- A drug-loaded nanoscale metal-organic framework with a tumor targeting agent for highly effective hepatoma therapy
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Drug delivery systems with targeting agents for precise drug release in cancer therapy are very significant and important. Herein, we report the rational design and synthesis of a DOX (doxorubicin) loaded UiO-68-type of nanoscale metal-organic framework (NMOF) with a tumor targeting agent (folic acid, FA), DOX@UiO-68-FA (3), as a multifunctional drug delivery system for hepatoma (Hep G2) therapy via tail-vein injection. Compared to free DOX, FA-unloaded DOX@Mi-UiO-68 (2), 3 exhibits a much higher antitumor efficacy, which was confirmed by cell imaging, standard 3-(4,5-dimethylthiahiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) proliferation and in vivo experiments.
- Li, Yan-An,Zhao, Xiao-Dong,Yin, Hai-Peng,Chen, Gong-Jun,Yang, Song,Dong, Yu-Bin
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Read Online
- An Azobenzene-Modified Photoresponsive Thorium-Organic Framework: Monitoring and Quantitative Analysis of Reversible trans-cis Photoisomerization
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Monitoring and quantification of the photoresponsive behavior of metal-organic frameworks that respond to a light stimulus are crucial to establish a clear structure-activity relationship related to light regulation. Herein, we report the first azobenzene-modified photoresponsive thorium-organic framework (Th-Azo-MOF) with the formula [Th6O4(OH)4(H2O)6L6] (H2L = (E)-2′-p-tolyldiazenyl-1,1′:4′,4′-terphenyl-4,4″-dicarboxylic acid), in which the utilization of a thorium cluster as a metal node leads to one of the largest pore sizes among all the azobenzene-containing metal-organic frameworks (MOFs). The phototriggered transformation of the trans isomer to the cis isomer is monitored and characterized quantitatively by comprehensive analyses of NMR and UV spectroscopy, which reveals that the maximum isomerization ratio of cisTh-Azo-MOF in the solid state is 19.7% after irradiation for 120 min, and this isomerization is reversible and can be repeated several times without apparent performance changes. Moreover, the isomerization-related difference in the adsorption of the Rhodamine B guest is also illustrated and a possible photoregulated mechanism is proposed. This work will shed light on new explorations for constructing functionalized actinide porous materials by the elegant combination of actinide nodes with tailored organic ligands and furthermore will provide a comprehensive understanding of photoisomerization processes in MOF solids and insight into the mechanism on photoregulated cargo adsorption and release by photoactive MOFs.
- Chai, Zhi-Fang,Feng, Wen,Geng, Jun-Shan,Hu, Kong-Qiu,Liang, Yuan-Yuan,Liu, Kang,Mei, Lei,Shi, Wei-Qun,Yu, Ji-Pan,Yuan, Li-Hua
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- Crystalline Nanochannels with Pendant Azobenzene Groups: Steric or Polar Effects on Gas Adsorption and Diffusion?
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An azobenzene-containing, zirconium-based metal-organic framework (AzoMOF), upon irradiation with ultraviolet (UV) light at 365 ± 10 nm, underwent trans-to-cis isomerization of its azobenzene pendants to furnish the cis-isomer content of 21% (AzoMOF21%) in 30 min at the photostationary state and underwent backward isomerization into AzoMOF1% upon either irradiation with visible light (420-480 nm) or heating. When the cis-isomer content increased, the diffusion rate and amount of CO2 adsorbed into the nanochannels of AzoMOF decreased considerably. When erythrosine B, a polarity-probing guest, was used, it showed a red shift upon exposure of AzoMOF20%?EB to visible light, indicating that the interior environment of AzoMOF turns less polar as the trans-isomer content becomes higher. In sharp contrast, the adsorption profiles of AzoMOF15% and AzoMOF1% for Ar having an analogous kinetic diameter to CO2 but no quadrupole moment and a smaller polarizability were virtually identical to one another. Therefore, it is likely that CO2 experiences a dominant effect of a polar effect rather than a steric effect in the crystalline nanochannels.
