@misc{oai:ir.soken.ac.jp:00000198,
 author = {青柳, 将 and アオヤギ, マサル and AOYAGI, Masaru},
 month = {2016-02-17, 2016-02-17},
 note = {This thesis describes the studies on the construction of various finite and infinite molecular architectures by accumulating metal-containing macrocyclic subunits.
  Macrocycles can bind small molecules in their cavities and have played an important role in the development of host-guest chemistry, molecular recognition chemistry, and supramolecular chemistry.  Recently, macrocylclic frameworks have been constructed quite efficiently through molecular self-assembly which is featured by spontaneous generation of highly ordered structures from well-designed small components under thermodynamic conditions.  Although a variety of metal containing macrocycles have been constructed by this method, further accumulation of the self-assembled macrocycles have been never investigated.  Thus, the author paid his special attention to the concept of "assembly of assembly", where self-assembled structures self-assemble into more complex systems, and designed the accumulation of macrocyclic complexes into higher ordered structures.  As described in Chapter 1, the construction of such hierarchical assembled systems by the accumulation of macrocyclic units is his basic concept throughout the work in this thesis (Figure 1).
  Among many metal-containing macrocycles, M4L4 (M: metal, L: ligand) square complexes, in which metal provides 90 degree at every corner of the square, are one of the simplest and hence well-studied macrocyclic coordination compounds.  He first examined infinite accumulation of the square motif by combining Cd(NO3)2 and 4, 4'-bpy (4, 4'-bpy = 4, 4'-bipyridine) as described in Chapter 2.  As a result, the variation of M:L ratios and concentrations led to the formation or two-dimensional {[Cd(4, 4'-bpy)2(H2O)2]･4H2O･2NO3}n (1), one-dimensional { [Cd(4, 4'-bpy)3(H2O)2]‥2(4, 4'-bpy)･2NO3･4.5H2O}n (2), and zero-dimensional [Cd2(4, 4'-bpy)5(NO3)2(H2O)4]･4H2O･2NO3 (3).  Complex 1 possesses a non-interpenetrated fused square grid network in which the square cavities are occupied by water molecules and nitrate ions (Figure 2a).  The structure of the framework is similar to that of a guest-encapsulated square grid complex, which is previously reported, except shortened interlayer distance.  The one-dimensional polymer 2 and zero-dimensional structure 3 forms two-dimensional networks with the　assistance of O-H…N hydrogen bonds. 　Whereas the square grid is a two-dimensional extension　of a square structure within a plane, he also designed the three-dimensional extension of a square　motif along its vertical direction. 　Thus, in Chapter 3, the formation of …Pt(II)…Br-Pt(IV)… mixed-valence complexes was utilized for the assembly of square compounds, [(en)M(4, 4'-bpy)]4(NO3)8(4-(NO3)8;  a: M = Pt(II), b: M = Pd(II)), into higher ordered infinite complexes.  The reaction of 4a8+ with cationic Pt(IV) complex, [PtBr2(en)2]2+ (5 2+), afforded a 1 :3 complex
4a･(5)3 14+.  Crystallographic analysis of this complex showed that two moieties of 5 2+ bridged at the cis corner of 4a8+ making a stair-like infinite network, whereas another moiety of 5" was accommodated in the cavity of 4a8+ (Figure 2b).  On the other hand, complexation of 4b with anionic Pt(IV) complex, PtX6 2- (6 2-;  a: X = Cl, b: X = Br), afforded a 1:4 complex 4･(6)4.  UV-vis observations suggested the formation of a linear tube structure, in which each corner of 4 8+ is bridged by the linear X-Pt-X motif of 6 2-.
  One of the most interesting structures derived from macrocyclic units is tubular assemblies.  In fact, tubular polymers, which are capable of ion transportation and catalysis, have been constructed by linking macrocyclic compounds.  However precise control of lengths have been unrealized yet.  In Chapter 4, coordination nanotubes, which possess very stable and discrete frameworks, were constructed by linking oligo (3, 5-pyridine)s (pentakis: 7a, tetrakis: 7b, iris: 7c) with a cis-protected Pd(II) building block, (en)Pd(NO3)2 (Figure 3).  This transformation was in fact accomplished with the remarkable template effect of biphenyl derivatives.  Thus, the reaction of 7 with (en)Pd(NO3)2 first resulted in the formation of uncharacterizable products.  However, the addition of sodium 4, 4-biphenylenedicarboxylate to the solution induced the smooth assembly of nanotubes 8a-8c wherein four molecules of 7 were held together with six to ten Pd(II) units.  A nanotube structure templated by a guest was confirmed by an X-ray crystallographic analysis. 
  The dynamics of guest molecule accommodated in the coordination tubes 8a and 8c was investigated in Chapter 5 by variable temperature NMR measurements at different host-guest ratios.  As the results, guest molecules are found to shuttle in the tube without flipping at low temperatures, but intermolecularly exchange at elevated temperatures.  Coordination nanotube 8b for which structural isomers can be considerable was isolated as a single isomer by recystallization.  The structure of a isomer was confirmed by X-ray crystallography.  This single isomer slowly turned into an equilibrium mixture of two structural isomers in aqueous media.
  To extend molecular nanotubes into solid tubular materials, in Chapter 6, the formation of the coordination polytubes were examined by combining 7b and a transition metal (CuI).  The X-ray crystallographic analyses showed that two types of non-interpenetration networks were induced by non-aromatic and aromatic guest molecules in the reaction media.  A non-aromatic guest CH3CN induced two-dimensional polytube [7b･(Cu2I2)･2G･H2O (9, G = CH3CN) with an accessible porosity of 32% (Figure 4a).  On the other hand, Aromatic guests such as nitrobenzene or cyanobenzene induced three-dimensional polytube structures [7b･(Cu2I2)]･2G (10a: G = nitrobenzene, 10b: G = cyanobenzene) with large accessible porosity of 48% (Figure 4b).  The cavities of 9 and 10 were occupied by guest molecules.  Thermogravimetric (TG) analysis, IR spectroscopy, and powder X-ray diffraction analysis of 1, application/pdf, 総研大甲第443号},
 title = {Construction of Nanoscale Coordination Systems by Accumulating Metal-Containing Macrocycles},
 year = {}
}