Nat. Commun: Modulating supramolecular binding of carbon dioxide in a redox-active porous metal-organic framework
Zhenzhong Lu, Harry G. W. Godfrey, Ivan da Silva, Yongqiang Cheng, Mathew Savage, Floriana Tuna, Eric J. L. McInnes, Simon J. Teat, Kevin J. Gagnon, Mark D. Frogley, Pascal Manuel, Svemir Rudić, Anibal J. Ramirez-Cuesta, Timothy L. Easun, Sihai Yang & Martin Schröder
Nature Communications 8, Article number: 14212 (2017)
doi:10.1038/ncomms14212
Received:19 July 2016
Accepted:05 December 2016
Published online:13 February 2017
Hydrogen bonds dominate many chemical and biological processes, and chemical modification enables control and modulation of host–guest systems. Here we report a targeted modification of hydrogen bonding and its effect on guest binding in redox-active materials. MFM-300(VIII) {[VIII2(OH)2(L)], LH4=biphenyl-3,3′,5,5′-tetracarboxylic acid} can be oxidized to isostructural MFM-300(VIV), [VIV2O2(L)], in which deprotonation of the bridging hydroxyl groups occurs. MFM-300(VIII) shows the second highest CO2 uptake capacity in metal-organic framework materials at 298 K and 1 bar (6.0 mmol g−1) and involves hydrogen bonding between the OH group of the host and the O-donor of CO2, which binds in an end-on manner, =1.863(1) Å. In contrast, CO2-loaded MFM-300(VIV) shows CO2 bound side-on to the oxy group and sandwiched between two phenyl groups involving a unique ···c.g.phenyl interaction [3.069(2), 3.146(3) Å]. The macroscopic packing of CO2 in the pores is directly influenced by these primary binding sites.
http://www.nature.com/articles/ncomms14212.pdf
Nat. Chem: Hypersensitive dual-function luminescence switching of a silver-chalcogenolate cluster-based metal–organic framework
Ren-Wu Huang, Yong-Sheng Wei, Xi-Yan Dong, Xiao-Hui Wu, Chen-Xia Du, Shuang-Quan Zang & Thomas C. W. Mak
AffiliationsContributionsCorresponding author
Nature Chemistry (2017) doi:10.1038/nchem.2718
Received 26 August 2016 Accepted 07 December 2016 Published online 13 February 2017
Silver(I) chalcogenide/chalcogenolate clusters are promising photofunctional materials for sensing, optoelectronics and solar energy harvesting applications. However, their instability and poor room-temperature luminescent quantum yields have hampered more extensive study. Here, we graft such clusters to adaptable bridging ligands, enabling their interconnection and the formation of rigid metal–organic frameworks. By controlling the spatial separation and orientation of the clusters, they then exhibit enhanced stability (over one year) and quantum yield (12.1%). Ultrafast dual-function fluorescence switching (<1 s) is also achieved, with turn-off triggered by O2and multicoloured turn-on by volatile organic compounds. Single-crystal X-ray diffraction of the inclusion materials, obtained by single-crystal-to-single-crystal transformation, enables precise determination of the position of the small molecules within the framework, elucidating the switching mechanism. The work enriches the cluster-based metal–organic framework portfolio, bridges the gap between silver chalcogenide/chalcogenolate clusters and metal–organic frameworks, and provides a foundation for further development of functional silver-cluster-based materials.
