Copper (I)–Organic Frameworks for Catalysis: Networking Metal Clusters with Dynamic Covalent Chemistry

Open AccessCCS ChemistryRESEARCH ARTICLE1 Jul 2021Copper (I)–Organic Frameworks for Catalysis: Networking Metal Clusters with Dynamic Covalent Chemistry Rong-Jia Wei†, Hou-Gan Zhou†, Zhi-Yin Zhang, Guo-Hong Ning and Dan Li Wei† College of Materials Science, Guangdong Provincial Key Laboratory Functional Supramolecular Coordination Applications, Jinan University, Guangzhou 510632 †R.-J. Wei H.-G. Zhou contributed equally to this work.Google Scholar More articles by author , Zhou† Zhang Google *Corresponding authors: E-mail Address: [email protected] https://doi.org/10.31635/ccschem.020.202000401 SectionsSupplemental MaterialAboutAbstractPDF ToolsAdd favoritesTrack Citations ShareFacebookTwitterLinked InEmail clusters exhibit diverse structures, emerging functions, applications; thus, incorporating into metal–organic frameworks (MOFs) brings tremendous merits. Although the construction cluster-based MOFs is sophisticated, reticular materials constructed from a combination chemistry metal covalent organic (COFs) remain unexplored. Herein, we prepared two Cu(I) cyclic trinuclear units (CTUs), termed JNM-1 JNM-2, either stepwise synthetic approach or one-pot reaction, networking dynamic chemistry, rarely utilized in MOF synthesis. The generated JNMs exhibited excellent stability could be used as recyclable catalysts palladium-free Sonogashira coupling reactions high efficiency tolerance (>90% yield nine examples), without loss performance at least five cycle runs. In addition, conjugated single molecular wires lengths ranging 1.6 2.7 nm were synthesized feasibly using catalyst. Download figure PowerPoint Introduction Reticular chemistry1 endows chemists link building blocks extended crystalline framework structures such (MOFs)2–6 (COFs)7–11 via strong coordinate bonds, respectively. Owing relatively weaker strengths compared are often suffering issues, especially harsh chemical environments bases acids, boiling water, involving highly reactive substrates.12 contrast, development (DCC), COFs achieve stabilities toward conditions.13 However, lack metals restricts their functionalities further applications. Therefore, it envisioned that “cream-skimming” coordination DCC would address these shortcomings might bring unprecedented structural complexity, along functional diversity. Recently, incorporation ion mononuclear complexes COFs, namely metal–covalent (MCOFs),14 was proposed even shown facilitate crystal growth unusual topology,15,16 leading applications catalysis, adsorption separation, optics, sensing.14 Compared units, polynuclear much more attractive because intriguing aesthetic well fascinating functions magnetism, catalytic activities, luminescence properties.17–19 preparation has been established,20,21 cluster-based, linkage bonds challenging scarcely explored.22–24 This due incompatibility condition cluster formation those DCC, solubility issues during synthesis crystallization. Cyclic (CTUs) d10 class exhibiting unique properties unsaturated centers medium oxidation state, metallophilic attraction, ?