Synthesis, Structure and Coordination Self-Assembly of Azacalix[4-n] pyridine[n] pyrazi nes （n=1 -- 3）  

作　　者：Jincheng Wu Liang Zhao Dexian Wang Meixiang Wang 

机构地区：[1]Key Laboratory of Bioorganic Phosphorus Chemistry & Chemical Biology (Ministry of Education), Department of Chemistry, Tsinghua University, Beijing 100084, China [2]Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China

出　　处：《Chinese Journal of Chemistry》2013年第5期589-597,共9页中国化学（英文版）

基　　金：Financial support by the National Natural Science Foundation of China，the National Basic Research Program of China (973 program,2011CB932501 and 2013CB834501) is gratefully acknowledged.This work is also supported by Tsinghua University Initiative Scientific Research Program

摘　　要：We herein report the synthesis and metal-directed coordination self-assembly behaviors of three new macrocyc- lic azacalix[4]aromatics that comprise various numbers of pyridine and pyrazine rings bridged by N-CH3 groups. Structural characterization of 1--3 explored that their conformations are fluxional in solution and each adopts a 1,3-alternate configuration in crystalline solids. The macrocyclic skeletons in azacalixaromatic 1--3 afford a good platform to designedly arrange coordination sites in a unique way relative to conventional multidentate ligands. Solid-state structures of three coordination self-assembled silver complexes （13--15） of 1 --3 determined by X-ray crystallography suggest that the nitrogen atoms on procumbent aromatics have better coordination ability than those on perpendicular aromatics and dictate the whole coordination self-assemblies. Unique discrete and 1D chain-like structures were thus obtained. This system may afford a deeper insight into the coordination self-assembly studies of heteroatom-bridged calixaromatics, possibly extending potential application of this novel macrocyclic polyden- tate organic compounds in the synthesis of functional metal organic framework formation.We herein report the synthesis and metal-directed coordination self-assembly behaviors of three new macrocyc- lic azacalix[4]aromatics that comprise various numbers of pyridine and pyrazine rings bridged by N-CH3 groups. Structural characterization of 1--3 explored that their conformations are fluxional in solution and each adopts a 1,3-alternate configuration in crystalline solids. The macrocyclic skeletons in azacalixaromatic 1--3 afford a good platform to designedly arrange coordination sites in a unique way relative to conventional multidentate ligands. Solid-state structures of three coordination self-assembled silver complexes （13--15） of 1 --3 determined by X-ray crystallography suggest that the nitrogen atoms on procumbent aromatics have better coordination ability than those on perpendicular aromatics and dictate the whole coordination self-assemblies. Unique discrete and 1D chain-like structures were thus obtained. This system may afford a deeper insight into the coordination self-assembly studies of heteroatom-bridged calixaromatics, possibly extending potential application of this novel macrocyclic polyden- tate organic compounds in the synthesis of functional metal organic framework formation.

关 键 词：CALIXARENES coordination networks SELF-ASSEMBLY MACROCYCLIC PYRAZINE 

分 类 号：O633[理学—高分子化学] TQ463.54[理学—化学]