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Crystal Structures of Two Calix[4]arene Isomers with Benzaldehyde Moiety and Their Photophysical Properties with Terbium(III) Ions
Author(s) -
Hao Wang,
HengYi Zhang,
Yu Liu
Publication year - 2005
Publication title -
chinese journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.28
H-Index - 41
eISSN - 1614-7065
pISSN - 1001-604X
DOI - 10.1002/cjoc.200590740
Subject(s) - chemistry , terbium , lanthanide , intramolecular force , benzaldehyde , moiety , alkoxy group , crystal structure , crystallography , absorption spectroscopy , acetonitrile , intermolecular force , photochemistry , ion , stacking , stereochemistry , molecule , organic chemistry , alkyl , catalysis , physics , quantum mechanics
Two calix[4]arene isomers with benzaldehyde moieties, i.e. , 5,11,17,23‐tetra‐ tert ‐butyl‐25,27‐bis[2‐( o ‐formyl‐phenoxy)ethoxy]‐26,28‐dihydroxycalix[4]arene ( 3 ) and 5,11,17,23‐tetra‐ tert ‐butyl‐25,27‐bis[2‐( p ‐formylphenoxy)‐ ethoxy]‐26,28‐dihydroxycalix[4]arene ( 4 ), were synthesized according to a newly designed route in high yields, and their crystal structures have been determined by X‐ray crystallographic study. The photophysical behavior on com‐plexation of calix[4]arene derivatives 3 and 4 with terbium(III) nitrate was investigated in anhydrous acetonitrile at 25°C by UV‐Vis and fluorescence spectroscopies. The crystallographic structure of 3 indicated that the eight oxygen atoms formed a preorganized ionophoric cavity due to intramolecular π‐π stacking, which could encapsulate lanthanide ions tightly. In sharp contrast, the compound 4 formed a linear array by intermolecular π‐π stacking, hence the oxygen atoms of pendant arms could not coordinate with metal ions, giving a poor binding ability to Tb 3+ . The absorption spectra of 3 with Tb 3+ showed clearly a new broad intense absorption at 385 nm. Interestingly, the narrow emission line spectrum has also been observed for compound 3 with Tb 3+ , and the results obtained were discussed from the viewpoint of energy transfer mechanism between host structures and the properties of lanthanide ions.