-acidity/basicity, properties. they potentially useful wide range applications, including sensing, full-color display, gas absorption, catalysis.25–28 2006, our group29 first introduced solvothermal Cu3Pz3 CTUs (pyrazolate ligand [Pz]), reaction conditions similar COF reasoned hierarchical assembly fashion COF, which adopted MOFs’ fabrication (Scheme 1).22–24 Unlike synthesis, clusters-based exclude disturbance other ions ligands; structure predictable designed precisely employing chemistry. Scheme 1 | Stepwise syntheses illustration JNMs. study, demonstrated two-dimensional (2D) CTU-based frameworks, JNM-2 (JNM represents material), imine condensation between Cu3L3 [1H-pyrazole-4-carbaldehyde (HL)] linkers [i.e., 1,3,5-tris(4-aminophenyl)benzene ( 1) 4,4?,4?-(1,3,5-triazine-2,4,6-triyl)trianiline 2) respectively], 1). Interestingly, featured higher porosity than CTUs, making them promising platforms study. Indeed activities broad substrate scope various groups palladium (Pd)-free cross-coupling reaction. Besides, showed better Cu3L3, applicable wires. Overall, strategy combining manner allowed us merge advantages constructing new types function-led rational design. Experimental Methods Synthesis complex A mixture 1H-pyrazole-4-carbaldehyde (HL) (24.0 mg, 0.25 mmol), Cu2O (14.3 0.1 4 mL ethanol, pyridine sealed an 8 Pyrex tube, heated oven 120 °C 72 h, then slowly cooled room temperature rate ?5 °C·h?1. light-yellow needle crystals formed filtered collected under microscope manually. Cu3L3: 23.7 mg (75.8%, based on Cu2O). Chemical formula, C12H9Cu3N6O3: C, 30.29; H, 1.91; N, 17.66. Found: 30.45; 2.13; 17.42. IR (KBr, cm?1): 3481 w, 3109 2782 1667 s, 1537 1416 m, 1337 1203 1044 872 767 625 w. Solid-state 13C cross-polarization/magic-angle spinning nuclear magnetic resonance (CP/MAS NMR) (400 MHz), ? (ppm) 124, 142, 184. 10 Schlenk tube charged (23.7 0.05 (26.3 0.075 mmol) (26.5 0.5 mesitylene, dioxane, 6 M aqueous acetic acid. Each containing 2 flash-frozen 77 K liquid nitrogen bath degassed three freeze-pump-thaw cycles. Upon warming temperature, each h. pale green solid isolated filtration, washed, solvent exchanged tetrahydrofuran (THF) fresh dimethylformamide (DMF). resultant solids dried vacuum 100 h give both powders. For JNM-1: Elemental analysis calcd (%) C36H24Cu3N9: 55.92; 3.11; 16.31. 53.58; 2.40; 15.71. Yield: 28.1 (73%, Cu3L3). (KBr pellets, 3355 3112 2872 1617 1539 1490 1375 1199 1050 863 748 641 m. JNM-2: C33H21Cu3N12: 51.06; 2.70; 21.66. 49.52; 2.01; 21.20. 29.5 (76%, 3369 m,1591 1507 1417 1369 1309 1246 1144 1071 1013 877 814 One-pot (10.7 HL (14.4 0.15 THF DMF. resultants powders experiments. General procedure Before experiment, About mol % 5 DMF added tube. Then phenylacetylene (0.5 mmol, 51.5 mg), iodobenzene (0.6 122.4 K2CO3 (1 138.2 mg) orderly. stirred 140 N2 atmosphere After that, 50 µL solution taken diluted CH2Cl2 mL, followed centrifugation 10,000 rpm·min?1 min. supernatant analyzed chromatography–mass spectrometry (GC–MS). conversion calculated reference substrate. Also, after completion quenched water. layer extracted ethyl acetate (3 × 150 mL), combined layers washed anhydrous MgSO4, filtered, concentrated reduced pressure. residue purified silica gel column chromatography white product. Different catalysts, solvents, temperatures, catalyst loading, others investigated procedure. Results Discussion initial attempts carried out manner, discrete, planar obtained conditions. crystallographic revealed packing intermolecular Cu?Cu distances 3.74 Å, indicating weak metal–metal interactions (Figures 1a–c). solvothermolysis suspension triangular 5?5?1 (v/v) 1,4-dioxane, acid led products hexagonal symmetry hxl lamellar Cu2O, HL, 2, where situ, hard remove unreacted remained impurities, confirmed powder X-ray di?raction (PXRD) patterns (see Supporting Information