http://www.nature.com/nchem/journal/vaop/ncurrent/full/nchem.2718.html
J. Am. Chem. Soc.: Postsynthetically Modified Covalent Organic Frameworks for Efficient and Effective Mercury RemovalQi Sun†, Briana Aguila†, Jason Perman† , Lyndsey D. Earl‡ , Carter W. Abney‡ , Yuchuan Cheng§, Hao Wei∥, Nicholas Nguyen†, Lukasz Wojtas†, and Shengqian Ma*†
† Department of Chemistry, University of South Florida, 4202 East Fowler Avenue, Tampa, Florida 33620, United States
‡ Chemical Sciences Division, Oak Ridge National Laboratory, P.O. Box 2008, Oak Ridge, Tennessee 37831, United States
§ Zhejiang Key Laboratory of Additive Manufacturing Materials, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, 1219 Zhongguan West Road, Ningbo, Zhejiang 315201, China
∥ School of Electronic Information and Electrical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China
J. Am. Chem. Soc., Article ASAP
DOI: 10.1021/jacs.6b12885
Publication Date (Web): February 13, 2017
Copyright © 2017 American Chemical Society
*sqma@usf.edu
A key challenge in environmental remediation is the design of adsorbents bearing an abundance of accessible chelating sites with high affinity, to achieve both rapid uptake and high capacity for the contaminants. Herein, we demonstrate how two-dimensional covalent organic frameworks (COFs) with well-defined mesopore structures display the right combination of properties to serve as a scaffold for decorating coordination sites to create ideal adsorbents. The proof-of-concept design is illustrated by modifying sulfur derivatives on a newly designed vinyl-functionalized mesoporous COF (COF-V) via thiol–ene 「click」 reaction. Representatively, the material (COF-S-SH) synthesized by treating COF-V with 1,2-ethanedithiol exhibits high efficiency in removing mercury from aqueous solutions and the air, affording Hg2+ and Hg0capacities of 1350 and 863 mg g–1, respectively, surpassing all those of thiol and thioether functionalized materials reported thus far. More significantly, COF-S-SH demonstrates an ultrahigh distribution coefficient value (Kd) of 2.3 × 109 mL g–1, which allows it to rapidly reduce the Hg2+ concentration from 5 ppm to less than 0.1 ppb, well below the acceptable limit in drinking water (2 ppb). We attribute the impressive performance to the synergistic effects arising from densely populated chelating groups with a strong binding ability within ordered mesopores that allow rapid diffusion of mercury species throughout the material. X-ray absorption fine structure (XAFS) spectroscopic studies revealed that each Hg is bound exclusively by two S via intramolecular cooperativity in COF-S-SH, further interpreting its excellent affinity. The results presented here thus reveal the exceptional potential of COFs for high-performance environmental remediation.
http://pubs.acs.org/doi/abs/10.1021/jacs.6b12885
Nat. Commun: Regulating the spatial distribution of metal nanoparticles within metal-organic frameworks to enhance catalytic efficiency
Qiu Yang, Wenxian Liu, Bingqing Wang, Weina Zhang, Xiaoqiao Zeng, Cong Zhang, Yongji Qin, Xiaoming Sun, Tianpin Wu, Junfeng Liu, Fengwei Huo & Jun Lu
Nature Communications 8, Article number: 14429 (2017)
doi:10.1038/ncomms14429
Received:06 September 2016
Accepted:28 December 2016
Published online:14 February 2017
Composites incorporating metal nanoparticles (MNPs) within metal-organic frameworks (MOFs) have broad applications in many fields. However, the controlled spatial distribution of the MNPs within MOFs remains a challenge for addressing key issues in catalysis, for example, the efficiency of catalysts due to the limitation of molecular diffusion within MOF channels. Here we report a facile strategy that enables MNPs to be encapsulated into MOFs with controllable spatial localization by using metal oxide both as support to load MNPs and as a sacrificial template to grow MOFs. This strategy is versatile to a variety of MNPs and MOF crystals. By localizing the encapsulated MNPs closer to the surface of MOFs, the resultant MNPs@MOF composites not only exhibit effective selectivity derived from MOF cavities, but also enhanced catalytic activity due to the spatial regulation of MNPs as close as possible to the MOF surface.
http://www.nature.com/articles/ncomms14429.pdf
Nat. Commun: Molecular weaving via surface-templated epitaxy of crystalline coordination networks.
Zhengbang Wang, Alfred Błaszczyk, Olaf Fuhr, Stefan Heissler, Christof Wöll & Marcel Mayor
Nature Communications 8, Article number: 14442 (2017)
doi:10.1038/ncomms14442
Received:01 September 2016
Accepted:29 December 2016
Published online:15 February 2017
One of the dream reactions in polymer chemistry is the bottom-up, self-assembled synthesis of polymer fabrics, with interwoven, one-dimensional fibres of monomolecular thickness forming planar pieces of textiles. We have made a major step towards realizing this goal by assembling sophisticated, quadritopic linkers into surface-mounted metal-organic frameworks. By sandwiching these quadritopic linkers between sacrificial metal-organic framework thin films, we obtained multi-heteroepitaxial, crystalline systems. In a next step, Glaser–Hay coupling of triple bonds in the quadritopic linkers yields linear, interwoven polymer chains. X-ray diffraction studies revealed that this topochemical reaction leaves the MOF backbone completely intact. After removing the metal ions, the textile sheets can be transferred onto different supports and imaged using scanning electron microscopy and atomic-force microscopy. The individual polymer strands forming the two-dimensional textiles have lengths on the order of 200 nm, as evidenced by atomic-force microscopy images recorded from the disassembled textiles.
