Citation: Chen Guanghui, He Yanping, Zhang Lei, Zhang Jian. Syntheses and Structural Studies of a Series of Ti₄(embonate)₆-based Complexes[J]. Acta Chimica Sinica, ;2020, 78(12): 1411-1417. doi: 10.6023/A20070337 shu

Syntheses and Structural Studies of a Series of Ti₄(embonate)₆-based Complexes

Chen Guanghui ^a,b ,
He Yanping ^a,, ,
Zhang Lei ^a ,
Zhang Jian ^a,,

a.
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China
b.
College of Materials Science and Engineering, Guilin University of Technology, Guilin 541004, China

Corresponding author: He Yanping, hyp041@163.com Zhang Jian, zhj@fjirsm.ac.cn
Received Date: 31 July 2020
Available Online: 6 August 2020
Fund Project: Project supported by the National Natural Science Foundation of China (No.21935010)the National Natural Science Foundation of China 21935010

Figures(6)

Metal-organic cages (MOCs) as a new type of molecular containers have attracted great interest because of their special cavities and wide applications in molecule recognition and separation, drug delivery and catalysis, etc. However, in the past decades, most researchers just devote to constructing discrete MOCs with special functions. Since many cage compounds are not soluble and stable in the solvent, the further assembly of cages into advanced materials is relatively less developed. In our previous study, we reported a water-soluble and ultrastable Ti₄L₆ (L=embonate) tetrahedron with coordination assembly function, which has been applied as the starting material to realize coordination assembly with different metal ions through two-step reaction. In this work, by employing the Ti₄L₆ cages to assemble with Mn²⁺, Nd³⁺, Ba²⁺ and Ca²⁺ ions, respectively, a series of Ti₄L₆-based complexes have been synthesized under different solvothermal reaction conditions, namely, (Me₂NH₂)₉(Me₄N)[Mn₃(Ti₄L₆)₂(H₂O)₉(DMF)₆]·Guests (PTC-241, DMF=N, N-dimethylformamide); (Me₂NH₂)₅- [Nd(Ti₄L₆)(H₂O)₂(DMF)₅]·Guests (PTC-242); (Me₂NH₂)₂[Ba₄(Ti₄L₆)(OH)₂(H₂O)₈(TEA)₅]·Guests (PTC-243, TEA=Triethanolamine); (Me₂NH₂)₂[Ca₃(Ti₄L₆)(H₂O)₈(DEA)₂]·Guests (PTC-242, DEA=Diethanolamine); (Me₂NH₂)₂[Ca₃(Ti₄L₆)-(H₂O)₁₅]·Guests (PTC-245). Their structures were characterized by X-ray single crystal diffraction, thermo gravimetric analyzer (TGA), infrared spectroscopy (IR) and powder X-ray diffraction (PXRD). Single-crystal analysis reveals that PTC-241 is a supramolecular homochiral architecture formed by the staggered accumulation of ΔΔΔΔ-[Ti₄L₆] and ΔΔΔΔ-[Ti₄L₆]-Mn₃ cages by weak interactions (such as hydrogen bonding and π-π stacking). PTC-242 is also a supramolecular structure, in which the Ti₄L₆-Nd cages are linked by (Me₂NH₂)⁺ cations and ethanediamine (en) molecules via the weak N-H…O hydrogen bonding force, giving rise to a 3D H-bonding framework with a honeycomb lattice of hexagonal channels along the b axis. PTC-243 is a linear Ti₄L₆-Ba₄ chain structure. Both PTC-242 and PTC-245 are two-dimensional (2D) Ti₄L₆-Ca₃ layers with honeycomb-like structures. In addition, we also investigated the fluorescent properties of PTC-242 and PTC-245 in the solid state, and the results show that both of them display strong emitting bands in the visible region.
- titanium-organic cage,
- stepwise assembly,
- synthesis,
- crystal structure
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Syntheses and Structural Studies of a Series of Ti₄(embonate)₆-based Complexes