京都大学 / 新制・課程博士 / 博士(工学) / 甲第24645号 / 工博第5151号 / 新制||工||1983(附属図書館) / 京都大学大学院工学研究科化学工学専攻 / (主査)准教授 渡邉 哲, 教授 佐野 紀彰, 教授 河瀬 元明 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

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Metal-Organic Frameworks (MOFs) are highly porous materials built from inorganic nodes joined by organic linkers forming extended crystalline networks. One of the distinguishing features of metal-organic frameworks is the ability to adaptively change their crystal structure in response to external stimuli with significant porosity switching. Such structural switchability of MOFs offers new opportunities in gas separation, selective recognition, sensing, and energy storage. However, there are still open questions in understanding factors affecting switchability. The electronic structure of the metal in the building blocks, host-guest interactions, but also particle size, morphology, surface, desolvation conditions are involved into the responsiveness of the system. One of the representative of switchable metal-organic frameworks is pillared-layer DUT-8 (M2(2,6-ndc)2(dabco), M = Ni, Co, Cu, Zn, 2,6-ndc = 2,6-naphthalenedicarboxylate, dabco = 1,4-diazabicyclo[2.2.2]octane). Depending on the metal node and particle size, it is possible to synthesize either switchable or rigid materials differing in physisorption isotherm profiles. In order to understand switching behaviour of DUT-8, the important parameters influencing structural switchability are addressed in my work. For this purpose, the impact of crystal size and morphology, as well as crystal surface on adsorption-induced structural transformations of DUT-8(Ni) were investigated. DUT-8(Ni) shows reversible structural transition between open (op) and closed pore phase (cp) upon adsorption/removal of guest molecules. To understand which particular crystal surfaces dominate the phenomena observed, crystals similar in size and differing in morphology were involved in a systematic study. The analysis of the data shows that the width of the rods (corresponding to the crystallographic directions along the layer) represents a critical parameter governing the dynamic properties upon adsorption of nitrogen at 77 K. This observation is related to the anisotropy of the channel-like pore system and the nucleation mechanism of the solid-solid phase transition triggered by gas adsorption. To investigate the influence of external surface on adsorption-induced switchability, DUT-8(Ni) samples were exposed to different treatment techniques. By means of analytical methods, it was revealed that the surface of samples was modified leading to a significant increase of the gate-opening pressure, reflecting the increase of activation barrier for phase switching form cp to op upon adsorption of nitrogen at 77 K. Furthermore, the properties of DUT-8(Zn) were studied precisely, focusing on the variation of particle size and morphology, host-guest interactions, desolvation conditions, selectivity and thermoresponsivity. Depending on the synthesis conditions, DUT-8(Zn) can be synthesised in macro-sized regime (150 µm) and micron-sized regime (0.5 µm). The solvent removal process (pore desolvation stress contracting the framework) significantly controls the cp/op ratio after desolvation and, subsequently, the adsorption induced switchability characteristics of the system. Among the applied desolvation techniques, the solvent exchange with subsequent heating causes phase transition from open (op) to closed pore phase (cp). After desolvation, the dense cp phase of DUT-8(Zn) shows no adsorption-induced reopening and therefore is non-porous for N2 at 77 K and CO2 at 195 K. However, polar molecules with a higher adsorption enthalpy, such as chloromethane at 249 K and dichloromethane (DCM) at 298 K can reopen the macro-sized crystals upon adsorption, while micron-sized crystals retain the cp phase. For macro-sized particles (160 µm), the outer surface energy is negligible and only the type of metal (Zn, Co, Ni) controls the DCM-induced gate opening pressure. The node hinge stiffness increases from Zn to Ni as confirmed by DFT calculations, X-ray crystal structural analysis, and low frequency Raman spectroscopy. This softer Zn-based node hinges and overall increased stabilization of cp vs. op phase shift the critical particle size at which switchability starts to become suppressed to even lower values. Hence, the three factors affecting switchability (energetics of the empty host, (Eop–Ecp) (i), particle size (ii), and desolvation stress (iii)) appear to be of the same order of magnitude and should be considered collectively, not individually. Crystal downsizing (0.5 µm) facilitates the responsivity of DUT-8(Zn) towards different guest molecules, not opening for macro-sized crystals. Among investigated adsorptives, the alcohols are in the center of attention due to ability to induce so called shape-memory effect in micron-sized crystals. The adsorption of alcohols stimulates the change of initial shape of pores (cp) into a temporary shape (op) which is maintained even after desorption. To brighten the crystal size range and to study the dependence of gate opening pressure from crystal size and morphology, differently shaped crystals in micron-sized regime were produced by face-selective coordination modulation. Morphology modification allowed to determine the critical parameter controlling switchable transformations in DUT-8(Zn). Thus, the crystal size engineering and morphology modification provide an opportunity not only to control the structural dynamics of MOFs, but also to tailor responsivity towards guest molecules, influencing the selective adsorption behaviour.