- Huang, Hubiao,Sato, Hiroshi,Aida, Takuzo
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- Zirconium-based MOF catalyst with double active sites and preparation method and application thereof
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The invention discloses a zirconium-based MOF catalyst loaded with double active sites as well as a preparation method and an application of the zirconium-based MOF catalyst. The method comprises thefollowing steps: adding zirconium salt and an organic ligand into an organic solvent, taking organic acid as a regulator, and carrying out self-assembly reaction to obtain a metal organic framework; adding salicylaldehyde for aldehyde amine condensation to obtain chelating coordination sites, adding palladium salt, and performing coordination through an impregnation method; reducing the obtained MOF in hydrogen to obtain an MOF loaded with Pd nanoparticles; reacting MOF and zinc salt in an organic solvent, and obtaining the catalyst. The Pd-Zn-coated UiO-68-NH2-CH3 catalyst synthesized by thepreparation method disclosed by the invention has efficient catalytic activity in a tandem alcohol oxidation/aldehyde cyanosilylation reaction. According to the catalyst, a metal organic framework UiO-68-NH2-CH3 is constructed, Pd nanoparticles and Zn are loaded by taking the metal organic framework UiO-68-NH2-CH3 as a carrier, the loading capacity of the Pd nanoparticles is 4-8wt%, and the loading capacity of the Zn is 3-5wt%.
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Paragraph 0050-0052
(2021/06/09)
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- Amino Acid-Functionalized Metal-Organic Frameworks for Asymmetric Base–Metal Catalysis
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We report a strategy to develop heterogeneous single-site enantioselective catalysts based on naturally occurring amino acids and earth-abundant metals for eco-friendly asymmetric catalysis. The grafting of amino acids within the pores of a metal-organic framework (MOF), followed by post-synthetic metalation with iron precursor, affords highly active and enantioselective (>99 % ee for 10 examples) catalysts for hydrosilylation and hydroboration of carbonyl compounds. Impressively, the MOF-Fe catalyst displayed high turnover numbers of up to 10 000 and was recycled and reused more than 15 times without diminishing the enantioselectivity. MOF-Fe displayed much higher activity and enantioselectivity than its homogeneous control catalyst, likely due to the formation of robust single-site catalyst in the MOF through site-isolation.
- Newar, Rajashree,Akhtar, Naved,Antil, Neha,Kumar, Ajay,Shukla, Sakshi,Begum, Wahida,Manna, Kuntal
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supporting information
p. 10964 - 10970
(2021/03/29)
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- Single-Site Cobalt-Catalyst Ligated with Pyridylimine-Functionalized Metal-Organic Frameworks for Arene and Benzylic Borylation
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We report a highly active single-site heterogeneous cobalt-catalyst based on a porous and robust pyridylimine-functionalized metal-organic frameworks (pyrim-MOF) for chemoselective borylation of arene and benzylic C-H bonds. The pyrim-MOF having UiO-68 topology, constructed from zirconium-cluster secondary building units and pyridylimine-functionalized dicarboxylate bridging linkers, was metalated with CoCl2 followed by treatment of NaEt3BH to give the cobalt-functionalized MOF-catalyst (pyrim-MOF-Co). Pyrim-MOF-Co has a broad substrate scope, allowing the C-H borylation of halogen-, alkoxy-, alkyl-substituted arenes as well as heterocyclic ring systems using B2pin2 or HBpin (pin = pinacolate) as the borylating agent to afford the corresponding arene- or alkyl-boronate esters in good yields. Pyrim-MOF-Co gave a turnover number (TON) of up to 2500 and could be recycled and reused at least 9 times. Pyrim-MOF-Co was also significantly more robust and active than its homogeneous control, highlighting the beneficial effect of active-site isolation within the MOF framework that prevents intermolecular decomposition. The experimental and computational studies suggested (pyrim?-)CoI(THF) as the active catalytic species within the MOF, which undergoes a mechanistic pathway of oxidative addition, turnover limiting σ-bond metathesis, followed by reductive elimination to afford the boronate ester.
- Akhtar, Naved,Antil, Neha,Balendra,Begum, Wahida,Kumar, Ajay,Manna, Kuntal,Newar, Rajashree,Shukla, Sakshi
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supporting information
p. 10473 - 10481
(2020/08/05)
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- Metal-organic frameworks containing nitrogen-donor ligands for efficient catalytic organic transformations
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Metal-organic framework (MOFs) compositions based on nitrogen donor-based organic bridging ligands, including ligands based on 1,3-diketimine (NacNac), bipyridines and salicylaldimine, were synthesized and then post-synthetically metalated with metal precursors, such as complexes of first row transition metals. Metal complexes of the organic bridging ligands could also be directly incorporated into the MOFs. The MOFs provide a versatile family of recyclable and reusable single-site solid catalysts for catalyzing a variety of asymmetric organic transformations. The solid catalysts can also be integrated into a flow reactor or a supercritical fluid reactor.
