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Metal ion complexation by tetraester derivatives of bridged calix [4] arenes
Author(s) -
Arnaudneu Francoise,
Böhmer Volker,
Guerra Lourdes,
McKervey M. Anthony,
Paulus Erich F.,
Rodriguez Amado,
Schwingweill MarieJosé,
Tabatabai Moniralsadat,
Vogt Walter
Publication year - 1992
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.610050809
Subject(s) - chemistry , calixarene , ethyl bromoacetate , methylene , potentiometric titration , monoclinic crystal system , methylene bridge , medicinal chemistry , metal , derivative (finance) , potassium , crystallography , crystal structure , stereochemistry , ion , organic chemistry , molecule , financial economics , economics
A series of bridged calix [4] arenes (5–10 methylene groups in the bridge) were synthesized and transformed into their tetraester derivatives by reaction with ethyl bromoacetate. The stability constants for complexes of the tetraester derivatives with sodium, potassium and silver cations, determined in methanol by spectroscopic or potentiometric techniques, show a drastic decrease (more than 10 5 for Na + ) for the shorter methylene chains. 1 H NMR studies demonstrate a conformational rearrangement of the calixarene part to fourfold symmetry to be necessary for the complexation of a cation, which is prevented by the shorter chains. This is further confirmed by the X‐ray structure of a tetraester derivative with a CH 2 CH 2 COCH 2 CH 2 bridge; crystals were monoclinic, space group P 2 1 / c , a = 11.847(2), b = 39.773(5), c = 12 · 127(2) Å, β = 109.24(1), V = 5395.1 Å 3 , Z = 4, D x = 1.186 Mg m −3 .