In this thesis, the CW and pulse EPR techniques are employed to understand several information, such as the local and electronic structure and magnetic interactions of metal ions in metalorganic frameworks as well as the guest-host framework interaction upon gas adsorption. Other characterization techniques, such as PXRD, SQUID, and quantum chemical calculation, are also outlined, which are complementary to the information provided by EPR. In situ EPR studies give valuable details on structural transition, which can’t be attained by other techniques always. EPR spectroscopy confirms that post-synthetic modification is possible in paddle wheel-based MOFs through the magnetic coupling of metal centers and also gives information about magnetic mixed paddle wheel units, which is often complicated to understand. The quite challenging divalent nickel-based MOF is studied along with NO adsorption, and the result highlights the capabilities of sophisticated EPR techniques in combination with quantum chemical calculations to provide fundamental insights into the non-obvious electronic structure of open-shell species docked in metal-organic frameworks. Finally, the inter- and intra-trimer interactions of high-spin chromium-based trimers are discussed in detail in combination with SQUID magnetometry.

To date, most two-dimensional conjugated metal–organic frameworks (2D c-MOFs) are based on planar polycyclic aromatic hydrocarbons (PAHs), which limits the ability to introduce additional substituents to control their properties. This thesis introduces a novel monomer ligand derived from highly substituted, core-twisted hexahydroxy-hexa-cata-benzocoronenes (6X-6OH-cHBCs), resulting in a new class of wavy 2D c-MOFs. The structural rigidity and self-complementary nature of the c-HBC ligand makes it a valuable monomer for constructing these novel 2D c-MOFs. Despite the wavy structure, effective conjugation between layers was achieved. This led to the formation of electronically conductive materials, as demonstrated by 6F-cHBC-Cu, which exhibited a conductivity of 1.82∙10-2 S/cm. Furthermore, the wavy motif of the c-HBC ligand promoted extended crystal growth in the z-direction. This was demonstrated by the formation of several micrometer-long single crystals of 6F-cHBC-Cu. The monomers were synthesized through a flexible three-step process, allowing for the incorporation of various substituents or functional groups, thus enabling control over ligand symmetry. This process enabled the synthesis of monomers with diverse symmetries: C6 symmetry (12OH-cHBC), C3 symmetry (6X-6OH-cHBC), and asymmetric monomers (e.g., 3F-6OH-cHBC). This structural variety allowed for systematic investigations into structure-property relationships, offering valuable insights into how monomer design influences the resulting MOF properties. The homologous 6X-cHBC-Cu MOF series (X = H, F, Cl, Br) illustrated that both the electron-withdrawing effect and the size of the substituent significantly impact crystallinity. This in turn enhances fundamental properties such as electronic conductivity, charge carrier mobility, accessible pore size, thermal stability, and morphology. Reactivity trends for the synthesized monomers were also established, showing that strong electron-withdrawing groups like fluorine or hydroxyl directly correlate with enhanced monomer reactivity, optimizing synthetic conditions. Incorporating fluorine into the monomer structure significantly improved the resulting MOF properties, providing a valuable design strategy for future monomers. Finally, this research demonstrated that wavy 2D c-MOFs can rival traditional flat ligands in terms of crystallinity and electronic properties, such as conductivity and charge carrier mobility, thereby expanding the potential for novel 2D c-MOF members.