Figures S2 S3). observation oxide impurities also reported previously approaches.22 Figure Cu3L3. (a) ORTEP diagram 50% level; (b) top view (c) side showing distance Å. (C, O, Cu atoms gray, light blue, red, white, orange, respectively.) Structural modeling (d) AA (e) AB modes space-filling models. (f) PXRD JNM-1. (black) refined (red) di?erence curve (blue), profiles displaying (purple) (green) modes. (filled) desorption (open) isotherm (g) (h) K. Inset, pore size distribution nonlocal DFT data, uniform 1.89 nm. ORTEP, Oak Ridge thermal ellipsoid plot; PXRD¸ di?raction; DFT, density theory. Fourier-transform infrared (FT-IR) spectra confirm linkages, supported disappearance N?H stretching signals located 3462–3208 cm?1 exhibition C=N bands 1623–1617 S4 S5). solid-state CP/MAS NMR vanish aldehyde carbon 184 ppm appearance characteristic peaks carbons 157 155 respectively, evidenced existence linkages S7 S8). Furthermore, scanning electron microscopy (SEM) transmission (TEM) displayed rod-shaped morphologies consisted nanolayered S9–S12). Energy-dispersive spectroscopy (EDS) elemental mapping JNM particles S13 S14). experiments theoretical simulations performed analyze microcrystals obtained. calculations BIOVIA Studio (Accelrys, San Diego, CA, USA; see S15–S19) eclipsed stacking (AA) staggered (AB) simulated 1d 1e). show intense peak 4.27° accompanied four small 7.42°, 8.55°, 11.43°, 25.98°, can attributed (100), (110), (200), (120), (001) diffractions. experimental good agreement model (Figure 1f), suggesting structure. particular, Pawley refinements gave space group P ¯ unit cell parameters = b 24.4344 c 4.2298 refinement Rp 3.84% Rwp 8.61%. match negligible difference plot 1f. details). isotherms, measurements illustrate Type IV curves featuring mesoporous nature 1g 1h). Brunauer?Emmett?Teller (BET) surface areas 534.61 505.32 m2·g?1 total volumes 0.28 0.39 cm3·g?1 (P/P0 0.99), eclipsed-stacked theory (DFT) suggested narrow average width ?1.89 1h), identical values predicted thereby supporting JNM-2. heat, air, spite common fast decomposition compounds when exposed air water.30–32 Thermal gravimetric analyses (TGA) proved had crystallinity up 320 S21–S24). It known underwent Cu(II) ions.31,32 superior over month. photoelectron (XPS) only sharp symmetrical 2p3/2 933.4 933.5 eV satellite peaks, implying intact within 2a S26). crystallinities sustained upon NaOH solutions 24 documented S27 S28). XPS month before H2O2; H2O2 (the asterisk peaks); oxidized NMP 160 °C. XPS, spectroscopy; NMP, N-methyl-2-pyrrolidone. We tested reversible redox reactivities initially treating S29). dark slight decrease JNM-1, vigorous stirring. asymmetrical deconvoluted contributions 932.9 934.8 eV, corresponding integrated Cu(I):Cu(II) ratio ?4?5, respectively 2b).32 These results able oxidize presence oxidant. When samples N-methyl-2-pyrrolidone (NMP) °C, entirely ion, 2c). promoted investigate further. Since discovery reaction,33 widely efficient method carbon–carbon bond formation. replacing Pd abundant, less toxic, cost-efficient attracted lots attention.34 Thus, Pd-free catalyzed exploration iodobenzene. optimized condition, solvent, time, loading. As Table S6, base, phenylacetylene, iodide, (4 %, CTU) product efficiently ?99% conversion. Decreasing reducing time lowered ?30% 33%, did not proceed absence Moreover, homocoupled byproduct through Glaser-type reaction35 detected, selectivity heterocoupled noteworthy smooth diphenyldiacetylene 90% Section 15-5 Catalyzed