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  • Kinetic separation of C4 olefins using Y-fum-fcu-MOF with ultra-fine-tuned aperture size

    Assen, Ayalew H.; Virdis, Thomas; De Moor, Wannes; Moussa, Ali; Eddaoudi, Mohamed; Baron, Gino; Denayer, Joeri F.M.; BELMABKHOUT, Youssef (Chemical Engineering Journal, Elsevier BV, 2020-10-18) [Article]
    The separation of C4 olefin mixtures into pure components is one of the most challenging processes in chemical industries. Adsorption-based separation, using ultra-microporous materials, is considered as a viable alternative to reduce the operating cost of the currently employed but energy intensive distillation technique. The understanding of structural properties-relationships for C4 olefins separation using solid state materials is still lacking particularly for microporous materials with purely cage-based structures. Herein, the adsorptive separation of C4 olefins (butene isomers and 1,3-butadiene) by the microporous MOF, Y-fum-fcu-MOF, containing octahedral and tetrahedral cages with triangular pore aperture size (≈4.7 Å), is studied. The adsorption capacities of the MOF for C4 olefins were assessed by measuring the single component adsorption isotherms at 30 °C which led to very similar equilibrium adsorption uptakes at saturation for the components (excluding isobutylene). However, adsorption breakthrough curves collected at 25 °C and Pulse Gas Chromatography experiments, conducted to define the guest–host affinity at very low concentration (Henry's region), evidenced kinetically driven separation of C4 olefins by Y-fum-fcu-MOF. In fact, a strong relation between pores window size, kinetic diameter of the components and their adsorption behavior was observed. The breakthrough capacity decreases at increasing molecular size, allowing the separation of cis- and trans-2-butene despite the quite similar adsorption enthalpies for these components (42.0 and 37.7 kJ/mol, respectively).
  • A Polymorphic Azobenzene Cage for Energy Efficient and Highly Selective p-Xylene Separation.

    Moosa, Basem; Alimi, Lukman Olawale; Shkurenko, Aleksander; Fakim, Aliyah; Bhatt, Prashant; Zhang, Gengwu; Eddaoudi, Mohamed; Khashab, Niveen M. (Angewandte Chemie (International ed. in English), Wiley, 2020-10-02) [Article]
    Developing the competency of molecular sorbents for energy-saving applications, such as C8 separations, requires efficient, stable, scalable and easily recyclable materials that can readily transition to commercial implementation. Here, we report an azobenzene-based cage for the selective separation of  p -xylene isomer across a range of C8 isomers in both vapor and liquid states with selectivity that is higher than the reported all-organic sorbents. Interestingly, the crystal structure shows non-porous cages that are separated by  p- xylene molecules through selective CH… p  interactions between the azo bonds and the methyl hydrogens of the xylene molecules. This cage is stable in solution and can be regenerated directly under vacuum to be used in multiple cycles. We envisage that this work will promote the investigation of the azo bond as well as guest induced crystal to crystal phase transition in non-porous organic solids for pivotal energy intensive separations.
  • Extension of the Surface Organometallic Chemistry to Metal-Organic Framework: development of well-defined single site [(≡Zr-O-)W(=O)(CH2tBu)3] olefin metathesis catalyst.