L’essor de la chimie supramoléculaire et plus particulièrement de la tectonique moléculaire a rendu la formation de matériaux poreux hautement organisés possible. La fonctionnalisation de tels composés favorise leur utilisation pour de nombreuses applications. Les travaux présentés dans cette thèse ont été consacrés aux réseaux moléculaires poreux homochiraux ainsi que leur utilisation pour le stockage de gaz, la reconnaissance et la séparation d’énantiomères.Le premier chapitre décrit la synthèse de divers ligands organiques optiquement purs et leur assemblage avec des sels de cuivre pour l’obtention de monocristaux. Les isothermes d’adsorption de chacun de ces composés cristallins ont été mesurés via des analyses BET et le stockage de N2,CO2 et CH4 ont été évalué.Le second chapitre s’intéresse à l’utilisation de ces mêmes composés chiraux pour la reconnaissance des énantiomères (L)- et (D)-tryptophane. Des tests de séparation énantiosélective de molécules aminées ou dérivées d’amides sont également exposés.Le dernier chapitre décrit la formation de réseaux moléculaire mono- et tridimensionnels par l’association de ligands organiques avec des sels métalliques variés. Leurs structures cristallines ont pu être déterminées par diffraction des rayons X sur monocristal. / The development in supramolecular chemistry and more particularly in molecular tectonics has madepossible the formation of porous and highly organized materials. The functionalization of suchcompounds favored their use for various applications. This PhD work is about the application ofporous homochiral coordination networks for storage, enantioselective recognition or separation.The first chapter deals with the synthesis of chiral ligands and their combinations with copper salts toenable the formation of single crystals. Their adsorption isotherms were evaluated by BETmeasurements. Storage of N2, CO2 and CH4 by these crystalline architectures was also evaluated.The second part describes the use of these chiral compounds for enantioselective recognition of (L)-and (D)-tryptophan. Tests of enantioselective separation of amines or amides were also carried out.The last part of this work deals with the formation of mono- or tridimensional coordination polymersby combinations of organic ligands and a variety of metallic salts. Their structures were determinedby X-ray diffraction on single crystal.

Made available in DSpace on 2014-12-17T15:42:25Z (GMT). No. of bitstreams: 1 VivianeOC_DISSERT.pdf: 3402531 bytes, checksum: e2e7a469bf001a9ef16d573773ea7bda (MD5) Previous issue date: 2014-01-24 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / Metal Organic Frameworks (MOFs) are supramolecular structures consisted of ions or metal clusters coordinated to organic ligands which are repeated in two or three dimensions. These structures have atracted much attention due to their properties such as low density, high specific surface area and large volume of pores. In this work, MOFs consisted of zinc clusters connected by ditopic ligands, terephthalic acid (1,4- H2BDC) or isophthalic acid (1,3-H2BDC) were synthesized. To obtain the proposed materials, different routes and synthetic parameters were tested, such as the molar ratio of the precursors, the addition of template molecules, the type of solvente, the addition of organic base or the type of a counter-ion of Zn salt. It was found that the variation of these parameters led to the formation of different metalorganic structures. The solids obtained were characterized by XRD, SEM and IR. For the samples identified as MOF- 5, it was verified that the structure was composed of both interpenetrated and non interpenetrated structures. These samples showed a low stability, becoming totally transformed into another structure within less than 72 hours. The addition of the nickel and/or cobalt was found to be a promissing method for increasing the stability of MOF- 5, which in this case, still remained unconverted to another structure even after 15 days of exposure to air. The samples prepared from 1,3-H2BDC were probably new, still unknown Metal Organic Frameworks / Redes Metalorg?nicas (MOFs) s?o estruturas supramoleculares constitu?das de ?ons ou clusters met?licos coordenados com