For more information visit: https://fmd3.kaust.edu.sa/Pages/Home.aspx

Recent Submissions

  • 25 years of Reticular Chemistry

    Freund, Ralph; Canossa, Stefano; Cohen, Seth M.; Yan, Wei; Deng, Hexiang; Guillerm, Vincent; Eddaoudi, Mohamed; Madden, David G.; Fairen-Jimenez, David; Lyu, Hao; Macreadie, Lauren K.; Ji, Zhe; Zhang, Yuanyuan; Wang, Bo; Haase, Frederik; Wöll, Christof; Zaremba, Orysia; Andreo, Jacopo; Wuttke, Stefan; Diercks, Christian S. (Angewandte Chemie International Edition, Wiley, 2021-03-29) [Article]
    At its core, reticular chemistry has translated the precision and expertise of organic and inorganic synthesis to the solid state. While initial excitement over metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) was undoubtedly fueled by their unprecedented porosity and surface areas, the most profound scientific innovation of the field has been the elaboration of design strategies for the synthesis of extended crystalline solids through strong directional bonds. In this contribution we highlight the different classes of reticular materials that have been developed, how these frameworks can be functionalized and how complexity can be introduced into their backbones. Finally, we show how the structural control over these materials is being extended from the molecular scale to their crystal morphology and shape on the nanoscale, all the way to their shaping on the bulk scale.
  • [Cu 15 (PPh 3 ) 6 (PET) 13 ] 2+ : a Copper Nanocluster with Crystallization Enhanced Photoluminescence

    Nematulloev, Saidkhodzha; Huang, Renwu; Yin, Jun; Shkurenko, Aleksander; Dong, Chunwei; Ghosh, Atanu; Alamer, Badriah Jaber; Naphade, Rounak; Hedhili, Mohamed N.; Maity, Partha; Eddaoudi, Mohamed; Mohammed, Omar F.; Bakr, Osman (Small, Wiley, 2021-03-19) [Article]
    Due to their atomically precise structure, photoluminescent copper nanoclusters (Cu NCs) have emerged as promising materials in both fundamental studies and technological applications, such as bio-imaging, cell labeling, phototherapy, and photo-activated catalysis. In this work, a facile strategy is reported for the synthesis of a novel Cu NCs coprotected by thiolate and phosphine ligands, formulated as [Cu<sub>15</sub> (PPh<sub>3</sub> )<sub>6</sub> (PET)<sub>13</sub> ]<sup>2+</sup> , which exhibits bright emission in the near-infrared (NIR) region (≈720 nm) and crystallization-induced emission enhancement (CIEE) phenomenon. Single crystal X-ray crystallography shows that the NC possesses an extraordinary distorted trigonal antiprismatic Cu<sub>6</sub> core and a, unique among metal clusters, "tri-blade fan"-like structure. An in-depth structural investigation of the ligand shell combined with density functional theory calculations reveal that the extended CH···π and π-π intermolecular ligand interactions significantly restrict the intramolecular rotations and vibrations and, thus, are a major reason for the CIEE phenomena. This study provides a strategy for the controllable synthesis of structurally defined Cu NCs with NIR luminescence, which enables essential insights into the origins of their optical properties.
  • [Ag9(1,2-BDT)6]3–: How Square-Pyramidal Building Blocks Self-Assemble into the Smallest Silver Nanocluster

    Alamer, Badriah Jaber; Bootharaju, Megalamane S.; Kozlov, Sergey M.; Cao, Zhen; Shkurenko, Aleksander; Nematulloev, Saidkhodzha; Maity, Partha; Mohammed, Omar F.; Eddaoudi, Mohamed; Cavallo, Luigi; Basset, Jean-Marie; Bakr, Osman (Inorganic Chemistry, American Chemical Society (ACS), 2021-03-17) [Article]
    The emerging promise of few-atom metal catalysts has driven the need for developing metal nanoclusters (NCs) with ultrasmall core size. However, the preparation of metal NCs with single-digit metallic atoms and atomic precision is a major challenge for materials chemists, particularly for Ag, where the structure of such NCs remains unknown. In this study, we developed a shape-controlled synthesis strategy based on an isomeric dithiol ligand to yield the smallest crystallized Ag NC to date: [Ag<sub>9</sub>(1,2-BDT)<sub>6</sub>]<sup>3-</sup> (1,2-BDT = 1,2-benzenedithiolate). The NC's crystal structure reveals the self-assembly of two Ag square pyramids through preferential pyramidal vertex sharing of a single metallic Ag atom, while all other Ag atoms are incorporated in a motif with thiolate ligands, resulting in an elongated body-centered Ag<sub>9</sub> skeleton. Steric hindrance and arrangement of the dithiolated ligands on the surface favor the formation of an anisotropic shape. Time-dependent density functional theory based calculations reproduce the experimental optical absorption features and identify the molecular orbitals responsible for the electronic transitions. Our findings will open new avenues for the design of novel single-digit metal NCs with directional self-assembled building blocks.
  • CCDC 2061331: Experimental Crystal Structure Determination : 7,14,25,32,43,50-hexaazadecacyclo[50.2.2.22,5.216,19.220,23.234,37.238,41.08,13.026,31.044,49]hexahexaconta-1(54),2,4,6,14,16,18,20,22,24,32,34,36,38,40,42,50,52,55,57,59,61,63,65-tetracosaene ethylbenzene solvate