    Thiam, Zeynabou; Abou-Hamad, Edy; Dereli, Busra; Liu, Lingmei; Emwas, Abdul-Hamid M.; Ahmad, Rafia; Jiang, Hao; Isah, Abdulrahman Adamu; Ndiaye, Papa Birame; Taoufik, Mostafa; Han, Yu; Cavallo, Luigi; Basset, Jean-Marie; Eddaoudi, Mohamed (Journal of the American Chemical Society, American Chemical Society (ACS), 2020-09-09) [Article]
    We report here the first step by step anchoring of a W(≡CtBu)(CH2 tBu)3 complex on a highly crystalline and mesoporous MOF, namely Zr-NU-1000, using Surface organometallic Chemistry (SOMC) concept and methodology. SOMC allowed us to selectively graft the complex on the Zr6 clusters and characterize the obtained single site material by using state of the art experimental methods including extensive solid-state NMR techniques and HAADF-STEM imaging. Further FT-IR spectroscopy revealed the presence of a W=O moiety arising from the in situ reaction of the W≡CtBu functionality with the coordinated water coming from the 8-connected hexanuclear Zr6 clusters. All the steps leading to the final grafted molecular complex have been identified by DFT. The obtained material was tested for gas phase and liquid phase olefin metathesis and exhibited higher catalytic activity than the corresponding catalysts synthesized by different grafting methods. This contribution establishes the importance of applying SOMC to MOF chemistry to get well defined single site catalyst on MOF inorganic secondary building units, in particular the in situ synthesis of W=O alkyl complexes from their W carbyne analogues.
  • Covalent Organic Frameworks as Negative Electrodes for High-Performance Asymmetric Supercapacitors

    Kandambeth, Sharath; Jia, Jiangtao; Wu, Hao; Kale, Vinayak Swamirao; Parvatkar, Prakash Tukaram; Czaban-Jozwiak, Justyna; Zhou, Sheng; Xu, Xiangming; Ameur, Zied Ouled; Abou-Hamad, Edy; Emwas, Abdul-Hamid M.; Shekhah, Osama; Alshareef, Husam N.; Eddaoudi, Mohamed (Advanced Energy Materials, Wiley, 2020-09-02) [Article]
    New covalent organic frameworks (COFs), encompassing redox-functionalized moieties and an aza-fused π-conjugated system, are designed, synthesized, and deployed as negative electrodes in asymmetric supercapacitors (ASC), for the first time. The Hex-Aza-COFs are synthesized based on the solvothermal condensation reaction of cyclohexanehexone and redox-functionalized aromatic tetramines with benzoquinone (Hex-Aza-COF-2) or phenazine (Hex-Aza-COF-3). The redox-functionalized Hex-Aza-COFs show a specific capacitance of 585 F g−1 for Hex-Aza-COF-2 and 663 F g−1 for Hex-Aza-COF-3 in a three-electrode configuration. These values are the highest among reported COF materials and are comparable with state-of-the-art pseudocapacitive electrodes. The Hex-Aza-COFs exhibit a wide voltage window (0 to −1.0 V), which allow the construction of a two-electrode ASC device by combining them with RuO2. The complementary potential windows of Hex-Aza-COF-3 and RuO2 enable an asymmetric device with a high voltage window of 1.7 V. The RuO2//Hex-Aza-COF-3 ASC device achieves an energy density value of 23.3 W h kg−1 at a power density of 661.2 W kg−1. The newly developed negative COF materials open new prospects for the development of high-performance ASCs.
  • Quest for Zeolite-like Supramolecular Assemblies: Self-Assembly of Metal–Organic Squares via Directed Hydrogen Bonding

    Li, Jiantang; Kan, Liang; Li, Jiyang; Liu, Yunling; Eddaoudi, Mohamed (Angewandte Chemie, Wiley, 2020-08-26) [Article]
    Our conceived approach based on the directed assembly of functional metal–organic squares (MOSs), 4-membered ring (4MR) building units, permitted the construction of two novel zeolite-like supramolecular assemblies (ZSAs), namely [Co4(ImDC)4(En)4]⋅9 H2O⋅1.5 DMF (ZSA-10) and [Co4(ImDC)4(En)4]⋅7 H2O (ZSA-11) (H3ImDC=4,5-imidazoledicarboxylic acid, En=ethylenediamine, DMF=N,N-dimethylformamide). The elected MOSs encompass both trans- and cis-coordinated nodes, offering complementary peripheral functional groups for their directed assembly into zeolite-like topologies via supramolecular hydrogen bonding interactions. Distinctly, ZSA-10 possesses the underling MER zeolite topology and is the only pure MER framework material (without any supporting templates) exhibiting permanent porosity up to now. ZSA-11 has the underlying ABW topology together with one type of narrow channel.
  • Quest for Zeolite-like Supramolecular Assemblies: Self-Assembly of Metal-Organic Squares via Directed Hydrogen Bonding.

