Flexible Host Frameworks with Diverse Cavities in Inclusion Crystals of Bile Acids and Their Derivatives

We have systematically investigated structures and properties of inclusion crystals of bile acids and their derivatives. These steroidal compounds form diverse host frameworks having zero-, one- and two-dimensional cavities, causing various inclusion behaviors towards many organic compounds. The diverse host frameworks exhibit the following guest-dependent flexibility. First, the frameworks mainly depend on the included guests in size and shape. The size-dependence is quantitatively estimated by the parameter PCcaviry, which is the volume ratio of a guest molecule to a host cavity. The resulting values of PCcaviry lie in the range of 42-76%. Second, each of the host frameworks has its own range of the values. Some guests can employ two different frameworks with the boundary values, explaining formation of polymorphic crystals. Third, the host frameworks are selected by host-guest interactions through weak hydrogen bonds, such as NH/pi and CH/O. The weak hydrogen bonds play an important role for various selective inclusion processes. Fourth, the host frameworks are dynamically exchangeable, resulting in intercalation and polymerization in the cavities. These static and dynamic structures of the frameworks demonstrate great potential of crystalline organic inclusion compounds as functional materials. (D 2009 The Japan Chemical journal Forum and Wiley Periodicals, Inc. Chem Rec 9: 124-135; 2009: Published online in Wiley InterScience (www.interscience.wiley.com) DOI 10.1002/tcr.20171