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§5. General Overview
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In this thesis, I tried to fabricate several kinds of the functional hydrogen-bonding supramolecular materials with diverse physical properties including in the molecular absorption, ionic conduction, and dielectric responses based on specific molecular frameworks of bis-urea, bithiazole, and crown ether.
Chapter 2. Bis-urea macrocycle derivative formed a variety of host-guest supramolecular assembly structures based on the hydrogen-bonding interaction between urea units. Through a simple crystallization technique from the corresponding organic solvents, bis-urea macrocycle showed a structural diversity according to the size and length of the guest molecules. In rod-like molecules such as acetic acid and 1,5-diaminophentane, the 1D columnar hydrogen-bonding assembly structure of bis-urea was observed in the 1D tubular structure. On the contrary, the crystallization from the small size aromatic molecules such as pyridine and pyrroles, the zig-zag 2D hydrogen-bonding layer structures were observed according to the guest molecules. Especially in, the complex formation with ethylenediamine formed a different type of 2D zig-zag hydrogen-bonding layer structure containing macrocycle dimers. All guest molecules were able to be removed in vacuum condition or thermal treatment. After removal of the guests, two kinds of vacant structures were confirmed in the 1D columnar (S1’) and shrinking 2D layer (S2’) structures, respectively. Interestingly, these two structures were transformable to each other by simple guest absorption-desorption process or thermal treatment. When the S1’ state was kept in the high temperature, the transformation from S1’ to S2’ was confirmed and the S2’ phase was thermally stable than the S1’
one. On the contrary, the absorption and desorption of acetic acid transformed the S2’ arrangement to S1’.
In addition, the sorption properties of the two vacant structures were evaluated and the S1’ phase showed a selective absorption for CO2 without N2 absorption. Whereas the S2’ did not show absorption for gas molecules neither CO2 nor N2, which was attributed to the shrinking arrangement of pores. Therefore, I proposed a dimensional crossover and structural transformation of hydrogen-bonding bis-urea macrocycle derivative, which was sensitive to the external stimuli such as heat and molecular sorption cycles.
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Chapter 3. Proton accepting 2,4-DABT and its structural isomer of 2,5-DABT were utilized to form acid-base ionic crystal, where the proton-donating phosphoric acid was mixed with these two isomers to form different cationic and anionic molecular assembly structures. The relationship between hydrogen-bonding networks and proton conductivity in crystalline state was discussed in detail. Through the adjustment of the acidity in the crystallization condition, five kinds of single crystals were obtained in the different cation - anion stoichiometry. Depending on the isomer and the formula of crystals, five kinds of the hydrogen-bonding network structures from 1D to 3D were observed in the single crystal X-ray structural analyses. The 1D single chain was observed in mono-cationic salt of 2,4-HDABT+ with H2PO4-, while the 1D two-leg ladder chain hydrogen-bonding interaction was conformed in di-cationic 2,4-H2DABT2+. The 2D hydrogen-bonding layer was observed in di-cationic 2,5-H2DABT2+ salt, while the 3D networks was constructed by the mixed state of anionic H2PO4- and neutral H3PO4 in the mixed proton-transferred salts of 2,4-H2DABT2+ and 2,5-H2DABT2+. In these 3D networks, the 2D layers were connected by the additional inter-layer hydrogen-bonding interaction. In the bulk state, the proton conductivity increased as the dimension grown of the hydrogen-bonding interactions. In addition, proton conductivity of three kinds of single crystals was evaluated to discuss the mechanism of conductivity.
Because the different hydrogen-bonding networks and proton transport pathways along the different crystal axis, anisotropic conductivity was confirmed according to the strength and uniformity of hydrogen-bonding interactions, where the magnitude of proton conductivity was two orders of magnitude difference to each other. Furthermore, through comparing in the conducting pathways for the different hydrogen-bonding networks, the high proton conductivity was found in the mixed protonated state and uniform hydrogen-bonding interaction. Therefore, the control in the hydrogen-bonding framework with uniform and mixed protonated state are essential for designing in the excellent proton conductor with high performance. The preset designing strategy will further provide the understanding in and innovation for
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the development of high and anisotropic organic proton conductors.