    Liu, Yunling; Li, Jiantang; Kan, Liang; Li, Jiyang; Eddaoudi, Mohamed (Angewandte Chemie (International ed. in English), Wiley, 2020-08-26) [Article]
    Our conceived approach based on the directed assembly of functional metal-organic squares (MOSs), 4-membered ring (4MR) building units, permitted the construction of two novel zeolite-like supramolecular assemblies (ZSAs), namely [Co 4 (ImDC) 4 (En) 4 ]·9H 2 O·1.5DMF ( ZSA-10 ) and [Co 4 (ImDC) 4 (En) 4 ]·7H 2 O ( ZSA-11 ) (H 3 ImDC = 4,5-imidazoledicarboxylic acid, En = ethylenediamine, DMF = N,N-dimethylformamide). The elected MOSs encompass both trans - and cis -coordinated nodes, offering complementary peripheral functional groups for their directed assembly into zeolite-like topologies via supramolecular hydrogen bonding interactions. Distinctly, ZSA-10 possesses the underling MER zeolite topology and is the only pure MER framework material (without any supporting templates) exhibiting permanent porosity up to now. ZSA-11 has the underlying ABW topology together with one type of narrow channel.
  • Solution processable metal–organic frameworks for mixed matrix membranes using porous liquids

    Knebel, Alexander; Bavykina, Anastasiya; Datta, Shuvo Jit; Sundermann, Lion; Garzon Tovar, Luis Carlos; Lebedev, Yury; Durini, Sara; Ahmad, Rafia; Kozlov, Sergey; Shterk, Genrikh; Karunakaran, Madhavan; Carja, Ionela-Daniela; Simic, Dino; Weilert, Irina; Klüppel, Manfred; Giese, Ulrich; Cavallo, Luigi; Rueping, Magnus; Eddaoudi, Mohamed; Caro, Jürgen; Gascon, Jorge (Nature Materials, Springer Science and Business Media LLC, 2020-08-10) [Article]
    The combination of well-defined molecular cavities and chemical functionality makes crystalline porous solids attractive for a great number of technological applications, from catalysis to gas separation. However, in contrast to other widely applied synthetic solids such as polymers, the lack of processability of crystalline extended solids hampers their application. In this work, we demonstrate that metal-organic frameworks, a type of highly crystalline porous solid, can be made solution processable via outer surface functionalization using N-heterocyclic carbene ligands. Selective outer surface functionalization of relatively large nanoparticles (250 nm) of the well-known zeolitic imidazolate framework ZIF-67 allows for the stabilization of processable dispersions exhibiting permanent porosity. The resulting type III porous liquids can either be directly deployed as liquid adsorbents or be co-processed with state-of-the-art polymers to yield highly loaded mixed matrix membranes with excellent mechanical properties and an outstanding performance in the challenging separation of propylene from propane. We anticipate that this approach can be extended to other metal-organic frameworks and other applications.
  • CCDC 1846427: Experimental Crystal Structure Determination : tetrakis(mu-4,5-dicarboxylatoimidazolato)-tetrakis(ethane-1,2-diamine)-tetra-cobalt dimethylformamide solvate dodecahydrate

    Liu, Yunling; Li, Jiantang; Kan, Liang; Li, Jiyang; Eddaoudi, Mohamed (Cambridge Crystallographic Data Centre, 2020-07-29) [Dataset]
  • CCDC 1846426: Experimental Crystal Structure Determination : tetrakis(mu-4,5-dicarboxylatoimidazolato)-tetrakis(ethane-1,2-diamine)-tetra-cobalt dimethylformamide solvate nonahydrate