    Dey, Avishek; Chand, Santanu; Maity, Bholanath; Bhatt, Prashant; Ghosh, Munmun; Cavallo, Luigi; Eddaoudi, Mohamed; Khashab, Niveen M. (Cambridge Crystallographic Data Centre, 2021-03-11) [Dataset]
  • CCDC 2061332: Experimental Crystal Structure Determination : 7,14,25,32,43,50-hexaazadecacyclo[50.2.2.22,5.216,19.220,23.234,37.238,41.08,13.026,31.044,49]hexahexaconta-1(54),2,4,6,14,16,18,20,22,24,32,34,36,38,40,42,50,52,55,57,59,61,63,65-tetracosaene ethenylbenzene solvate

    Dey, Avishek; Chand, Santanu; Maity, Bholanath; Bhatt, Prashant; Ghosh, Munmun; Cavallo, Luigi; Eddaoudi, Mohamed; Khashab, Niveen M. (Cambridge Crystallographic Data Centre, 2021-03-11) [Dataset]
  • CCDC 2061332: Experimental Crystal Structure Determination : 7,14,25,32,43,50-hexaazadecacyclo[50.2.2.22,5.216,19.220,23.234,37.238,41.08,13.026,31.044,49]hexahexaconta-1(54),2,4,6,14,16,18,20,22,24,32,34,36,38,40,42,50,52,55,57,59,61,63,65-tetracosaene ethenylbenzene solvate

    Dey, Avishek; Chand, Santanu; Maity, Bholanath; Bhatt, Prashant; Ghosh, Munmun; Cavallo, Luigi; Eddaoudi, Mohamed; Khashab, Niveen M. (Cambridge Crystallographic Data Centre, 2021-03-11) [Dataset]
  • CCDC 2061333: Experimental Crystal Structure Determination : 7,14,25,32,43,50-hexaazadecacyclo[50.2.2.22,5.216,19.220,23.234,37.238,41.08,13.026,31.044,49]hexahexaconta-1(54),2,4,6,14,16,18,20,22,24,32,34,36,38,40,42,50,52,55,57,59,61,63,65-tetracosaene unknown solvate

    Dey, Avishek; Chand, Santanu; Maity, Bholanath; Bhatt, Prashant; Ghosh, Munmun; Cavallo, Luigi; Eddaoudi, Mohamed; Khashab, Niveen M. (Cambridge Crystallographic Data Centre, 2021-03-11) [Dataset]
  • A reticular chemistry guide for the design of periodic solids

    Jiang, Hao; Alezi, Dalal; Eddaoudi, Mohamed (Nature Reviews Materials, Springer Nature, 2021-03-10) [Article]
    Reticular chemistry — the linking of well-defined molecular building blocks by strong bonds into crystalline extended frameworks — has enabled the synthesis of diverse metal–organic frameworks (MOFs) and covalent organic frameworks, in which the pore shape, size and functionality can be tailored towards specific applications. Structural design methodologies are based on three main requisites: building blocks, targeted nets and isoreticular chemistry. In this Review, we highlight the well-developed and cutting-edge methodologies in reticular chemistry for the structural design and discovery of periodic solids. We illustrate the diversity of building blocks and delineate the suitable blueprint nets — namely, edge-transitive nets — for the design of MOFs. These edge-transitive nets are classified into three categories to help rationalize existing MOFs and to provide guidelines for the design of new structures. Two emerging topological concepts, namely, the merged-net approach and net-coded building units, are highlighted for their potential in synthesizing intricate or multi-component MOFs. We also consider isoreticular design strategies for the modification, expansion and contraction of building blocks, and identify challenges and opportunities in the assembly of increasingly intricate frameworks.
  • Adsorptive Molecular Sieving of Styrene over Ethylbenzene by Trianglimine Crystals

    Dey, Avishek; Chand, Santanu; Maity, Bholanath; Bhatt, Prashant; Ghosh, Munmun; Cavallo, Luigi; Eddaoudi, Mohamed; Khashab, Niveen M. (Journal of the American Chemical Society, American Chemical Society (ACS), 2021-03-10) [Article]
    The separation of styrene (ST) and ethylbenzene (EB) mixtures is of great importance in the petrochemical and plastics industries. Current technology employs multiple cycles of energy-intensive distillation due to the very close boiling points of ST and EB. Here, we show that the molecular sieving properties of easily scalable and stable trianglimine crystals offer ultrahigh selectivity (99%) for styrene separation. The unique molecular sieving properties of trianglimine crystals are corroborated by DFT calculations, suggesting that the incorporation of the nonplanar EB requires a significant deformation of the macrocyclic cavity whereas the planar ST can be easily accommodated in the cavity.
  • Penetrant competition and plasticization in membranes: How negatives can be positives in natural gas sweetening

