1,4,7-Trithiacyclononane ([9]aneS3) reacts with molecular diiodine in CH2Cl2 to form a 1:1 adduct. The formation constant and the thermodynamic parameters of this adduct have been determined by UV-visible spectra of several solutions at the temperatures of 15, 20, 25, 30, and 35-degrees-C. The C-13 NMR spectra show that adducts with higher ligand/diiodine molar ratios are formed. Two neutral charge-transfer molecular compounds having formula 2[9]aneS3 . 4I2 (I) and [9]aneS3 . 3I2 . (II) have been obtained as crystals. The crystals of I are triclinic (a = 8.498(2) angstrom, b = 13.984(4) angstrom, c = 14.898(6) angstrom, alpha = 65.57(2)degrees, beta = 89.19(2)degrees, gamma = 81.26(2)degrees, Z = 2, space group P1BAR; R = 0.025) and contain units formed by two [9]aneS3 molecules connected by a diiodine molecule; one [9]aneS3 binds two other diiodine molecules, while the second binds only one other diiodine molecule. The crystals of II are monoclinic (a = 13.810(2) angstrom, b = 9.829(4) angstrom, c = 16.198(6) angstrom, beta = 113.41(2)degrees, Z = 4, space group P2(1)/c; R = 0.019) and contain molecules of [9]aneS3 binding three diiodine molecules. FT-Raman spectra in the characteristic nu(I-I) region, carried out on the solid adducts, are discussed in comparison with the structural parameters.
F. Cristiani, F. Demartin, F. A. Devillanova, F. Isaia, V. Lippolis, G. Verani Spectroscopic studies of charge-transfer complexes of 1,4,7-trithiacyclononane with diiodine.
ISAIA, FRANCESCO;
1993-01-01
Abstract
1,4,7-Trithiacyclononane ([9]aneS3) reacts with molecular diiodine in CH2Cl2 to form a 1:1 adduct. The formation constant and the thermodynamic parameters of this adduct have been determined by UV-visible spectra of several solutions at the temperatures of 15, 20, 25, 30, and 35-degrees-C. The C-13 NMR spectra show that adducts with higher ligand/diiodine molar ratios are formed. Two neutral charge-transfer molecular compounds having formula 2[9]aneS3 . 4I2 (I) and [9]aneS3 . 3I2 . (II) have been obtained as crystals. The crystals of I are triclinic (a = 8.498(2) angstrom, b = 13.984(4) angstrom, c = 14.898(6) angstrom, alpha = 65.57(2)degrees, beta = 89.19(2)degrees, gamma = 81.26(2)degrees, Z = 2, space group P1BAR; R = 0.025) and contain units formed by two [9]aneS3 molecules connected by a diiodine molecule; one [9]aneS3 binds two other diiodine molecules, while the second binds only one other diiodine molecule. The crystals of II are monoclinic (a = 13.810(2) angstrom, b = 9.829(4) angstrom, c = 16.198(6) angstrom, beta = 113.41(2)degrees, Z = 4, space group P2(1)/c; R = 0.019) and contain molecules of [9]aneS3 binding three diiodine molecules. FT-Raman spectra in the characteristic nu(I-I) region, carried out on the solid adducts, are discussed in comparison with the structural parameters.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.