Chapter 4. Alkylamide-substituted (−NHCOC10H21) hydrogen-bonding dibenzo[18]crown-6 derivative (1) was prepared to stabilize the one-dimensional (1D) ionic channel structure, which were consistent with the formations of organogel, nanofiber, and discotic hexagonal columnar (Colh) liquid crystal phase. The 1D hydrogen-bonding chains of 1 were not suitable for the ferroelectric response through the dipole inversion of the N−H•••O= hydrogen-bonding direction. The introduction of M+X− salts into the ionic channel of 1: M+ = Na+, K+, Cs+ and X− = Br−, I−, SCN−, AcO−, PF6−, and CO3−, enhanced the ionic conductivity of Colh phase of M+•(1)•X− salts, where the highest ionic conductivity reached at ~10−6 S cm-1 for K+•(1)•I− and Na+•(1)•PF6−
and was approximately 5 orders of magnitude higher than that of 1. The partially occupied (K+)0.5•(1)•(SCN−)0.5 salt indicated much higher K+ conductivity than the fully K+ occupied (K+)•(1)•(SCN−) to reduce the Coulomb repulsive between the nearest-neighboring K+ ions. The 1D hydrogen-bonding Colh domain of 1 was non-ferroelectric state, while the introduction of 1 into ferroelectric 3BC formed the ferroelectric response at mixed Colh phase of (1)x(3BC)1-x with x = 0.1 and 0.2. The M+X− doping into the ferroelectric mixed Colh phase of (3BC)0.9(1)0.1 modulated the magnitude of ferroelectric polarization assisted by the ion displacements in the 50% filled ionic channel of (3BC)0.9[(M+)0.05•(1)0.1•(X−n)0.05/n] salts. Both the Na+ and K+ cations effectively enhanced the magnitude of the polarization due to the Na+ and K+ motions along the ionic channel to generate the ionic polarization, while significantly large Cs+ cation in the ionic channel showed only a subtle ion displacement to contribute the small magnitude of ionic polarization. The ionic motions assisted the polarization behaviors of the ion conducting liquid crystalline molecular ferroelectrics. Such new kinds of multi-functional organic materials have a potential to control the polarization state in the flexible memory devices.
178 General Conclusion
In the present thesis, several hydrogen-bonding supramolecular assemblies were designed and fabricated to form a variety of functional organic molecules. Interesting molecular absorption properties and its structural transformation (Chapter 2), proton conducting properties (Chapter 3), and the hybrid ionic conductivity and ferroelectricity (Chapter 4) were proposed in the structural transformation, intramolecular proton transportation, and ionic and molecular motions in the hydrogen-bonding molecular assemblies. Detail structural information based on the single crystal X-ray structural analysis revealed the structural diversity and also enable us to discuss the relationship between the molecular assemblies and physical properties. Because of the symmetric hydrogen-bonding sites of bis-urea macrocycle derivative, the molecule constructed diverse molecular assemblies, which was sensitive to the external stimuli of heating and guest molecular sorption. Through the controlling in structural transformation, the adsorption abilities for molecules were reversibly conformed and the second example of bithiazole derivative isomers also formed a variety of hydrogen-bonding molecular assembly frameworks, showing high and anisotropic proton conductivity. The importance of the uniform hydrogen-bonding networks and mixed proton transferred state effectively enhanced the magnitude of proton conductivity. Finally, the 1D channel of crown-ether assembly by the N-H···O hydrogen-bonding interaction provided an efficient ionic transport channel, which helped us to understand a formation of 1D uniform hydrogen-bonding channel and further combination such as ionic conductivity and ferroelectricity to fabricate multi-functional material.
Therefore, the design of functional molecule and control in the molecular assembly structures are one of the essential points of view to achieve novel molecular material. Furthermore, the establishment of such molecular designing strategy will be one of important fundamental scientific point of view for the developing and innovating the next-generation functional molecular materials.
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