Informative similarities/differences between self-assembled and single-crystal-to-single-crystal (SCSC) guest-exchanged crystals based on both the molecular structure and adsorption nature are observed. The self-assembly of Ni(ClO4)2 with a dicyclopentyldi(pyridine-3-yl)silane bidentate ligand (L) in a mixture of toluene and acetonitrile gives rise to purple crystals consisting of double-stranded ellipsoidal tubes, [Ni6(ClO4)4(CH3CN)8L12]·8ClO4·4CH3CN·5C7H8. The coordinated acetonitriles as well as the solvates are removed at 170 °C to transform the purple crystals into blue crystals of [Ni(ClO4)2L2]n that return to the original crystals in the mixture of toluene and acetonitrile. Further, the toluene and acetonitrile solvates of the original crystals are replaced by o-, m-, and p-xylene isomers within 5 min in a SCSC manner. In the present study, SCSC xylene-exchanged crystals were compared with crystals obtained from direct self-assembly in a mixture of each xylene isomer and acetonitrile.
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