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

doi:10.6023/A20070337

Acta Chimica Sinica ›› 2020, Vol. 78 ›› Issue (12): 1411-1417.DOI: 10.6023/A20070337 Previous Articles Next Articles

Article

系列Ti₄L₆-笼基配合物的合成与结构研究

陈光辉^a,b, 何燕萍^a, 张磊^a, 张健^a

a 中国科学院福建物质结构研究所结构化学国家重点实验室福州 350002;
b 桂林理工大学材料科学与工程学院桂林 541004

投稿日期:2020-07-31 发布日期:2020-08-11
通讯作者: 何燕萍, 张健 E-mail:hyp041@163.com;zhj@fjirsm.ac.cn
基金资助:
项目受国家自然科学基金（No.21935010）资助.

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

Received:2020-07-31 Published:2020-08-11
Supported by:
Project supported by the National Natural Science Foundation of China (No. 21935010).

1. Supporting Information-A20070337.pdf(1823KB)

Abstract

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-244, 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-244 and PTC-245 are two-dimensional (2D) Ti₄L₆-Ca₃ layers with honeycomb-like structures. In addition, we also investigated the fluorescent properties of PTC-244 and PTC-245 in the solid state, and the results show that both of them display strong emitting bands in the visible region.

Key words: titanium-organic cage, stepwise assembly, synthesis, crystal structure

Cite this article

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.

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系列Ti₄L₆-笼基配合物的合成与结构研究

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

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系列Ti4L6-笼基配合物的合成与结构研究