Cross-Coupling Reactiona Entry Catalyst Loading Solvent Temperature (°C) Conversion 66 3 84 99 70 0 EtOH 7 dioxane 9 30 60 11 12 aReaction conditions: (1.2 equiv), K2CO3(2 equiv); (5 atmosphere, here Gas (GC–MS) analysis. (Table 1, 12), decomposed 1H NMR. resulting implied irreversible Cu(II). possessed recyclability; runs, integrity unchanged, S34); also, recycle filtration reused runs any S35). valence recycled signal confirming involved recoverable S30). With hand, studied substituted aryl iodides 2). activated electron-withdraw 4b 4c) deactivated electron-donating substituents 4d 4e), coupled terminal alkynes, proceeded yields (97–99%). groups, disturb ions. Specifically, aldehyde, amine, pyridyl 4f, 4g, 4h) yields, 97%. electron-withdrawing, electron-donating, heterocycles, all tolerated Scope mmol 1.2 equiv mol% catalyst, K2CO3. Solvent: presented yields. powerful wire rigid oligo(phenylene-ethynylenes) (OPE’s),36 fundamentally interesting understanding transport single-molecular junctions, but crucial fabricating single-molecule electronics.37 attempted prepare utilizing 3). Surprisingly, performance, 1,4-diethynylbenzene 6a), 2.2 molar iodobenzene, bis-coupling 8a) 81%, whereas 20% Such low latter ascribed substrates diethynyl resulted massive unknown products. 8b length 80% still preparing 8c stable, efficient, Conjugated Molecular Wirea 8a: 6a, 2.4 7a; 8b: 6b, 7b; 8c: 7c, 6b cCu3L3 8a level, ball-stick model. H cyan, respectively). plot. Conclusion developed linking 2D MOFs. MOFs, namely, stability, clusters, while feature reactivity provided CTUs. Taking advantage porous materials, catalyzing tolerance. shows importantly, performance. research provides novel bonds. available. Conflict Interest authors declare no conflict interest. Funding study financially National Natural Science Foundation China (nos. 21731002, 21975104, 21901085), Major Project Basic Applied Research (no. 2019B030302009). G.-H.N. thankful financial support 2019B151502024), Province Pearl River Funded (2019), Fundamental Funds Central Universities 21619315). Acknowledgments thank Prof. W. Wang S.-Y. Ding (Lanzhou University) helpful discussions. References 1. Yaghi O. M.; Kalmutzki M. J.; Diercks C. S.Introduction Chemistry: Metal–Organic Organic Frameworks; Wiley-VCH: Weinheim, 2019; p. 509. 2. O’Keeffe Ockwig N. W.; Chae H. K.; Eddaoudi Kim J.Reticular Design New Materials.Nature2003, 423, 705–714. 3. Kitagawa S.; Kitaura R.; Noro S.-I.Functional Porous Polymers.Angew. Chem. Int. Ed.2004, 43, 2334–2375. 4. Farha Hupp J. T.Rational Design, Synthesis, Purification, Activation Framework Materials.Acc. Res.2010, 1166–1175. 5. Stock N.; Biswas S.Synthesis (MOFs): Routes Various Topologies, Morphologies, Composites.Chem. Rev.2012, 112, 933–969. 6. Furukawa H.; Cordova E.; M.The Applications Frameworks.Science2013, 341, 1230444. 7. Côté A. P.; Benin I.; Matzger M.Porous, Crystalline, Frameworks.Science2005, 310, 1166–1170. 8. Feng X.; Jiang D.Covalent Frameworks.Chem. Soc. 41, 6010–6022. 9. S. Y.; W.Covalent (COFs): From Applications.Chem. Rev.2013, 42, 548–568. 10. Waller P. Ga?dara F.; M.Chemistry Frameworks.Acc. Res.2015, 48, 3053–3063. 11. Segura L.; Mancheno Zamora F.Covalent Based Schiff-Base Properties Potential Rev.2016, 45, 5635–5671. 12. Vikrant Kumar V.; K.-H.; Kukkar D.Metal–Organic Challenges Capture Abatement Ammonia.J. Mater. A2017, 5, 22877–22896. 13. Guan Ma Xue Fang Q.; Yan Valtchev Qiu S.Chemically Stable Polyarylether-Based Frameworks.Nat. Chem.2019, 11, 587–594. 