http://www.nature.com/articles/ncomms14442.pdf
Nat. Commun: Selective sulfur dioxide adsorption on crystal defect sites on an isoreticular metal organic framework series
L. Marleny Rodríguez-Albelo, Elena López-Maya, Said Hamad, A. Rabdel Ruiz-Salvador, Sofia Calero & Jorge A.R. Navarro
Nature Communications 8, Article number: 14457 (2017)
doi:10.1038/ncomms14457
Received:28 June 2016
Accepted:29 December 2016
Published online:15 February 2017
The widespread emissions of toxic gases from fossil fuel combustion represent major welfare risks. Here we report the improvement of the selective sulfur dioxide capture from flue gas emissions of isoreticular nickel pyrazolate metal organic frameworks through the sequential introduction of missing-linker defects and extra-framework barium cations. The results and feasibility of the defect pore engineering carried out are quantified through a combination of dynamic adsorption experiments, X-ray diffraction, electron microscopy and density functional theory calculations. The increased sulfur dioxide adsorption capacities and energies as well as the sulfur dioxide/carbon dioxide partition coefficients values of defective materials compared to original non-defective ones are related to the missing linkers enhanced pore accessibility and to the specificity of sulfur dioxide interactions with crystal defect sites. The selective sulfur dioxide adsorption on defects indicates the potential of fine-tuning the functional properties of metal organic frameworks through the deliberate creation of defects.
http://www.nature.com/articles/ncomms14457.pdf
Impact of Shape Persistence on the Porosity of Molecular CagesTimothy P. MoneypennyII† , Nathan P. Walter‡, Zhikun Cai‡, Yu-Run Miao†, Danielle L. Gray§ , Jordan J. Hinman†, Semin Lee∥ , Yang Zhang*‡∥, and Jeffrey S. Moore*†∥
† Department of Chemistry, University of Illinois at Urbana—Champaign, Urbana, Illinois 61801, United States
‡ Department of Nuclear, Plasma, and Radiological Engineering, University of Illinois at Urbana—Champaign, Urbana, Illinois 61801, United States
§ School of Chemical Sciences, University of Illinois at Urbana—Champaign, Urbana, Illinois 61801, United States
∥ Beckman Institute for Advanced Science and Technology, University of Illinois at Urbana—Champaign, Urbana, Illinois 61801, United States
J. Am. Chem. Soc., Article ASAP
DOI: 10.1021/jacs.7b00189
Publication Date (Web): February 3, 2017
Copyright © 2017 American Chemical Society
*zhyang@illinois.edu, *jsmoore@illinois.edu
Porous materials provide a plethora of technologically important applications that encompass molecular separations, catalysis, and adsorption. The majority of research in this field involves network solids constructed from multitopic constituents that, when assembled either covalently or ionically, afford macromolecular arrangements with micro- or meso-porous apertures. Recently, porous solids fabricated from discrete organic cages have garnered much interest due to their ease of handling and solution processability. Although this class of materials is a promising alternative to network solids, fundamental studies are still required to elucidate critical structure–function relationships that govern microporosity. Here, we report a systematic investigation of the effects of building block shape-persistence on the porosity of molecular cages. Alkyne metathesis and edge-specific postsynthetic modifications afforded three organic cages with alkynyl, alkenyl, and alkyl edges, respectively. Nitrogen adsorption experiments conducted on rapidly crystallized and slowly crystallized solids illustrated a general trend in porosity: alkynyl > alkenyl > alkyl. To understand the molecular-scale origin of this trend, we investigated the short and long time scale molecular motions of the molecular cages using ab initio molecular dynamics (AIMD) and classical molecular dynamics (MD) simulations. Our combined experimental and computational results demonstrate that the microporosity of molecular cages directly correlates with shape persistence. These findings discern fundamental molecular requirements for rationally designing porous molecular solids.
