorganica Chimica Acta 2013-08, Vol.405, p.302-308
• Main Authors: Huang, Rong-Yi, Xue, Chen, Wang, Zhu-Qinq, Xu, Heng, Wu, Gen-Hua, Ye, Shi-Yong
• Format: Article
• Language: English
• Subjects: Crystal structure; Homometallic cluster; In situ ligand synthesis; Luminescent property; Quantum chemical calculation; Tetrazole
• ISSN: 0020-1693; 1873-3255
• DOI: 10.1016/j.ica.2013.06.024

A novel zinc(II) coordination polymer containing tetranuclear zinc(II) clusters based on a simultaneous in situ and self-assembly reaction under the hydrothermal condition. Complex 1 presents a fascinating 2D entangled (4,4) topology network with both polyrotaxane and polycatenane characters. The obtained complex exhibits a strong green luminescent emission. [Display omitted] •A zinc(II) tetrazole-based complex has been synthesized via in situ hydrothermal reaction.•The complex shows a twofold entangled (4, 4) topology network based on Zn4 clusters.•An unusual polyrotaxane and polycatenane characters in complex have been obtained.•The nature of coordinate bonds in complex was further investigated by DFT/B3LYP.•The complex shows a strong green emission originating from interligand charge transition. A new 2D coordination polymer, Zn2(OH)(SDBA)(PTZ) (1), (H2SDBA=4,4′-dicarboxybiphenyl sulfone, PTZ=5-(4-pyridyl)tetrazolate) was synthesized via in situ hydrothermal reaction of zinc(II) salt, NaN3, 4-cyanopyridine and H2SDBA, and characterized by elemental analysis, IR, X-ray powder diffraction (XPRD) and single crystal X-ray diffraction. The structure of complex 1 shows a 2D twofold entangled network with (4, 4) topology based on the tetranuclear zinc(II) clusters, which contains unusual both polyrotaxane and polycatenane characters, and further forms a 3D supramolecular architecture by weak π⋯π stacking interactions. Meanwhile, the nature of coordinate bonds in complex 1 has been deeply investigated by high level theoretical calculations. The result of theoretical computation indicates that all coordinate bonds are basically intermediate and covalent dominant interactions in complex 1, and complex 1 has the high thermal stability, which coincides with the result of thermogravimetric analysis (TGA) of complex 1. The photoluminescent property of complex 1 has also been investigated in the solid state at ambient temperature.