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Page/Page column 41-42
(2020/06/03)
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- Catalysis through Dynamic Spacer Installation of Multivariate Functionalities in Metal-Organic Frameworks
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We demonstrate herein a facile strategy to engineer versatile catalytically active coordination interspace in the same primitive metal-organic framework (MOF) for variable heterogeneous catalysis. Different functional ligands can be reversibly inserted into and removed from proto-LIFM-28 individually or successively to bring in single or binary catalytic sites for specific reactions and switch the parent MOF to multipurpose catalysts. Alcohol-oxidation, Knoevenagel-condensation, click, acetal, and Baylis-Hillman reactions are achievable through simple exchange of a single catalytic spacer, while sequential or stepwise reactions are designable via selective combination of two catalytic spacers with different functionalities, thus making proto-LIFM-28 a multivariate MOF for multiuse and economic catalysis.
- Cao, Chen-Chen,Chen, Cheng-Xia,Wei, Zhang-Wen,Qiu, Qian-Feng,Zhu, Neng-Xiu,Xiong, Yang-Yang,Jiang, Ji-Jun,Wang, Dawei,Su, Cheng-Yong
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supporting information
p. 2589 - 2593
(2019/03/04)
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- Different functional group modified zirconium frameworks for the photocatalytic reduction of carbon dioxide
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Conversion of carbon dioxide (CO2) into useful chemicals is an important and urgent task from the energy and environment perspective. Herein, through a post-synthetic modification (PSM) approach, we synthesized three new metal-organic frameworks (MOFs) UiO-68-PSMs with different functional groups, namely, UiO-68-F, UiO-68-CH3 and UiO-68-OCH3, for the photocatalytic reduction of CO2. By introducing electron-withdrawing and electron-donating groups, UiO-68-PSMs showed different performance for the selective photocatalytic reduction of CO2 to CO because of change in charge separation and band gap of UiO caused by the presence of different functional groups.
- Wei, Yuan-Ping,Liu, Yi,Guo, Fan,Dao, Xiao-Yao,Sun, Wei-Yin
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supporting information
p. 8221 - 8226
(2019/06/18)
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- Thermally activated delayed fluorescence of a Zr-based metal-organic framework
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The first metal-organic framework exhibiting thermally activated delayed fluorescence (TADF) was developed. The zirconium-based framework (UiO-68-dpa) uses a newly designed linker composed of a terphenyl backbone, an electron-accepting carboxyl group, and an electron-donating diphenylamine and exhibits green TADF emission with a photoluminescence quantum yield of 30% and high thermal stability.
- Mieno,Kabe,Allendorf,Adachi
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supporting information
p. 631 - 634
(2018/02/06)
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- Synthesis method for increasing Pd content of metal organic framework based on Zr(IV) ions
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The invention discloses a synthesis method for increasing the Pd content of a metal organic framework based on Zr(IV) ions. The method comprises the following steps: performing a coordination polymerization reaction between an organic ligand (I) and ZrCl4, and performing post-synthesis modification of the product, wherein the post-synthesis modification comprises the following specific steps: enabling a coordination polymerization reaction product, 2-pyridylaldehyde or salicylaldehyde and a catalyst formic acid in a molar ratio of 1:(1-4):(0.1-0.3) to react in an organic solvent; performing centrifugal washing of the product and dispersing in an organic solvent; adding palladium nitrate in a molar ratio of 1:(0.8-1.2); after the reactions, centrifuging and drying to obtain powder; dispersing the obtained powder into water; adding sodium borohydride in a molar ratio of 1:(0.5-1.5); and after the reactions, centrifuging, washing and drying to obtain the product. In the invention, the synthesized compound is an organic-inorganic composite supermolecular material and has a metal organic framework which is easy to operate and low in cost and has nanoscale particle size; and the compound has very high efficiency when being used as a catalytic material for benzyl alcohol oxidation and benzaldehyde condensation.
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Paragraph 0037; 0038
(2016/10/27)
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- Pd(0)@UiO-68-AP: Chelation-directed bifunctional heterogeneous catalyst for stepwise organic transformations
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A bifunctional heterogeneous catalyst Pd(0)@UiO-68-AP based on a chelation-directed post-synthetic approach is reported. It exhibits typical heterogeneous catalytic behaviour and can promote benzyl alcohol oxidiation-Knoevenagel condensation in a stepwise way.
