DABCO-induced self-assembly of a trisporphyrin double-decker cage:: Thermodynamic characterization and guest recognition

被引:86
作者
Ballester, P [1 ]
Oliva, AI
Costa, A
Deyà, PM
Frontera, A
Gomila, RM
Hunter, CA
机构
[1] ICREA, Tarragona 43007, Spain
[2] Inst Chem Res Catalonia ICIQ, Tarragona 43007, Spain
[3] Univ Illes Balears, Dept Quim, Palma de Mallorca 07122, Spain
[4] Univ Sheffield, Ctr Chem Biol, Krebs Inst Biomolec Res, Dept Chem, Sheffield S3 7HF, S Yorkshire, England
关键词
D O I
10.1021/ja060608t
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
This paper describes the thermodynamic characterization of the self-assembly of a Zn trisporphyrin induced by coordination with 1,4-diazabicyclo[2.2.2]octane (DABCO) to form a stable 2:3 double-decker molecular coordination cage that recognizes benzene- 1, 3,5-tricarboxamides. The self-assembly process has been studied using UV-vis and (1)H NIVIR spectroscopy and quantitatively characterized in terms of a single stability constant that describes the strength of the individual coordination interactions and two effective molarities (EM) that describe the additional stability imparted by intramolecular cyclization. The EM values of the two consecutive cyclic intramolecular interactions are very similar. At micromolar concentrations, the formation of the fully assembled coordination cage is highly favored over the formation of intermediate species stabilized by fewer interactions, and so self-assembly is an all-or-nothing process. In contrast, at millimolar concentrations, the relative stability of intermediate species increases, leading to a stepwise self-assembly process, and a 2:2 intermediate can be clearly identified using (1)H NIVIR spectroscopy. The molecular recognition of benzene-1,3,5-tricarboxam ides by the cage was investigated using (1)H NMR spectroscopy. The tricarboxamides bind inside the central cavity of the cage complex, and isothermal titration calorimetry (ITC) allowed the quantification of the stoichiometry and binding affinities.
引用
收藏
页码:5560 / 5569
页数:10
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