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These macrocycles with five\u2010fold symmetry show solvent\u2010dependent tautomerization and dimerization or aggregation. In this paper, we have prepared new soluble campestarenes that do not aggregate. The initial single\u2010crystal X\u2010ray diffraction study of a campestarene reveals that these macrocycles are nearly flat. The tautomeric behavior of the campestarenes has been extensively studied by variable\u2010temperature, multinuclear NMR spectroscopy, UV\/Vis spectroscopy, and IR spectroscopy. In polar solvents, such as DMF, the molecules exist predominantly in their keto\u2010enamine form, but the enol\u2010imine tautomer is dominant in non\u2010polar solvents. A detailed computational study of the tautomeric forms of campestarenes provides a theoretical basis for their behavior and corroborates the experimental data. The results of this study give the first comprehensive understanding of the electronic and spectroscopic properties of these pentagonal macrocycles.<\/jats:p>","DOI":"10.1002\/chem.201603231","type":"journal-article","created":{"date-parts":[[2016,10,27]],"date-time":"2016-10-27T05:37:16Z","timestamp":1477546636000},"page":"17657-17672","source":"Crossref","is-referenced-by-count":23,"title":["The Rich Tautomeric Behavior of Campestarenes"],"prefix":"10.1002","volume":"22","author":[{"given":"Zhengyu","family":"Chen","sequence":"first","affiliation":[{"name":"Department of Chemistry University of British Columbia  2036 Main Mall Vancouver BC V6T 1Z1 Canada"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7439-209X","authenticated-orcid":false,"given":"Samuel","family":"Guieu","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of British Columbia  2036 Main Mall Vancouver BC V6T 1Z1 Canada"}]},{"given":"Nicholas G.","family":"White","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of British Columbia  2036 Main Mall Vancouver BC V6T 1Z1 Canada"}]},{"given":"Francesco","family":"Lelj","sequence":"additional","affiliation":[{"name":"La. 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