- Li, Yan-An,Yang, Song,Liu, Qi-Kui,Chen, Gong-Jun,Ma, Jian-Ping,Dong, Yu-Bin
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supporting information
p. 6517 - 6520
(2016/06/01)
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- NANOPARTICLES FOR PHOTODYNAMIC THERAPY, X-RAY INDUCED PHOTODYNAMIC THERAPY, RADIOTHERAPY, CHEMOTHERAPY, IMMUNOTHERAPY, AND ANY COMBINATION THEREOF
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Metal-organic frameworks (MOFs) comprising photosensitizers are described. The MOFs can also include moieties capable of absorbing X- rays and/or scintillation. Optionally, the photosensitizer or a derivative thereof can form a bridging ligand of the MOF. Further optionally, the MOF can comprise inorganic nanoparticles in the cavities or channels of the MOF or can be used in combination with an inorganic nanoparticle. Also described are methods of using MOFs and/or inorganic nanoparticles in photodynamic therapy or in X-ray induced photodynamic therapy, either with or without the co-administration of one or more immunotherapeutic agent and/or one or more chemotherapeutic agent.
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Page/Page column 91
(2016/05/24)
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- Preparation method for light-control medicine-release metal organic frame compound
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The invention provides a preparation method for a light-control medicine-release metal organic frame compound. The preparation method comprises the following steps: azo ligand, acetic acid and zirconium tetrachloride are utilized to be dissolved in N,N-dimethyl formamide to obtain a metal organic frame, and then medicines and beta cyclodextrin are introduced so as to prepare the compound. Beta cyclodextrin can be combined with trans azo, so that the system does not release when not accepting the outside stimulus, and only release when accepting ultraviolet radiation or being added with amantadine, that is, the prepared metal organic frame compound can realize controllable medicine release.
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Paragraph 0020; 0044; 0045; 0046
(2016/10/10)
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- NANOSCALE CARRIERS FOR THE DELIVERY OR CO-DELIVERY OF CHEMOTHERAPEUTICS, NUCLEIC ACIDS AND PHOTOSENSITIZERS
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Nanoscale coordination polymer nanoparticles for the co-delivery of multiple therapeutic agents are described. The multiple therapeutic agents can include a combination of different chemotherapeutic agents, a combination of one or more chemotherapeutic agents and one or more nucleic acids, such as small interfering RNA (siRNA) or microRNA, a combination of one or more chemotherapeutic agents and a photosensitizer (i.e., for use in photodynamic therapy), or a plurality of different siRNAs. Pharmaceutical formulations including the nanoparticles, methods of using the nanoparticles to treat cancer, and methods of making the nanoparticles are also described.
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Page/Page column 67
(2015/05/26)
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- Nanoscale metal-organic frameworks for the co-delivery of cisplatin and pooled siRNAs to enhance therapeutic efficacy in drug-resistant ovarian cancer cells
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Ovarian cancer is the leading cause of death among women with gynecological malignancies. Acquired resistance to chemotherapy is a major limitation for ovarian cancer treatment. We report here the first use of nanoscale metal-organic frameworks (NMOFs) for the co-delivery of cisplatin and pooled small interfering RNAs (siRNAs) to enhance therapeutic efficacy by silencing multiple drug resistance (MDR) genes and resensitizing resistant ovarian cancer cells to cisplatin treatment. UiO NMOFs with hexagonal-plate morphologies were loaded with a cisplatin prodrug and MDR gene-silencing siRNAs (Bcl-2, P-glycoprotein [P-gp], and survivin) via encapsulation and surface coordination, respectively. NMOFs protect siRNAs from nuclease degradation, enhance siRNA cellular uptake, and promote siRNA escape from endosomes to silence MDR genes in cisplatin-resistant ovarian cancer cells. Co-delivery of cisplatin and siRNAs with NMOFs led to an order of magnitude enhancement in chemotherapeutic efficacy in vitro, as indicated by cell viability assay, DNA laddering, and Annexin V staining. This work shows that NMOFs hold great promise in the co-delivery of multiple therapeutics for effective treatment of drug-resistant cancers.
- He, Chunbai,Lu, Kuangda,Liu, Demin,Lin, Wenbin
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supporting information
p. 5181 - 5184
(2014/05/06)
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- A metal-organic framework containing unusual eight-connected Zr-oxo secondary building units and orthogonal carboxylic acids for ultra-sensitive metal detection
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Two metal-organic frameworks (MOFs) with Zr-oxo secondary building units (SBUs) were prepared by using p,p′-terphenyldicarboxylate (TPDC) bridging ligands pre-functionalized with orthogonal succinic acid (MOF-1) and maleic acid groups (MOF-2). Single-crystal X-ray structure analysis of MOF-1 provides the first direct evidence for eight-connected SBUs in UiO-type MOFs. In contrast, MOF-2 contains twelve-connected SBUs as seen in the traditional UiO MOF topology. These structural assignments were confirmed by extended X-ray absorption fine structure (EXAFS) analysis. The highly porous MOF-1 is an excellent fluorescence sensor for metal ions with the detection limit of 2+and three to four orders of magnitude greater sensitivity for metal ions than previously reported luminescent MOFs.