ligantes org?nicos que se repetem em duas (2D) ou tr?s (3D) dimens?es. Essas estruturas t?m atra?do muita aten??o devido ?s suas propriedades, como por exemplo, baixa densidade, elevada ?rea superficial espec?fica e elevado volume de poro livre. Neste trabalho foram sintetizadas MOFs formadas por clusters met?licos de zinco conectados por ligantes dit?picos, ?cido tereft?lico (1,4- H2BDC) ou isoft?lico (1,3-H2BDC). Para a obten??o dos materiais propostos foram testadas diferentes rotas e par?metros de s?ntese, tais como, raz?o molar dos precursores, adi??o de mol?culas de molde, tipo de solvente, adi??o de base org?nica ou do contra-?on do sal de Zn. Constatou-se que a varia??o destes par?metros pode conduzir a forma??o de diferentes estruturas metalorg?nicas. Os s?lidos obtidos foram caracterizados por DRX, MEV e IV e TG. Para as amostras onde foi identificada a rede metalorg?nica MOF-5 verificou-se a exist?ncia de por??es de estrutura interpenetrada, assim como de estrutura n?o interpenetrada. Estas amostras apresentaram baixa estabilidade, convertendo-se totalmente em outra estrutura num per?odo de tempo inferior a 72 h. A adi??o de n?quel e/ou cobalto mostrou-se promissora para o aumento de estabilidade da MOF-5, a qual foi identificada mesmo ap?s 15 dias de exposi??o ao ar. Dentre as amostras preparadas com 1,3-H2BDC apenas uma estrutura foi identificada, com base nos bancos de dados de estruturas conhecidas, levando a crer que tr?s redes metalorg?nicas obtidas apresentam estruturas in?ditas

MOF-5 ist der Archetyp einer neuartigen Klasse hochporöser Materialien, den Metal Organic Frameworks, die unter anderem zur Anwendung als effektive Gasspeicher geeignet sind. Im Rahmen dieser Arbeit werden die seiner Bildung zugrunde liegenden Reaktionen untersucht. Aus den Erkenntnissen dieser Untersuchungen wurden zwei neue Syntheseverfahren entwickelt. Eines der Verfahren beruht auf der Phasenumwandlung von Zinkterephthalaten und ermöglichte die Laborsynthese von MOF-5 in 100 g-Mengen. Ein zweites Verfahren bedient sich des Strukturaufbaus mit Hilfe vorgefertigter anorganischer Cluster, wodurch erstmals die Synthese von MOF-5-Homologen anderer Metalle als Zink gelang.

Submitted by ANA KARLA PEREIRA RODRIGUES (anakarla_@hotmail.com) on 2017-08-01T12:29:24Z No. of bitstreams: 1 arquivototal.pdf: 4942842 bytes, checksum: f0ad011fa73c8b3eb2a49c98e8ca9de4 (MD5) / Made available in DSpace on 2017-08-01T12:29:24Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 4942842 bytes, checksum: f0ad011fa73c8b3eb2a49c98e8ca9de4 (MD5) Previous issue date: 2017-02-15 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / Currently several works have been developed in order to provide alternative routes for the synthesis of several organic compounds. These new protocols are generally aimed at obtaining softer and more eco-friendly reactive conditions, better yields and / or reactional times, and mechanistic studies, among others. This work consists of the study of synthesis routes of cyanohydrins and tetrahydropyrans, using lanthanide catalysts and ionic liquids, respectively. As cyanohydrins are products that can be transformed into important organic intermediates. They are obtained by the cyanosilylation of aldehydes reaction, which is synthetically viable only in the presence of a Lewis acid. In this work, the MOF [Eu2 (MELL)(H2O)6] was used as a heterogeneous catalyst in the cyanosilylation of aldehydes reaction. The catalytic assays were optimized using a thermally activated MOF in acetonitrile. Different aldehydes several structurally provided their respective cyanohydrins ranging from 1 to 6 hours and yields of 62 to 100%. The MOF was recycled in the addition reaction of TMSCN to 2-furfuraldehyde without loss of activity for five cycles. Tetrahydropyran rings (THP) are common in many natural products, so various strategies are being developed to synthesize them. In this work we also describe the study to obtain 2,4,6-trisubstituted tetrahydropyrans in a single step promoted by the ionic liquid (IL) BMIM][PF6] between the allyl bromide and aldehydes, through the Barbier-Prins reaction. The tests were performed under different conditions and optimized using 1: 4 benzaldehyde and allyl bromide. The use