Missing-link macrocycles: hybrid heterocalixarene analogues formed from several different building blocks.
The synthesis and structural characterization of hybrid heterocalix[4]arene analogues containing pyrrole, benzene, methoxy-substituted benzene, and pyridine subunits is described. Macrocycles 1 and 2, examples of calix[2]benzene[2]pyrrole and calix[1]benzene[3]pyrrole systems, respectively, are synthesized by the condensation of pyrrole and an appropriate phenylbis(carbinol). Macrocycles 3 and 7, examples of calix[2]benzene[1]pyridine[1]pyrrole and calix[1]pyridine[3]pyrrole, respectively, are synthesized by the use of a carbene-based pyrrole-to-pyridine ring-expansion procedure. Single-crystal X-ray analysis reveals that compounds 1a, 1b, and 2b adopt 1,3-alternate conformations in the solid state, whereas compounds 3 and 7 display structures that are best described as "flattened partial cones" in terms of their conformation. (Series a refers to pure benzene-derived systems, whereas series b indicates macrocycles containing 5-methoxyphenyl subunits). In the solid state, the methoxy-functionalized macrocycles 1b and 2b, and the chloropyridine-containing macrocycle 7 exist as dimers. In the case of 1a and 7, these compounds interact with neutral solvent in the solid state. The conformations of the macrocycles in solution were explored by temperature-dependent proton NMR and NOESY spectral analysis. At 188 K, macrocycles 1a and 2a adopt flattened 1,3-alternate conformations, whereas macrocycles 3 and 7 exist in the form of flattened partial-cone conformations. Standard proton NMR titration analyses were carried out in the case of macrocycles 1a and 2a, and reveal that at least the second of these systems is capable of binding fluoride and chloride anions in CD(2)Cl(2) solution at room temperature (K(a)=571 and 17M(-1) in the case of 2a and F(-) and Cl(-), respectively).
Sessler
Jonathan L
JL
Department of Chemistry and Biochemistry, Institute for Cellular and Molecular Biology, The University of Texas at Austin, Austin, TX 78712-1167, USA. sessler@mail.utexas.edu
Cho
Won-Seob
WS
Lynch
Vincent
V
Král
Vladimír
V
D001952:Bridged-Ring Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D018360:Crystallography, X-Ray; D006860:Hydrogen Bonding; D007202:Indicators and Reagents; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D011725:Pyridines / Q000138:chemical synthesis* / Q000737:chemistry; D011758:Pyrroles / Q000138:chemical synthesis* / Q000737:chemistry
D001952:Bridged-Ring Compounds; D007202:Indicators and Reagents; D011725:Pyridines; D011758:Pyrroles