@misc{oai:ir.soken.ac.jp:00000211,
 author = {藤田,  典史 and フジタ, ノリフミ and FUJITA, Norifumi},
 month = {2016-02-17, 2016-02-17},
 note = {This thesis deals with chemical construction of functional nano-structures through spontaneous assembly of small molecular components.  The author focuses his special attention on metal-directed self-assembly which has been recognized during the last decade as a promising way to the precise construction of well-defined nanometer-scale architectures.  Of many target structures, the author is particularly interested in both challenging and functional architectures which have been never synthesized by conventional synthesis.  In view of synthetic challenge, the author has studied the construction of topologically complex, interlocked molecules (catenanes) by self-assembly.  The efficient synthetic methodologies obtaining [2] catenane by interlocking two macrocycles have been recently established.  However, construction of their three-dimensional analog which is also a [2] catenane but composed of two macrobicyclic three-dimensional cages instead of two macrocycles has never been achieved.  The author furnishes a surprisingly efficient method for the synthesis of such 3D-interlocked compound using the self-assembly strategy.
  After the synthesis of the 3D-catenane, the author's interest shifted towards systems which are challenging as well as functional.  Thus a novel system was designed where porphyrin array is incorporated into a catenane structure.  He synthesized a porphyrin catenane that constitutes multi-component, photo-induced electron transfer system where components are assembled and arrayed through catenation.  Finally, he prepared a porphyrin-based hollow framework by self-assembly.  The entity has a prism-like framework composed of three porphyrin units and six metal centers.  Various organic molecules can be included in the large hydrophobic cavity where new photo- and electrochemistry, through host-guest interaction, are highly expected.
  The thesis is composed of six chapters.  Chapter 1 is an introduction and general summary whose synopsis has been mentioned above.  Brief summaries of all other chapters are described as follows.
  Chapter 2 describes preparation of a three dimensionally interlocked compound by metal-mediated self-assembly.  The framework  of each cage us assembled from five components:  two tridentate ligands held together with three metal ions.  Because each cage framework can bind an aromatic ring, two cage units will bind one another during their assembly process through the formation of a quadruple aromatic stack, giving rise to the ten-component interlocked supermolecule.  Both solution and solid state structures are characterized conclusively by NMR, ESI-MS and X-ray analysis.
  When the cage component does not possess C3v symmetry, the resulting 3-D interlocked structure is obtained as a diastereomeric mixture which are shown to exchange rapidly on the NMR NOESY timescale.  The 3-D interlocked compound involves two different ligands, each of which gives its own assembly upon complexation with metal ions.  Interestingly, two different assemblies preformed by treating the two ligands with metal ions independently are found to re-assemble into the combined 3D-interlocked structure.  Such a dynamic behavior of the multi-component assemblies is discussed in Chapter 3.
  Porphyrin assemblies take essential role in biological systems for oxygen transport, electron transfer, and energy migration and conversion.  In this regard, designing molecular assemblies using porphyrin units is a promising approach for constructing artificial functional systems.  Described in Chapter 4 is the construction of [2] catenane composed of Zn(II) and Au(III) porphyrin-incorporated macrocycles which is capable of intramolecular photo induced electron transfer between donor and acceptor components.
  As an extension of artificial porphyrin assemblies, making a porphyrin-based hollow framework is also expected to open a new porphyrin chemistry through host-guest interaction.  Chapter 5 describes a construction of prism-like hollow structure composed of three porphyrin units and six cationic Pd(II) complex.  All these components surround a large hydrophobic cavity where various organic compounds can be included in aqueous solution.  Pyrene inclusion induces D3h → C2 structural change in the assembly making it chiral.  Upon the inclusion of optically active pyrene, chiral induction of the host structure is observed by CD spectrum.  Even after guest exchange into achiral pyrene, C2 chirality of the host retains with the lifetime of several hours.  This memory storage ability of the porphyrin prism is discussed in Chapter 6., application/pdf, 総研大甲第512号},
 title = {Metal-Mediated Construction of Highly Ordered Molecular Arrays: from Synthetic Challenge to Functional Assemblies},
 year = {}
}