New molecular receptors with cyclophosphazene subunits: Synthesis, reactivity, and structure-property relationships

被引:17
作者
Brandt, K
Porwolik-Czomperlik, I
Siwy, M
Kupka, T
Shaw, RA
Davies, DB
Bartsch, RA
机构
[1] Polish Acad Sci, Inst Polymer Chem, PL-41800 Zabrze, Poland
[2] Univ London Birkbeck Coll, Dept Chem, London WC1H 0PP, England
[3] Texas Tech Univ, Dept Chem & Biochem, Lubbock, TX 79409 USA
关键词
P-pivot lariat ethers; synthesis; nucleophilic substitution; metal ion complexation; molecular receptors;
D O I
10.1023/A:1008155200984
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
A series of hydrophopic (2 and 3) and new hydrophilic (4-7) molecular receptors of the PNP-lariat ether with tetra-substituted cyclotriphosphazene subunits have been prepared by the complete nucleophilic substitution of chlorine atoms in the reactive PNP-crown precursor 1 with the respective sodium cation-paired oxyanions (phenoxy --> 2, beta-naphthoxy --> 3, and methoxytrioxyethylenoxy --> 4) and aliphatic amines (n-propylamine --> 5 aziridine --> 6, and pyrrolidine --> 7). Their structures were established by MS and P-31 NMR spectroscopy and their metal ion complexing properties tested by a TLC method. Comparison of the complexation behaviour for ligands 1-7 shows that the affinity for particular cations is strongly substituent-dependent and, in general, is significantly enhanced by cooperation of the side arm donor atoms (O or N) with the parent PNP-crown structure in the binding process. The remarkable affinity of some ligands for selected cations, in particular lithium, cesium, and silver ions, is interpreted in terms of structure-property relationships.
引用
收藏
页码:281 / 289
页数:9
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