@misc{oai:ir.soken.ac.jp:00000209,
 author = {梅本, 和彦 and ウメモト, カズヒコ and UMEMOTO, Kazuhiko},
 month = {2016-02-17, 2016-02-17},
 note = {Well-organized, functional nanostructures define an interesting aspect of current chemistry, biology, and physics.  For constructing molecular-based nanostructures, self-assembly through weak non-covalent interaction has been recognized as a powerful method.  In particular, the metal-directed self-assembly has been showing remarkable potential for the spontaneous generation of well-defined metallo-supramolecular architectures from organic ligands and metal ions.
  Of many molecular-based nanostructures, the author paid his attention to nano-sized polyhedral molecules because such molecules possess inner space within the closed shell structure.  Thus the author designed and synthesized a family of triangular exo-polydentate ligands, which can be termed as "molecular panels." Subsequently, he achieved the molecular self-assembly of these panels into metal-linked polyhedral architectures through metal coordination, establishing a new concept of "molecular paneling."  In principle, this concept engages a family of polyhedral structures with some novel properties at will.  Thus, in this thesis, the author shows an efficient method for the construction of 3D polyhedral architectures by paneling a family of triangular molecules as briefly summarized below.

Chapter 2.  A Nanometer-sized Hexahedral Coordination Capsule Assembled from 24 Components
  Molecular capsules consist of closed, hollow frameworks in which encapsulated molecules are isolated from any external species.  Following the general introduction, Chapter 2 describes the self-assembly of a stable, nanometer-scale capsule from small components;  eighteen metal ions and six triangular.  Thus, the complexation of exo-hexadentate ligand, triangular unit 2 with Pd(II) complex 1 gives edge-sharing hexahedron 3 with the dimension of 3.0 x 2.5 x 2.5 nm.  The internal space has a volume of 900 Å and is fully closed.

Chapter 3.  M15L6 Coordination Capsule; Reversible Guest Inclusion
  In chapter 3, pentadentate triangular ligand 4 is also found to assemble into (1)15(4)6 hexahedron coordination capsule 5 upon complexation with Pd(II) building block 1.  Whereas coordination capsule 3 is too rigid to encapsulate organic guests, capsule 5 can reversibly accommodate guest molecules such as CBr4 because it possesses non-linked gates for guest inclusion.  Moreover, the capsule can be applicable to the encapsulation/exchange of guest molecules with adding excess EtOH.

Chapter 4.  Guest-Induced Assembly of Coordination Capsule and Bowl from Identical Small Components
  A planar and triangular ligand 6 which possesses four donor sites on the two edges of the triangle, is linked by Pd(II) complex 1, in two ways:  parallel and antiparallel fashions.  The parallel link is induced by some large guest molecules such as 9 to give an open cone (tetragonal pyramidal) structure 7・9.
  On the other hand, anti-parallel link is selected by some small tetrahedral guests such as 10 giving closed tetrahedron structure 8・10.  Both structures have the same M8L4 composition.  Such dynamic molecular paneling is discussed in Chapter 4.

Chapter 5.  Side Chain-Directed Molecular Paneling
  In Chapter 5, the author examines the control of the two options by the structure of the panelitself.  Namely, the molecular panel 11 containing a directing group (a methyl substituent) on the pyrimidine is allowed to orient only in the anti-parallel fashion because of steric repulsion between the methyl groups attached on the pyrimidine ring.  Accordingly, only cage complex 12 is selectively formed upon the addition of suitable guest molecules, but a square pyramidal open cone structure like 13 is never assembled in the
presence of any guests.
  In particular, this concept provides very efficient ways for constructing large and hollow polyhedral architectures within which any species are isolated from external events and are expected to show new properties and functions., application/pdf, 総研大甲第510号},
 title = {Assembly of Polyhedra by Molecular Paneling via Coordination},
 year = {}
}