    Liu, Yunling; Li, Jiantang; Kan, Liang; Li, Jiyang; Eddaoudi, Mohamed (Cambridge Crystallographic Data Centre, 2020-07-29) [Dataset]
  • CCDC 1846425: Experimental Crystal Structure Determination : tetrakis(mu-4,5-dicarboxylatoimidazolato)-tetrakis(ethane-1,2-diamine)-tetra-cobalt heptahydrate

    Liu, Yunling; Li, Jiantang; Kan, Liang; Li, Jiyang; Eddaoudi, Mohamed (Cambridge Crystallographic Data Centre, 2020-07-29) [Dataset]
  • Recent Progress on Microfine Design of Metal-Organic Frameworks: Structure Regulation and Gas Sorption and Separation.

    Li, Jiantang; Bhatt, Prashant M; Li, Jiyang; Eddaoudi, Mohamed; Liu, Yunling (Advanced materials (Deerfield Beach, Fla.), Wiley, 2020-07-16) [Article]
    Metal-organic frameworks (MOFs) have emerged as an important and unique class of functional crystalline hybrid porous materials in the past two decades. Due to their modular structures and adjustable pore system, such distinctive materials have exhibited remarkable prospects in key applications pertaining to adsorption such as gas storage, gas and liquid separations, and trace impurity removal. Evidently, gaining a better understanding of the structure-property relationship offers great potential for the enhancement of a given associated MOF property either by structural adjustments via isoreticular chemistry or by the design and construction of new MOF structures via the practice of reticular chemistry. Correspondingly, the application of isoreticular chemistry paves the way for the microfine design and structure regulation of presented MOFs. Explicitly, the microfine tuning is mainly based on known MOF platforms, focusing on the modification and/or functionalization of a precise part of the MOF structure or pore system, thus providing an effective approach to produce richer pore systems with enhanced performances from a limited number of MOF platforms. Here, the latest progress in this field is highlighted by emphasizing the differences and connections between various methods. Finally, the challenges together with prospects are also discussed.
  • Quest for an optimal methane hydrates formation in the pores of hydrolytically stable MOFs

    Cuadrado-Collados, Carlos; Mouchaham, Georges; Daemen, Luke L.; Cheng, Yongqiang; Ramirez-Cuesta, Anibal J.; Aggarwal, Himanshu; Missyul, Alexander; Eddaoudi, Mohamed; Belmabkhout, Youssef; Silvestre-Albero, Joaquin (Journal of the American Chemical Society, American Chemical Society (ACS), 2020-07-11) [Article]
    Porous MOFs capable of storing relatively high amount of dry methane (CH4) in adsorbed phase are largely explored, however solid CH4 storage in confined pores of MOFs in the form of hydrates is yet to be discovered. Here we report a rational approach to form CH4 hydrates by taking advantage of the optimal pore confinement in relatively narrow cavities of hydrolytically stable MOFs. Unprecedentedly, we were able to isolate methane hydrate (MH) nanocrystals with a sI structure encapsulated inside MOF pores with an optimal cavity dimension. It was found, that confined nanocrystals require cavities slightly larger than the unit cell crystal size of MHs (1.2 nm), as exemplified in the experimental case study performed on Cr-soc-MOF-1 vs smaller cavities of Y-shp-MOF-5. Under these conditions, the excess amount of methane stored in the pores of Cr-soc-MOF-1 in the form of MH was found to be 50% larger than the corresponding dry adsorbed amount at 10 MPa. More importantly, the pressure gradient driving the CH4 storage/delivery process could be drastically reduced compared to the conventional CH4 adsorbed phase storage on the dry Cr-soc-MOF-1 (≤3 MPa vs. 10 MPa)
  • Topology Meets Reticular Chemistry for Chemical Separations: MOFs as a Case Study