    Liu, Yang; Chen, Zhijie; Qiu, Wulin; Liu, Gongping; Eddaoudi, Mohamed; Koros, William J. (Journal of Membrane Science, Elsevier BV, 2021-02) [Article]
    Membranes are attractive for upgrading natural gas; however, the gas permeation processes through membranes are challenging to control. The coexistence of condensable H2S and CO2 typically causes membrane performance to decline under practical feed conditions, due to uncontrolled penetrate competition and undesired plasticization of the membrane polymer matrix. In this paper, we report a strategy to successfully transform these apparent negatives, i.e. plasticization and penetrate competition, into positives that boost the natural gas sweetening efficiency of membranes greatly. Our strategy is to disperse engineered metal organic framework (MOF) fillers into designed polymer matrices to form hybrid membranes, which promote the permeation of both H2S and CO2 but hinder CH4 permeation. Moreover, uniformly dispersed MOF fillers also significantly alter the plasticization responses of polymer matrices, enabling controlled plasticization benefits. Ultimately, we illustrate a highly tunable MOF-polymer hybrid membrane platform that meets the diverse natural gas sweetening requirements under aggressive conditions.
  • Coating of Conducting and Insulating Threads with Porous MOF Particles through Langmuir-Blodgett Technique

    Rauf, Sakandar; Andrés, Miguel A.; Roubeau, Olivier; Gascón, Ignacio; Serre, Christian; Eddaoudi, Mohamed; Salama, Khaled N. (Nanomaterials, MDPI AG, 2021-01-10) [Article]
    The Langmuir-Blodgett (LB) method is a well-known deposition technique for the fabrication of ordered monolayer and multilayer thin films of nanomaterials onto different substrates that plays a critical role in the development of functional devices for various applications. This paper describes detailed studies about the best coating configuration for nanoparticles of a porous metal-organic framework (MOF) onto both insulating or conductive threads and nylon fiber. We design and fabricate customized polymethylmethacrylate sheets (PMMA) holders to deposit MOF layers onto the threads or fiber using the LB technique. Two different orientations, namely, horizontal and vertical, are used to deposit MIL-96(Al) monolayer films onto five different types of threads and nylon fiber. These studies show that LB film formation strongly depends on deposition orientation and the type of threads or fiber. Among all the samples tested, cotton thread and nylon fiber with vertical deposition show more homogenous monolayer coverage. In the case of conductive threads, the MOF particles tend to aggregate between the conductive thread’s fibers instead of forming a continuous monolayer coating. Our results show a significant contribution in terms of MOF monolayer deposition onto single fiber and threads that will contribute to the fabrication of single fiber or thread-based devices in the future.
  • CCDC 2011034: Experimental Crystal Structure Determination : catena-(bis(mu-hydroxo)-tris(mu-12,16,32,36-tetramethyl[11,21:23,31-terphenyl]-14,34-dicarboxylato)-bis(mu-oxo)-tri-zirconium dimethylformamide solvate)

    Alsadun, Norah Sadun; Mouchaham, Georges; Guillerm, Vincent; Czaban-Jozwiak, Justyna; Shkurenko, Aleksander; Jiang, Hao; Bhatt, Prashant; Parvatkar, Prakash Tukaram; Eddaoudi, Mohamed (Cambridge Crystallographic Data Centre, 2020-11-24) [Dataset]
  • CCDC 2011035: Experimental Crystal Structure Determination : catena-(bis(mu-hydroxo)-tris(mu-4,4'-(2,4,6-trimethylpyridine-3,5-diyl)dibenzoato)-bis(mu-oxo)-tri-zirconium dimethylformamide solvate)

    Alsadun, Norah Sadun; Mouchaham, Georges; Guillerm, Vincent; Czaban-Jozwiak, Justyna; Shkurenko, Aleksander; Jiang, Hao; Bhatt, Prashant; Parvatkar, Prakash Tukaram; Eddaoudi, Mohamed (Cambridge Crystallographic Data Centre, 2020-11-24) [Dataset]
  • CCDC 2011036: Experimental Crystal Structure Determination

    Alsadun, Norah Sadun; Mouchaham, Georges; Guillerm, Vincent; Czaban-Jozwiak, Justyna; Shkurenko, Aleksander; Jiang, Hao; Bhatt, Prashant; Parvatkar, Prakash Tukaram; Eddaoudi, Mohamed (Cambridge Crystallographic Data Centre, 2020-11-24) [Dataset]
  • 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.

View more