Yes / Three highly porous Zr(IV)-based metal–organic frameworks, UBMOF-8, UBMOF-9, and UBMOF-31, were synthesized by using 2,2′-diamino-4,4′-stilbenedicarboxylic acid, 4,4′-stilbenedicarboxylic acid, and combination of both linkers, respectively. The mixed-linker UBMOF-31 showed excellent hydrogen uptake of 4.9 wt% and high selectivity for adsorption of CO2 over N2 with high thermal stability and moderate water stability with permanent porosity and surface area of 2552 m2 g−1. / University of Bath; Royal Society of Chemistry; Engineering and Physical Sciences Research Council

Yes / The synthesis of metal–organic frameworks with large three-dimensional channels that are permanently porous and chemically stable offers new opportunities in areas such as catalysis and separation. Two linkers (L1=4,4′,4′′,4′′′-([1,1′-biphenyl]-3,3′,5,5′-tetrayltetrakis(ethyne-2,1-diyl)) tetrabenzoic acid, L2=4,4′,4′′,4′′′-(pyrene-1,3,6,8-tetrayltetrakis(ethyne-2,1-diyl))tetrabenzoic acid) were used that have equivalent connectivity and dimensions but quite distinct torsional flexibility. With these, a solid solution material, [Zr6O4(OH)4(L1)2.6(L2)0.4]⋅(solvent)x, was formed that has three-dimensional crystalline permanent porosity with a surface area of over 4000 m2 g−1 that persists after immersion in water. These properties are not accessible for the isostructural phases made from the separate single linkers. / Financial support from EPSRC under EP/H000925, access to the HPC service ARCHER via EP/L000202. S.N. thanks the EU for a Marie Curie fellowship (PIEF-GA-2010-274952). C.M.-G. thanks the Spanish MINECO for a Ramón y Cajal Fellowship (RYC-2012-10894).

Yes / Pesticide contamination is a global issue, affecting nearly 44% of the global farming population, and disproportionately affecting farmers and agricultural workers in developing countries. Despite this, global pesticide usage is on the rise, with the growing demand of global food production with increasing population. Different types of porous materials, such as carbon and zeolites, have been explored for the remediation of pesticides from the environment. However, there are some limitations with these materials, especially due to lack of functional groups and relatively modest surface areas. In this regard, metal-organic frameworks (MOFs) provide us with a better alternative to conventionally used porous materials due to their versatile and highly porous structure. Recently, a number of MOFs have been studied for the extraction of pesticides from the environment as well as for targeted and controlled release of agrochemicals. Different types of pesticides and conditions have been investigated, and MOFs have proved their potential in agricultural applications. In this review, the latest studies on delivery and extraction of pesticides using MOFs are systematically reviewed, along with some recent studies on greener ways of pest control through the slow release of chemical compounds from MOF composites. Finally, we present our insights into the key issues concerning the development and translational applications of using MOFs for targeted delivery and pesticide control.

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京都大学 / 新制・課程博士 / 博士(工学) / 甲第25015号 / 工博第5192号 / 新制||工||1991(附属図書館) / 京都大学大学院工学研究科合成・生物化学専攻 / (主査)教授 古川 修平, 教授 生越 友樹, 教授 杉安 和憲 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

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Metal-Organic Frameworks (MOFs) are hybrid materials and are acknowledged as an important class of functional solid-state materials with high scientific interest in academia and industry alike. Their modular nature in terms of structural and compositional diversity, tunability, high surface area, and controlled pore size renders MOFs as the ideal candidate to address various persistent challenges pertaining to gas storage/separation, catalysis, drug delivery, and smart sensing. Through the field of reticular chemistry, targeted structures can be constructed through multiple design approaches, based on preselected building blocks prior to the assembly process. This thesis illustrates the merit of the supermolecular building layer (SBL) approach for the rational construction and discovery of highly connected and porous MOFs based on rare earth cations. Specifically, the emphasis of this study is on (i) the rational design and synthesis of 3-periodic MOFs based on SBLs pillared by ditopic ligands through post-synthetic modification (PSM) and in situ reactions. (ii) The investigation of the mixed-ligand system with different lengths and geometry of ditopic ligands on the isolation of metal clusters with distinct pore sizes. (iii) Gaining an overall insight into the exploration of different synthetic pathways that control the assembly of rare earth MOFs.

The work is focused on the investigation of synthesis and structure of crystalline coordination networks by combining first a row transition metal ion with one anionic and one neutral bridging ligand. In the field of crystalline coordination networks, the goal is to synthesize porous 3D crystalline coordination networks with molecular sized cavities. The materials are characterized by XRD and TGA. It is important to understand the structural topologies to develop practical applications, such as gas storage, gas separation, and catalysis. The bi- and tetra-dentate flexible imidazole ligands, 9,10-bis(imidazol-1-ylmethyl)anthracene (Chapter 2) and 1, 2, 4, 5-tetrakis(imidazol-1ylmethyl)benzene (Chapter 3), are synthesized and used as linkers to construct 1D, 2D, and 3D crystalline coordination networks with cobalt(II) or zinc(II) cations and H3BTC anions under solvothermal conditions. Two 1D chain networks, [M(HBTC²⁻)(C₂₂H₁₈N₄)(H₂O)₂]•H₂O, are constructed from M(Zn(II) or Co(II)), H₃BTC, and 9,10-bis(imidazol-1-ylmethyl)anthracene (Compound 2.1 and 2.2). These two 1D zigzag chains are linked into infinite 2D sheets by inter-chain π•••π stacking and hydrogen bonding. ⁺ Two 2D and one 3D cobalt(II) coordination networks are constructed from the tetradentate imidazole ligand and H3BTC. Compound 3.1 has a 2D corrugated sheet structure that is linked by inter-layer π•••π stacking and hydrogen bonding. Compound 3.2 has a 2D sheet structure. These sheets are interconnected by hydrogen bonds at the free acid group of the HBTC²⁻ ligand. Compound 3.3 forms a two fold interpenetrated 3D network structure. Void spaces in the structure are filled with six water molecules. Six 3D cobalt (II) coordination networks are constructed with bidentate rigid imidazole containing neutral ligands, 1,4-bis(imidazol-1-yl)benzene(L1), 1,4-bis(imidazol-1-yl)naphthalene(L2), and 9,10-bis(imidazol-1-yl)anthracene(L3), and H₂BDC or H₃BTC anion (Chapter 4). In 4.1-4.3, L1-L3 affects on degree of interpenetrations constructed with H₂BDC ligand. In 4.1 and 4.2 are interpenetrating 3D networks with no accessible void space. In 4.3, void spaces of 3D networks are filled with 2D sheets. Compounds 4.4-4.6 are prepared by different concentrations of starting materials and different solvents. In 4.4-4.6, L3 serves as a pillar building block to construct 3D networks by applying with H₃BTC ligand. The solvent exchange experiment for 4.4 is further discussed. / Ph. D.