of IL [BMIM][PF6] provided THPs of various aldehydes in good yields ranging from 40% to 75% in 8 hours of reaction. In addition, IL [BMIM][PF6] was recovered and reused in the preparation of 4-bromo-2,6-diphenyl-tetrahydro-2H-pyran by up to 5 times without significant loss of yield of that product. The influence of the PF6- anion on the reaction between benzaldehyde and allyl bromide under the Barbier reaction conditions was investigated, as well as the influence of SnBr2 salt on the Prins cyclization reaction between homoallylic alcohol and benzaldehyde. The results show evidence that PF6- acts by accelerating the Barbier reaction and the excess of SnBr2 acts as Lewis acid in the Prins cyclization reaction. Subsequently, the use of KI in the reaction between benzaldehyde and allyl bromide was investigated, and it was found that depending on the ratio used between KI and SnBr2, the preferential formation of homoalyl alcohol or THP compound could occur. / Atualmente vários trabalhos têm sido desenvolvidos no intuito de possibilitar rotas alternativas para a síntese de diversos compostos orgânicos. Esses novos protocolos visam geralmente a obtenção de condições reacionais mais brandas e eco-amigáveis, melhores rendimentos e/ou tempos reacionais, estudos mecanísticos entre outros. Este trabalho consiste no estudo de rotas de síntese de cianoidrinas e tetraidropiranos, utilizando catalisadores de lantanídeos e líquidos iônicos, respectivamente. As cianoidrinas são substâncias que podem ser transformadas em intermediários orgânicos importantes. São geralmente obtidas através da reação de cianossililação de aldeídos, que é sinteticamente viável apenas na presença de um ácido de Lewis. Nesse trabalho, a MOF [Eu2(MELL)(H2O)6] foi utilizada como catalisador heterogêneo na reação de cianossililação de aldeídos. Os ensaios catalíticos foram otimizados utilizando a MOF ativada termicamente em acetonitrila. Diversos aldeídos estruturalmente diferentes forneceram suas respectivas cianoidrinas variando de 1 a 6 horas e com rendimentos de 62 a 100%. A MOF foi reciclada na reação de adição de TMSCN à 2-furfuraldeído sem perda de atividade durante cinco ciclos. Anéis tetraidropirânicos (THP) são comuns em vários produtos naturais, portanto várias estratégias estão sendo desenvolvidas para sintetizá-los. Nesse trabalho descrevemos também o estudo para a obtenção de tetraidropiranos 2,4,6-trissubstituídos meso em uma única etapa promovida pelo líquido iônico (LI) BMIM][PF6] entre o brometo de alila e aldeídos, através da reação Barbier-Prins. Os testes foram realizados sob diferentes condições e foi otimizado utilizando-se o benzaldeído e brometo de alila na proporção 1:4. A utilização LI [BMIM][PF6] forneceu produtos THPs de vários aldeídos com bons rendimentos variando-se de 40% a 75% em 8 horas de reação. Adicionalmente o LI [BMIM][PF6] foi recuperado e reutilizado na preparação do 4-bromo-2,6-difenil-tetraidro-2H-pirano em até 5 vezes sem perda significativa dos rendimentos desse produto. Foi investigado a influência isolada do ânion PF6- na reação entre o benzaldeído e o brometo de alila nas condições reacionais de Barbier, assim como a influência do sal SnBr2 na reação de ciclização de Prins entre o álcool homoalílico e o benzaldeído. Os resultados mostram evidências que o PF6- atua acelerando a reação de Barbier e o excesso de SnBr2 atua como ácido de Lewis na reação de ciclização de Prins. Posteriormente foi investigado a utilização do KI na reação entre o benzaldeído e o brometo de alila, e verificou-se que dependendo da proporção utilizada entre o KI e o SnBr2 pode ocorrer a formação preferencial do álcool homoalílico ou do composto THP.Atualmente vários trabalhos têm sido desenvolvidos no intuito de possibilitar rotas alternativas para a síntese de diversos compostos orgânicos. Esses novos protocolos visam geralmente a obtenção de condições reacionais mais brandas e eco-amigáveis, melhores rendimentos e/ou tempos reacionais, estudos mecanísticos entre outros. Este trabalho consiste no estudo de rotas de síntese de cianoidrinas e tetraidropiranos, utilizando catalisadores de lantanídeos e líquidos iônicos, respectivamente. As cianoidrinas são substâncias que podem ser transformadas em intermediários