| Summary: | The synthesis and characterization of new tetramethoxy resorcinarene
derivatives are described. The new compounds are obtained and characterized
in solution and solid state, along with halogen bonded networks. In the coming
pages the structural and photophysical properties of newly synthesized
tetramethodxy resorcinarene derivatives will be presented.
A previously unknown derivative of the tetramethoxy resorcinarene
platform, methyl tetramethoxy resorcinarene, was synthesized completing the
family of tetramethoxy resorcinarenes. Methyl C1- and ethyl C2-tetramethoxy
resorcinarenes were used as platforms for the syntheses of five different
pyridine and benzyl functionalized resorcinarene tetrapodands, and for the
crown-ether bridged benzofuran resorcinarene derivative. The structural
properties of these compounds were studied in solution by NMR spectroscopy
and in the solid state by X-ray crystallography. Only one carbon difference in
the lower rim alkyl groups, methyl vs. ethyl, was observed to affect the
dynamic behavior of resorcinarene podands in solution. In the solid state,
methyl tetramethoxy resorcinarene obeyed compact “brick”-like packing made
possible by the small methyl group at the lower rim.
The pyridine functionalized resorcinarene podands were used in the
construction of solid state halogen bonded architectures with halobenzene
linkers. The structural characteristics of the resorcinarene scaffold and the
podand arms allowed the formation of multidimensional networks showing
potentially porous properties. In solution, although no formation of larger
assemblies were observed, halogen bonding between resorcinarenes and the
linkers was confirmed; and the observed interactions were supported by
computational methods.
In the synthesis of crown bridged resorcinarenes, a side product was
isolated that contained an unusual benzofuran fused macrocyclic structure. The
modified macrocycle had characteristic fluorescence properties and the study
showed that emission/excitation matrix spectroscopy is a valid tool for
structure analysis in solution.
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