    Bhatt, Prashant; Guillerm, Vincent; Datta, Shuvo Jit; Shkurenko, Aleksander; Eddaoudi, Mohamed (Chem, Elsevier BV, 2020-07-09) [Article]
    Chemical separations are of prime industrial importance; however, they consume a large portion of total industrial energy. Credibly, adsorbent-based separation methods offer the prospective to drastically lessen the energy demand of conventional energy-intensive separation processes. Prominently, a special class of porous materials, namely metal-organic frameworks (MOFs), are reasonably positioned to address various demanding separations in an energy-efficient manner. Out of a myriad of possible topologies for the construction of MOFs, face-transitive nets affording a sole type of window, preferably defined by three- or four-membered rings, can be regarded as ideal blueprints for the construction of MOFs for targeted separations. Intricate separations by MOFs based on some of these topologies are discussed, highlighting the effect of appropriate pore aperture and channel size with prerequisite functional groups on their separation performance. MOFs based on face-transitive nets offer great potential as effective fillers for the construction of practical mixed-matrix membranes (MMMs) with improved separation properties over conventional polymeric membranes.
  • A Highly Selective Metal-Organic Framework Textile Humidity Sensor

    Rauf, Sakandar; Vijjapu, Mani Teja; Andres, Miguel Angel; Gascón, Ignacio; Roubeau, Olivier; Eddaoudi, Mohamed; Salama, Khaled N. (ACS Applied Materials & Interfaces, American Chemical Society (ACS), 2020-06-19) [Article]
    The increase in demand and popularity of smart textiles brings new and innovative ideas to develop a diverse range of textile-based devices for our daily life applications. Smart textile-based sensors (TEX sensors) become attractive due to the potential to replace current solid-state sensor devices with flexible and wearable devices. We have developed a smart textile sensor for humidity detection using a metal-organic framework (MOF) as an active thin-film layer. We show for the first time, the use of the Langmuir-Blodgett (LB) technique for the deposition of a MIL-96(Al) MOF thin film directly onto the fabrics containing interdigitated textile electrodes for the fabrication of a highly selective humidity sensor. The humidity sensors were made from two different types of textiles, namely, linen and cotton, with the linen based sensor giving the best response due to better coverage of MOF. The TEX sensor showed a reproducible response after multiple cycles of measurements. After three weeks of storage, the sensor showed a moderate decrease in response. Moreover, TEX sensors showed a high level of selectivity for the detection of water vapors in the presence of several volatile organic compounds (VOCs). Interestingly, the selectivity is superior to some of the previously reported MOF coated solid-state interdigitated electrode devices and textile sensors. The method herein described is generic and can be extended to other textiles and coating materials for the detection of toxic gases and vapors.
  • Nanoporous Fluorinated Metal-Organic Framework-Based Membranes for CO2Capture

    Chernikova, Valeriya; Shekhah, Osama; Belmabkhout, Youssef; Eddaoudi, Mohamed (ACS Applied Nano Materials, American Chemical Society (ACS), 2020-06-12) [Article]
    The search for effective carbon-capture materials has permitted the disclosure and institution of nanoporous fluorinated metal-organic frameworks (MOFs) with a contracted pore system as benchmark CO2-selective adsorbents. Namely, the SIFSIX-3-M (M = Zn, Cu, and Ni) MOF adsorbents, encompassing a periodic arrangement of fluorine moieties in a confined one-dimensional channels, exhibit a remarkable CO2 adsorption-based selectivity over CH4 and H2 in various industrially related gas mixtures. Here, we report the successful transplantation/integration of this distinctive CO2 selectivity, distinguishing this class of nanoporous MOF adsorbents to pure MOF membranes for carbon capture. Markedly, the liquid-phase epitaxy (LPE) growth approach permitted, for the first time, the building of continuous, homogeneous, and defect-free MOF membranes based on the SIFSIX-3-M platform, MSiF6(Pyz)2 with M = Ni or Cu, on a porous alumina substrate. Single and mixed-gas permeation tests revealed that the resulting nanoporous MOF membrane is a CO2-selective membrane, exhibiting the foreseen favorable CO2-selectivity toward carbon dioxide over H2, and CH4, governed by the CO2-selective adsorption in the functional and contracted channels of the SIFSIX-3-M.
  • Phenanthroline Covalent Organic Framework Electrodes for High-Performance Zinc-Ion Supercapattery

