Synthesis and Solid-State Study of Supramolecular Host-Guest Assemblies: Bis[6-O,6-O'-(1,2:3,4-diisopropylidene-a-D-galactopyranosyl)thiophosp horyl] Dichalcogenides.

[摘要]：A complementary approach for studying structural details of complex solid materials formed by sym. and unsym. dichalcogenides, which employs both X-ray diffraction (XRD) and solid-state NMR (SS NMR), is presented. The new diagnostic technique allows reversible crystallog. space group change and very subtle distortion of host geometry to be followed during guest migration in the crystal lattice. Bis[6-O,6-O'-(1,2:3,4-diisopropylidene-a-D-galactopyranosyl)]thiophosp horyl selenenyl sulfide I (X = S, Y = Se), a representative of wheel-and-axle host (WAAH) mols., can be synthesized in the solid state by grinding and gentle heating of disulfide I (X = Y = S) and in the solid phase has been reported (J. Org. Chem.1995, , ). In the current work, the synthesis and both XRD and SS NMR studies of the isostructural diselenide substrate I (X = Y = Se) are presented. A 31P cross polarization magic angle spinning expt. is employed to follow the progress of synthesis of selenenyl sulfide I (X = S, Y = Se) in the solid state. It is concluded that selenenyl sulfide exists in equil. with disulfide and diselenide in a 1:1:1 ratio in both the liq. and the powd. solid. A mixt. of isostructural dichalcogenides crystd. from different solvents form three-component host-guest inclusion complexes with columnar architecture. In the host-guest complex of diselenide I (X = Y = Se) with toluene (space group C2), columns of host mols. are in parallel orientations along all the axes, whereas in the structures of diselenide I (X = Y = Se) with propan-2-ol and propan-1-ol (space group P32), the columns of host mols. lay along the 3-fold symmetry axis. Thermal processes effecting structural changes in the host lattice and the kinetics of reversible guest mol. diffusion were investigated using SS NMR spectroscopy. Finally, the Se/S scrambling phenomenon and limitations in the X-ray structure refinement of org. compds. contg. selenium and sulfur in chains are discussed.

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