- Carboni, Michal,Lin, Zekai,Abney, Carter W.,Zhang, Teng,Lin, Wenbin
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supporting information
p. 14965 - 14970
(2015/02/19)
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- Salicylaldimine-based metal - Organic framework enabling highly active olefin hydrogenation with iron and cobalt catalysts
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A robust and porous Zr metal - organic framework, sal-MOF, of UiO topology was synthesized using a salicylaldimine (sal)-derived dicarboxylate bridging ligand. Postsynthetic metalation of sal-MOF with iron(II) or cobalt(II) chloride followed by treatment with NaBEt3H in THF resulted in Fe- and Co-functionalized MOFs (sal-M-MOF, M = Fe, Co) which are highly active solid catalysts for alkene hydrogenation. Impressively, sal-Fe-MOF displayed very high turnover numbers of up to 145000 and was recycled and reused more than 15 times. This work highlights the unique opportunity of developing MOF-based earth-abundant catalysts for sustainable chemical synthesis.
- Manna, Kuntal,Zhang, Teng,Carboni, Micha?l,Abney, Carter W.,Lin, Wenbin
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supporting information
p. 13182 - 13185
(2015/03/30)
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- Stepwise ligand exchange for the preparation of a family of mesoporous MOFs
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A stepwise ligand exchange strategy is utilized to prepare a series of isoreticular bio-MOF-100 analogues. Specifically, in situ ligand exchange with progressively longer dicarboxylate linkers is performed on single crystalline starting materials to synthesize products with progressively larger mesoporous cavities. The new members of this series of materials, bio-MOFs 101-103, each exhibit permanent mesoporosity and pore sizes ranging from ~2.1-2.9 nm and surface areas ranging from 2704 to 4410 m2/g. The pore volume for bio-MOF 101 is 2.83 cc/g. Bio-MOF-102 and 103 have pore volumes of 4.36 and 4.13 cc/g, respectively. Collectively, these data establish this unique family of MOFs as one of the most porous reported to date.
- Li, Tao,Kozlowski, Mark T.,Doud, Evan A.,Blakely, Maike N.,Rosi, Nathaniel L.
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supporting information
p. 11688 - 11691
(2013/09/02)
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- Modulated synthesis of Zr-based metal-organic frameworks: From nano to single crystals
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We present an investigation on the influence of benzoic acid, acetic acid, and water on the syntheses of the Zr-based metal-organic frameworks Zr-bdc (UiO-66), Zr-bdc-NH2 (UiO- 66-NH2), Zr-bpdc (UiO-67), and Zr- tpdc-NH2 (UiO-68-NH2) (H2bdc: terephthalic acid, H2bpdc: biphenyl-4,4'- dicarboxylic acid, H2tpdc: terphenyl- 4,4"-dicarboxylic acid). By varying the amount of benzoic or acetic acid, the synthesis of Zr-bdc can be modulated. With increasing concentration of the modulator, the products change from intergrown to individual crystals, the size of which can be tuned. Addition of benzoic acid also affects the size and morphology of Zr-bpdc and, additionally, makes the synthesis of Zr-bpdc highly reproducible. The control of crystal and particle size is proven by powder XRD, SEM and dynamic light scattering (DLS) measurements. Thermogravimetric analysis (TGA) and Ar sorption experiments show that the materials from modulated syntheses can be activated and that they exhibit high specific surface areas. Water proved to be essential for the formation of well-ordered Zr-bdc-NH2. Zr- tpdc-NH2, a material with a structure analogous to that of Zr-bdc and Zr- bpdc, but with the longer, functionalized linker 2'-amino-1,1':4',1"-terphenyl- 4,4"-dicarboxylic acid, was obtained as single crystals. This allowed the first single-crystal structural analysis of a Zr-based metal-organic framework. Copyright
- Schaate, Andreas,Roy, Pascal,Godt, Adelheid,Lippke, Jann,Waltz, Florian,Wiebcke, Michael,Behrens, Peter
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experimental part
p. 6643 - 6651
(2011/08/08)
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