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Syntheses of Macrocyclic Compounds Possessing Fluorine Atoms in Their Cavities: Structures and Complexation with Cations
Author(s) -
Takemura Hiroyuki,
Kariyazono Hiroyuki,
Yasutake Mikio,
Kon Noriyoshi,
Tani Keita,
Sako Katsuya,
Shinmyozu Teruo,
Inazu Takahiko
Publication year - 2000
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/(sici)1099-0690(200001)2000:1<141::aid-ejoc141>3.0.co;2-n
Subject(s) - chemistry , fluorine , picrate , crystallography , molecule , octahedron , ion , crystal structure , fluorine 19 nmr , inorganic chemistry , nuclear magnetic resonance spectroscopy , stereochemistry , organic chemistry
Novel fluorine‐containing macrocyclic molecules have been synthesized in order to clarify the interaction or coordination ability of the C‐F unit towards metal ions. The cage compounds 1 and 2 were prepared by direct coupling reactions between the appropriate diamines and dibromides, while bond isomers of the cage compounds were synthesized via fluorinated diaza[3.3]metacyclophanes. Complex formation with alkali metal cations, NH 4 + , and Ag + ions has been assessed by picrate extraction experiments. Comparison of the cation affinities of hosts 1 , 2 , and 4 , shows that the spatial arrangement of the fluorine atoms strongly affects the donor ability of the host molecules. The hexafluoro cage compound 1 , with six fluorine atoms in an octahedral geometry, exhibits relatively strong coordination ability towards K + , NH 4 + , and Ag + ions, while compound 2 , with four fluorine atoms in a structure similar to that of 1 shows only poor affinity for these ions. Compound 4 , which has six fluorine atoms arranged in a quasi planar fashion, was found to show weak affinity towards NH 4 + and Ag + ions. Thus, octahedrally arranged fluorine atoms evidently provide the best fit for spherical cations. Compound 1 shows characteristic 1 H‐, 13 C‐, and 19 F‐NMR‐spectral changes upon complexation. The crystal structure of 1 has been elucidated and compared to that of the K + complex. The C‐F bonds are found to be slightly elongated in the K + complex, which is clearly indicative of coordination of the fluorine atom to K + .