http://pubs.acs.org/doi/abs/10.1021/jacs.7b00189
Applying the Power of Reticular Chemistry to Finding the Missing alb-MOF Platform Based on the (6,12)-Coordinated Edge-Transitive NetZhijie Chen†, Łukasz J. Weseliński† , Karim Adil†, Youssef Belmabkhout†, Aleksander Shkurenko†, Hao Jiang†, Prashant M. Bhatt†, Vincent Guillerm†, Emilie Dauzon†, Dong-Xu Xue† , Michael O』Keeffe‡, and Mohamed Eddaoudi*†
† Functional Materials Design, Discovery and Development Research Group (FMD3), Advanced Membranes and Porous Materials Center (AMPMC), Division of Physical Sciences and Engineering (PSE), King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Kingdom of Saudi Arabia
‡ School of Molecular Sciences, Arizona State University, Tempe, Arizona 85287, United States
J. Am. Chem. Soc., Article ASAP
DOI: 10.1021/jacs.7b00219
Publication Date (Web): February 5, 2017
Copyright © 2017 American Chemical Society
*mohamed.eddaoudi@kaust.edu.sa
Highly connected and edge-transitive nets are of prime importance in crystal chemistry and are regarded as ideal blueprints for the rational design and construction of metal–organic frameworks (MOFs). We report the design and synthesis of highly connected MOFs based on reticulation of the sole two edge-transitive nets with a vertex figure as double six-membered-ring (d6R) building unit, namely the (4,12)-coordinated shp net (square and hexagonal-prism) and the (6,12)-coordinated alb net (aluminum diboride, hexagonal-prism and trigonal-prism). Decidedly, the combination of our recently isolated 12-connected (12-c) rare-earth (RE) nonanuclear [RE9(μ3-OH)12(μ3-O)2(O2C–)12] carboxylate-based cluster, points of extension matching the 12 vertices of hexagonal-prism d6R, with 4-connected (4-c) square porphyrinic tetracarboxylate ligand led to the formation of the targeted RE-shp-MOF. This is the first time that RE-MOFs based on 12-c molecular building blocks (MBBs), d6R building units, have been deliberately targeted and successfully isolated, paving the way for the long-awaited (6,12)-c MOF with alb topology. Indeed, combination of a custom-designed hexacarboxylate ligand with RE salts led to the formation of the first related alb-MOF, RE-alb-MOF. Intuitively, we successfully transplanted the alb topology to another chemical system and constructed the first indium-based alb-MOF, In-alb-MOF, by employing trinuclear [In3(μ3-O)(O2C–)6] as the requisite 6-connected trigonal-prism and purposely made a dodecacarboxylate ligand as a compatible 12-c MBB. Prominently, the dodecacarboxylate ligand was employed to transplant shp topology into copper-based MOFs by employing the copper paddlewheel [Cu2(O2C–)4] as the complementary square building unit, affording the first Cu-shp-MOF. We revealed that highly connected edge-transitive nets such shp and alb are ideal for topological transplantation and deliberate construction of related MOFs based on minimal edge-transitive nets.
http://pubs.acs.org/doi/abs/10.1021/jacs.7b00219
Terpyridine-Based, Flexible Tripods: From a Highly Symmetric Nanosphere to Temperature-Dependent, Irreversible, 3D Isomeric Macromolecular NanocagesSourav Chakraborty†⊥ , Wei Hong†⊥ , Kevin J. Endres†, Ting-Zheng Xie†, Lukasz Wojtas§, Charles N. Moorefield∥, Chrys Wesdemiotis*†‡ , and George R. Newkome*†‡
†Department of Polymer Science and ‡Department of Chemistry, The University of Akron, Akron, Ohio 44256, United States
§ Department of Chemistry, University of South Florida, 4202 East Fowler Avenue, Tampa, Florida 33620, United States
∥ Dendronex, LLC, 109 Runway Drive, Lubbock, Texas 79416, United States
J. Am. Chem. Soc., Article ASAP
DOI: 10.1021/jacs.6b11784
Publication Date (Web): February 6, 2017
Copyright © 2017 American Chemical Society
*wesdemiotis@uakron.edu, *newkome@uakron.edu
A three-dimensional, highly symmetric sphere-like nanocage was synthesized using a terpyridine (tpy)-based, flexible tris-dentate ligand and characterized by single crystal X-ray analysis. To introduce more rigidity, one of the tpy units of the tris-dentate ligand was preblocked by stable <tpy-Ru2+-tpy> connectivity to form the corresponding Ru2+-dimer. The complexation between Ru2+-dimer and Fe2+ demonstrates an unexpected temperature-dependent assembly between two irreversible isomeric 3D nanocages. Investigation of the coordination process and structural configurations of the metal–ligand framework, affected by the introduction of rigidity and in the presence of external stimuli (temperature), is reported.
http://pubs.acs.org/doi/abs/10.1021/jacs.6b11784
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