    Wang, Wenxi; Kale, Vinayak Swamirao; Cao, Zhen; Kandambeth, Sharath; Zhang, Wenli; Ming, Jun; Parvatkar, Prakash Tukaram; Abou-Hamad, Edy; Shekhah, Osama; Cavallo, Luigi; Eddaoudi, Mohamed; Alshareef, Husam N. (ACS Energy Letters, American Chemical Society (ACS), 2020-06-08) [Article]
    Aqueous zinc-ion batteries and capacitors are potentially competitive grid-scale energy storage devices because of their great features such as safety, environmental friendliness, and low cost. Herein, a completely new phenanthroline covalent organic framework (PA-COF) was synthesized and introduced in zinc-ion supercapatteries (ZISs) for the first time. Our as-synthesized PA-COF shows a high capacity of 247 mAh g-1 at a current density of 0.1 A g-1, with only 0.38% capacity decay per cycle during 10※000 cycles at a current density of 1.0 A g-1. Although covalent organic frameworks (COFs) are attracting great attention in many fields, our PA-COF has been synthesized using a new strategy involving the condensation reaction of hexaketocyclohexanone and 2,3,7,8-phenazinetetramine. Detailed mechanistic investigations, through experimental and theoretical methods, reveal that the phenanthroline functional groups in PA-COF are the active zinc ion storage sites. Furthermore, we provide evidence for the cointercalation of Zn2+ (60%) and H+ (40%) into PA-COF using inductively coupled plasma atomic emission spectroscopy and deuterium solid-state nuclear magnetic resonance (NMR). We believe that this study opens a new avenue for COF material design for zinc-ion storage in aqueous ZISs.
  • A new Titanium Metal Organic Framework with visible-light responsive photocatalytic activity.

    Cadiau, Amandine; Kolobov, Nikita; Srinivasan, Sivaranjani; Goesten, Maarten Gerard; Haspel, Henrik; Bavykina, Anastasiya; Tchalala, Mohamed; Maity, Partha; Goryachev, Andrey; Poryvaev, Artem; Eddaoudi, Mohamed; Fedin, Matvey; Mohammed, Omar F.; Gascon, Jorge (Angewandte Chemie (International ed. in English), Wiley, 2020-05-27) [Article]
    We report the one step synthesis and characterization of a new and robust titanium-based Metal Organic Framework, ACM-1 . In this new structure, based on infinite Ti-O chains and 4,4',4″,4″'-(pyrene-1,3,6,8-tetrayl) tetrabenzoic acid as a photosensitizer ligand, the combination of highly mobile photogenerated electrons and a strong hole localization at the organic linker results in large charge separation lifetimes. The suitable energies for band gap and CBM offer great potential for a wide range of photocatalytic reactions, from hydrogen evolution to the selective oxidation of organic substrates.
  • Fully Integrated Organic Field-Effect Transistor Platform to Detect and to Quantify NO 2 Gas

