Guest controlled aggregation of amphiphilic sulfonatomethylated calix[4]resorcinarenes in aqueous solutions

► NMR study of aggregation of amphiphilic calixarenes and different guests is present. ► The 'head-to-tail' aggregation unusual for amphiphilic calixarenes is observed. ► The binding of guest molecules by 'head-to-tail' packed aggregates is more efficient. ► The structural control of the guest inclusion into capsule is shown. ► Lifetime of incapsulated methylviologen cation-radical ca.14-fold increases.