Complexation of porphyrin-appended guests by calix[4]arene-appended cyclodextrins

J.J. Michels, R. Fiammengo, P. Timmerman, Jurriaan Huskens, David Reinhoudt

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18 Citations (Scopus)

Abstract

A calix[4]arene based β-cyclodextrin dimerand tetramer (1 and2, Figure 1) were synthesized by covalentattachment of amono(2-O-xylylamino)-β-cyclodextrinderivative to calix[4]areneplatforms, bi- or tetrafunctionalized withcarboxylic acid groups at their upperrims. The complexation of porphyrin-basedguest molecules by these hosts inwater was studied using microcalorimetry.Tetrakis(4-phenylsulfonato)porphyrin(TsPP) binds to 2 in a 1 : 2 (host : guest)fashion with enhanced bindingstrength (K1 = 6.6 × 106 M -1) ascompared to the monomeric TsPP–CDinteraction (K = 8.8 × 105 M -1). Thisenhancement is attributed tothe involvement of two cyclodextrin units in theaccommodation of one TsPP guest.Increase of the number of 4-sulfonatophenyl siteson the guest by generating theμ-oxo-dimer of the iron(III) complex of TsPPled to further increase of thebinding strength owing to participation of threeβ-cyclodextrin cavities of2 (K = 1.5 × 107 M -1). The geometricincompatibility betweenhost and guest, stemming from the fact that both TsPPand its μ-oxo-dimer arefairly small compared to the multi-cyclodextrin hosts,probably explains why theenhancement is still moderate. A much more pronouncedincrease in complexationstrength was achieved with p- and m-pyridylporphyrinextended withp-tert-butylbenzyl guest sites. Theseguests are large enough to accommodatethree to four β-cyclodextrin units. The bettermatch in size between host and guestgave association constants up 108 and 109 M -1for the β-cyclodextrindimer and tetramer, respectively. In fact, the 1 : 1complex betweentetrakis(p-tert-butylbenzyl)-p-pyridylporphyrinand 2(K = 5 × 109 M -1) is the strongestreported for cyclodextrin–porphyrininteractions.
Original languageUndefined
Pages (from-to)163-172
JournalJournal of inclusion phenomena and macrocyclic chemistry
Volume41
Issue number1-4
DOIs
Publication statusPublished - 2001

Keywords

  • Porphyrins
  • microcalorimetry
  • Cyclodextrins
  • IR-37893
  • Calix[4]arenes
  • METIS-205738

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