Energies of charge transfer and supramolecular interactions of some mono O-substituted calix[6]arenes with [60]fullerene by absorption spectrometric method

Equilibria for the formation of supramolecular complexes of 60]fullerene with a series of mono O-substituted calix6]arenes, namely: (i) 37-methoxy-38,39,40,41,42-pentahydroxy-5,11,17,23,29,35-hexa(4-tert-butyl)calix6]arene (1), (ii) 37-allyl-38,39,40,41,42-pentahydroxy-5,11,17,23,29,35-hexa(4-tert-butyl)calix6]arene (2), (iii) 37-phenacyl-38,39,40,41,42-pentahydroxy-5,11,17,23,29,35-hexa(4-tert-butyl)calix6]arene (3), (iv) 37-ethylester-38,39,40,41,42-pentahydroxy-5,11,17,23,29,35-hexa(4-tert-butyl)calix6]arene (4) and (v) 37-benzyl-38,39,40,41,42-pentahydroxy-5,11,17,23,29,35-hexa(4-tert-butyl)calix6]arene (5) have been studied in CCl4 medium by absorption spectroscopic technique. The stoichiometry has been found to be 1:1 (60]fullerene:calix6]arene) in each case. An absorption band due to charge transfer (CT) transition is observed in each case in the visible region. The vertical ionisation potentials (I(D)(v)) of all the calix6]arenes under study have been estimated utilising CT transition energy. The experimental I(D)(v) values also yield a good estimate of the electron affinity of 60]fullerene. The degrees of CT in the ground state of the complexes have been found to be very low (about 0.15%). Resonance energy of the complexes have been estimated. Thermodynamic parameters for the supramolecular complex formation of 60]fullerene with mono O-substituted calix6]arene receptors are reported. It is observed that among the calix6]arenes under the present study, only 1 and 4 form inclusion complexes with 60]fullerene. This has also been substantiated by theoretical calculation using PM3 method. Thus presence of one substituent group (of different types) on the lower rim of the calix6]arene molecule has been shown to govern the host-guest complexation process.