orgânicos importantes. São geralmente obtidas através da reação de cianossililação de aldeídos, que é sinteticamente viável apenas na presença de um ácido de Lewis. Nesse trabalho, a MOF [Eu2(MELL)(H2O)6] foi utilizada como catalisador heterogêneo na reação de cianossililação de aldeídos. Os ensaios catalíticos foram otimizados utilizando a MOF ativada termicamente em acetonitrila. Diversos aldeídos estruturalmente diferentes forneceram suas respectivas cianoidrinas variando de 1 a 6 horas e com rendimentos de 62 a 100%. A MOF foi reciclada na reação de adição de TMSCN à 2-furfuraldeído sem perda de atividade durante cinco ciclos. Anéis tetraidropirânicos (THP) são comuns em vários produtos naturais, portanto várias estratégias estão sendo desenvolvidas para sintetizá-los. Nesse trabalho descrevemos também o estudo para a obtenção de tetraidropiranos 2,4,6-trissubstituídos meso em uma única etapa promovida pelo líquido iônico (LI) BMIM][PF6] entre o brometo de alila e aldeídos, através da reação Barbier-Prins. Os testes foram realizados sob diferentes condições e foi otimizado utilizando-se o benzaldeído e brometo de alila na proporção 1:4. A utilização LI [BMIM][PF6] forneceu produtos THPs de vários aldeídos com bons rendimentos variando-se de 40% a 75% em 8 horas de reação. Adicionalmente o LI [BMIM][PF6] foi recuperado e reutilizado na preparação do 4-bromo-2,6-difenil-tetraidro-2H-pirano em até 5 vezes sem perda significativa dos rendimentos desse produto. Foi investigado a influência isolada do ânion PF6- na reação entre o benzaldeído e o brometo de alila nas condições reacionais de Barbier, assim como a influência do sal SnBr2 na reação de ciclização de Prins entre o álcool homoalílico e o benzaldeído. Os resultados mostram evidências que o PF6- atua acelerando a reação de Barbier e o excesso de SnBr2 atua como ácido de Lewis na reação de ciclização de Prins. Posteriormente foi investigado a utilização do KI na reação entre o benzaldeído e o brometo de alila, e verificou-se que dependendo da proporção utilizada entre o KI e o SnBr2 pode ocorrer a formação preferencial do álcool homoalílico ou do composto THP.

Made available in DSpace on 2016-03-15T19:38:12Z (GMT). No. of bitstreams: 1 Igor da Silva Ramos.pdf: 1622777 bytes, checksum: 186a77eaabf846baf8466f41da580a23 (MD5) Previous issue date: 2009-02-03 / Fundo Mackenzie de Pesquisa / This work studies, through systemic modeling a microstructured optical fiber used in a module for dispersion compensation and Raman amplification for optical communication systems. The use of this device compensates the dispersion in a range of frequencies not covered by conventional dispersion compensating fibers and, simultaneously, amplifies the signal in order to reach longer transmission distances. In particular, dispersion compensation and amplification is demonstrated in the O Band (1260 nm up to 1360 nm) for systems operating at 10 and 40 Gbps. For this purpose, the parameters of a real microstructured optical fiber model are used in the VPI TransmissionMaker numerical simulation software through which is possible to evaluate the performance of the device. The performance evaluation is carried out through Bit Error Rate (BER) as a function of link distance and transmission channel wavelength. / Este trabalho estuda através de modelamento sistêmico, uma fibra óptica microestruturada utilizada em um módulo de compensação de dispersão e amplificação Raman de sistemas ópticos. O uso deste dispositivo compensa a dispersão em faixas de freqüência não cobertas por fibras de compensação de dispersão convencionais e simultaneamente amplifica o sinal a fim de permitir maiores distâncias de transmissão. Em particular, compensação de dispersão e amplificação são demonstradas na banda O (1260 nm a 1360 nm) para sistemas operando a taxas de 10 e 40 Gbps. Para isso, são utilizadas as características de um modelo de fibra microestruturada real no software de simulação numérica VPI TransmissionMaker por meio do qual é possível avaliar o desempenho deste dispositivo. A avaliação de desempenho é feita através de curvas de taxa de erro de bits (BER, do inglês Bit Error Rate) em função do comprimento do enlace e comprimento de onda do canal de transmissão.