14. Dong Han Liu Cui Y.Metal-Covalent (MCOFs): Bridge Between Frameworks.Angew. Ed.2020, 59, 13722–13733. 15. Y. Z.; Zhao B.; Sun X. Gandara Zhu Suenaga Oleynikov Alshammari Terasaki O.; M.Weaving Threads Crystalline Framework.Science2016, 351, 365–369. 16. Xu H.-S.; Luo See Chen T.; Liang Leng Abdelwahab Shi Lu C.; Loh P.Single Crystal One-Dimensional Metallo-Covalent Framework.Nat. Commun.2020, 1434. 17. Chakraborty Pradeep T.Atomically Precise Noble Metals: Emerging Link Atoms Nanoparticles.Chem. Rev.2017, 117, 8208–8271. 18. W.Sub-Nanometre Sized Clusters: Synthetic Unique Property Discoveries.Chem. 3594–3623. 19. Jin Zeng Y.Atomically Colloidal Nanoclusters Nanoparticles: Fundamentals Opportunities.Chem. 116, 10346–10413. 20. W.-X.; Liao P.-Q.; Lin R.-B.; Y.-S.; M.-H.; X.-M.Metal Cluster-Based Polymers.Coord. Rev.2015, 293, 263–278. 21. Bai Dou Xie L.-H.; Rutledge J.-R.; H.-C.Zr-Based Frameworks: Structure, 2327–2367. 22. Nguyen Gándara Doan T. L. M.A Titanium–Organic Exemplar Combining Metal– Covalent–Organic Frameworks.J. Am. Soc.2016, 138, 4330–4333. 23. Pei Lyu Ji Vertices Polyoxometalate Linkers Solid-State Electrolyte.J. Soc.2019, 141, 17522–17526. 24. Yang Bu Jia P.A Tale Two Trimers Worlds: COF-Inspired Strategy Pore-Space Partitioning MOFs.Angew. Ed.2019, 58, 6316–6320. 25. Omary A.; Mohamed Rawashdeh-Omary Fackler P.Photophysics Binary Stacks Consisting Electron-Rich Trinuclear Au(I) Complexes Electrophiles.Coord. Rev.2005, 249, 1372–1381. 26. Zheng D.The ?-Acidity/Basicity Units (CTUs): Theoretical Perspective Commun.2019, 55, 7134–7146. 27. Galassi Dias V. A.Homoleptic Complexes: Self-Association Metallophilic Excimeric Bonding Breakage Thereof Oxidative Addition, Dative Bonding, Quadrupolar, Heterometal Interactions.Comments Inorg. 39, 287–348. 28. Wu G.-H.; D.Coinage-Metal-Based Metal–Metal Interactions: Theories Experiments, Structures Functions.Chem. Rev.2020, 120, 9675–9742. 29. He Yin Y.-G.; D.; Huang X.-C.Design Solvothermal Luminescent Copper(I)–Pyrazolate Oligomer Polymer Commun.2006, 38, 2845–2847. 30. J.-P.; Horike S.A Flexible Functionalized Unsaturated Clusters.Angew. Ed.2007, 46, 889–892. 31. S.Supramolecular Isomerism, Flexibility, Center, Ag(I)/Cu(I) 3,3?,5,5?-Tetramethyl-4,4?-Bipyrazolate.J. Soc.2008, 130, 907–917. 32. Tu Pang Weng Q.Reversible Redox Activity Multicomponent Constructed Copper Pyrazolate Building Blocks.J. Soc.2017, 139, 7998–8007. 33. Tohda Hagihara N.A Convenient Acetylenes: Catalytic Substitutions Acetylenic Hydrogen Bromoalkenes, Iodoarenes Bromopyridines.Tetrahedron Lett.1975, 16, 4467–4470. 34. Maria Thomas Sujatha Anilkumar G.Recent Advances Perspectives Copper-Catalyzed Coupling Reactions.RSC Adv.2014, 4, 21688–21698. 35. Siemsen Livingston R. Diederich F.Acetylenic Coupling: Powerful Tool Construction.Angew. Ed.2000, 2632–2657. 36. Kaliginedi Moreno-Garcia Valkenier Hong Garcia-Suarez Buiter Otten Hummelen Lambert Wandlowski T.Correlations Structure Single-Junction Conductance: Case Study Oligo(phenylene-ethynylene)-Type Wires.J. Soc.2012, 134, 5262–5275. 37. Diaz-Fernandez Gschneidtner Westerlund Lara-Avila Moth-Poulsen K.Single-Molecule Electronics: Devices.Chem. Rev.2014, 7378–7411. Previous articleNext article FiguresReferencesRelatedDetails Issue AssignmentVolume 3Issue 7Page: 2045-2053Supporting Copyright & Permissions© 2020 Chinese SocietyKeywordscovalent frameworkscyclic unitsmetal–organic frameworksheterogeneous catalysisAcknowledgmentsThe Downloaded 2,804 times ...