[picture: see text] The syntheses of the first 2,3-dialkoxy-substituted naphthalene ring-based macrocycles which have calixarene-like structures are reported. The complexation properties of these octahomotetraoxaisocalix[4]naphthalenes were investigated. These new members of the calixnaphthalene family did not demonstrate any appreciable complexation with C(60) or C(70) under the conditions studied, but did so with the tetramethylammonium cation, showing relatively strong association constants suggesting among other considerations that stronger cation-pi interactions versus pi-pi interactions are operative with these hosts. An X-ray crystal structure of the octa-O-ethoxy derivative revealed a structure having a "flattened partial-cone" conformation in which two acetonitrile guest molecules are trapped.

Pentakis(1,4-benzodithiino)corannulene (6) in CS2 formed the strongest 1:1 complexes with C60 and C70 of any corannulene derivative yet reported. The 1,3,5,7,9-pentakis(propylthio)corannulene (4b) formed weaker 1:1 complexes with C60 and C70 in CS2, whereas the decakis(propylthio)corannulene (5b) and unsubstituted corannulene (1) showed no evidence for complexation with either C60 or C70 in CS2.

This Account is dedicated to Professor George Just (McGill University) and to the memory of the late Professors Guido Perold (University of the Witwatersrand) and Satoru Masamune (University of Alberta and M.I.T.) for giving me the initial opportunities to undertake research in chemistry under their guidance; and also to Janette, Melissa, Andreas, Noulla and Menelaos. SYNLETT 2005, No. 6, pp 0879-08910 6 . 0 4 . 2 0 0 5 Advanced online publication: 23.03.2005Abstract: The first naphthalene ring-based analogues of the betterknown and extensively studied calixarenes were synthesized in 1993. Since that time, our group has focused its research on the design and synthesis of other 'calixnaphthalenes'. These endeavours are motivated partly due to the synthetic challenges which they provide, and to the challenges in deciphering their structural and complexation properties. Calixnaphthalenes offer several advantages over their calixarene analogues. Among these are the facts that they can form deeper, more electron-rich and in some cases, chiral, cavities. They also provide a wide range of potential new scaffolds upon which to design and build new receptors for neutral, or charged guest species. Their supramolecular complexation properties have barely been explored as yet since in most cases, only relatively small quantities only of these compounds have been obtained. In this review, all of the known, and previously unreported calixnaphthalenes are described. As well, some of the compounds, which are described, are still subjects of ongoing research.