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The present article reports the spectroscopic investigations on non-covalent interaction of fullerenes C(60) and C(70) with a macrocyclic receptor molecule, namely, 1,3,5,7-tetrahomo-p-tert-butylcalix[8]arene (1) in toluene. Jobs method of continuous variation reveals 1:1 stoichiometry for the fullerene complexes of 1. The most fascinating feature of the present study is that 1 binds selectively C(60) compared to C(70) as obtained from binding constant (K) data of C(60)-1 (K(C60-1)) and C(70)-1 (K(C70-1)) complexes which are enumerated to be 265,000 dm(3) mol(-1) and 63,43 dm(3) mol(-1), respectively, and selectivity in binding (K(C60-1)/K(C70-1)) is estimated to be 4.18 as obtained from UV-Vis study. Steady state fluorescence studies reveal quenching of fluorescence of 1 in presence of fullerenes and the K value of the C(60)-1 and C(70)-1 complexes are estimated to be 80,760 and 68,780 dm(3) mol(-1), respectively, with selectivity in binding (K(C60-1)/K(C70-1)) ~1.18. (1)H NMR analysis provides very good support in favor of strong binding between C(60) and 1. The high value of K value for C(60)-1 complex indicates that 1 forms an inclusion complex with C(60)., (Copyright © 2011 Elsevier B.V. All rights reserved.)

Abstract: The present article reports the spectroscopic investigations on non-covalent interaction of fullerenes C60 and C70 with a macrocyclic receptor molecule, namely, 1,3,5,7-tetrahomo-p-tert-butylcalix[8]arene (1) in toluene. Jobs method of continuous variation reveals 1:1 stoichiometry for the fullerene complexes of 1. The most fascinating feature of the present study is that 1 binds selectively C60 compared to C70 as obtained from binding constant (K) data of C60-1 (K C60-1 ) and C70-1 (K C70-1 ) complexes which are enumerated to be 265,000dm3 mol−1 and 63,430dm3 mol−1, respectively, and selectivity in binding (K C60-1 /KC70-1 ) is estimated to be 4.18 as obtained from UV–Vis study. Steady state fluorescence studies reveal quenching of fluorescence of 1 in presence of fullerenes and the K value of the C60-1 and C70-1 complexes are estimated to be 80,760 and 68,780dm3 mol−1, respectively, with selectivity in binding (KC60-1 /KC70-1 ) ∼1.18. 1H NMR analysis provides very good support in favor of strong binding between C60 and 1. The high value of K value for C60-1 complex indicates that 1 forms an inclusion complex with C60. [Copyright &y& Elsevier]

Abstract: A novel and convenient protocol for the synthesis of hexahydroxy[2.1.2.1.2.1]- and octahydroxy[2.1.2.1.2.1.2.1]metacyclophanes from 4-substituted phenol in four steps has been developed. The synthetic route involved the preparation of the key intermediate 1,2-bis(5-substituted-2-hydroxyphenyl)ethanes in good yields via (i) formylation of 4-substituted phenol, (ii) reductive deoxygenation of 5-substituted 2-hydroxy aromatic aldehydes with low-valent titanium reagent and (iii) catalytic hydrogenation. The metacyclophanes were prepared by base-catalyzed macrocyclization of the above intermediates with formaldehyde in refluxing xylene in high yields. [Copyright &y& Elsevier]