    Yuvaraja, Saravanan; Surya, Sandeep Goud; Vijjapu, Mani Teja; Chernikova, Valeriya; Shekhah, Osama; Eddaoudi, Mohamed; Salama, Khaled N. (physica status solidi (RRL) – Rapid Research Letters, Wiley, 2020-05-04) [Article]
    Herein, the gas sensing characteristics of PDVT-10 organic field-effect tran sistor(OFET) devices are explored and integrated to build a compact analog-to-digitalconverter (ADC) gas detection system. The electrical characteristics of thepristine PDVT-10 OFET exhibitIon/Ioffratio and threshold voltage as 104and12 V, respectively. Through the coatin g of a metal-organic framework (MOF) onthe surface of PDVT-10, theIon/Ioffimproves by one order of magnitudeaccompanied by significant positive threshold shift measured around 4 V. MOF isadded as a pre-concentrating material, and the device exhibits excellent selectivityand good sensitivity toward the target NO2gas. Most of the reports available inthe literature generally focus on the gas sensing performance of individualsensors, which does not have the potential to solve real-time sensing problems.Hence, for the first time, a fully integrated ADC system is designed with just twoOFETs. The integrated ADC system not only detects the NO2gas with highsensitivity and selectivity but also generates a 5 bit digital output correspondingto different NO2gas concentrations from 25 ppb to 1 ppm.
  • Access to Highly Efficient Energy Transfer in Metal-Organic Frameworks via Mixed Linkers Approach.

    Jia, Jiangtao; Gutierrez Arzaluz, Luis; Shekhah, Osama; Alsadun, Norah Sadun; Czaban-Jozwiak, Justyna; Zhou, Sheng; Bakr, Osman; Mohammed, Omar F.; Eddaoudi, Mohamed (Journal of the American Chemical Society, American Chemical Society (ACS), 2020-04-18) [Article]
    Herein, we report a new light-harvesting mixed-ligand Zr(IV)-based metal-organic framework (MOF),with underlying fcu topology, encompassing the [Zr6(μ3-O)4(μ3-OH)4(O2C-)12] cluster and an equimolar mixture of thiadiazole- and benzimidazole-functionalized ligands. The successful integration of ligands with similar structural features but with notable chemical distinction afforded the attainment of a highly efficient energy transfer (ET). Notably, the very strong spectral overlap between the emission spectrum of benzimidazole (energy donor) and the absorption spectrum of thiadiazole (energy acceptor) provided an ideal platform to achieve very rapid (picosecond time scale) and highly efficient energy transfer (around 90% efficiency), as evidenced by time-resolved spectroscopy. Remarkably, the ultrafast time-resolved experiments quantified for the first time the anticipated close proximity of the two linkers with an average distance of 17 Å. This finding paves the way for the design and synthesis of periodic MOFs affording very efficient and fast ET to mimic natural photosynthetic systems.
  • Reticular Chemistry 3.2: Typical Minimal Edge-Transitive Derived and Related Nets for the Design and Synthesis of Metal–Organic Frameworks

    Chen, Zhijie; Jiang, Hao; Li, Mian; O’Keeffe, Michael; Eddaoudi, Mohamed (Chemical Reviews, American Chemical Society (ACS), 2020-04-17) [Article]
    Reticular chemistry has proven as a notable/distinctive discipline aimed at the deliberate assembly of periodic solids, offering great opportunities to effectively deploy the gained knowledge on net-topologies as a guide and toolbox for designed syntheses, based on the assembly of molecular building blocks into targeted and anticipated structures of crystalline extended solids. The effective practice of reticular chemistry has enriched the repertoire of crystal chemistry and afforded notable accelerating development of crystalline extended frameworks, especially metal−organic frameworks (MOFs). Here, we review a special class of trinodal MOF structures based on the reticulation of special minimal edgetransitive nets (nets with transitivity [3 2], three distinct nodes and two kind of edges) derived from edge-transitive nets (one kind of edge). The rationale for deriving these special minimal edge-transitive nets is reviewed, and their associated net-coded building (net-cBUs) for the design of trinodal MOFs is presented and discussed. The resultant inclusive list of the enumerated minimal edge-transitive nets provides a unique toolbox for the material’s designer as it offers ideal blueprints for the deliberate design and rational assembly of building blocks with embedded multiple branch points into intricate trinodal MOFs

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