Topological Strain-Induced Regioselective Linker Elimination in a Chiral Zr(IV)-Based Metal-Organic Framework

•Highly flexible 18-crown-6-ether functionality was embedded into a chiral Zr-MOF•An unprecedented solid-state topology transition behavior observed•The process captured by single-crystal and powder X-ray diffraction•The resultant Zr-MOF can enantioseparate lansoprazole, with up to 98% ee Zr-carboxylate metal-organic frameworks (MOFs) are well known as structurally robust materials strong coordination bonds that have been widely investigated in the MOF community since 2008. The of these 3D makes transitions involving Zr–O bond cleavage formation extremely challenging rare. Here, we demonstrate introducing highly homochiral Zr-MOF, able target an SC-SC virtue topological strain. transition, which occurs without any external stimuli through regioselective-linker-elimination process, diffraction studies. As result, porous stable phase fluorite is attained be employed solid adsorbent for enantioadsorptive solid-phase extractive separation excellent enantioselectivity. materials, part due their bonds. regioselective between architectures thus heretofore unexplored. In this work, functionalities report 4,10-connected framework undergoes rapid thermodynamically more 4,8-connected analog under ambient conditions. unambiguously unraveled studies, proposed possible mechanism based on various control experiments theoretical calculations. chemical stability substantially expanded porosity pore apertures endowed transformed exceptional capacity racemic drug molecule lansoprazole 93% ee, respectively. Metal-organic (MOFs), composed metal ions/clusters multitopic organic linkers, contain reminiscent those zeolites.1Yaghi O.M. Kalmutzki M.J. Diercks C.S. Introduction Reticular Chemistry: Metal-Organic Frameworks Covalent Organic Frameworks. 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Ultraporous, water Stable, breathing zirconium-based ftw topology.J. 2015; 137: 13183-13190Crossref (113) Scholar,21Krause stimuli-responsive design.Angew. 56: 10676-10680Crossref (50) or reduction cluster connectivity.22Zhang X. Lyu Otake K.I. Redfern L.R. Malliakas C.D. Islamoglu 4-connected Zr6 nodes.J. 2018; 140: 11179-11183Crossref (102) Using approaches, predominantly limited undergoing swelling and/or contraction, commonly referred “gating” “breathing,” overall remains undisrupted. Although often comes penalty reduced robustness, circumvent drawback owing However, among Thus far, two examples reported. Užarevi? colleagues demonstrated first 12-connected porphyrinic Zr6-based MOF-525 underwent dramatic from cubic hexagonal liquid-assisted grinding.23Karadeniz Žili? Huski? Germann L.S. Fidelli A.M. Muratovi? Lon?ari? Etter Dinnebier R.E. Bariši? al.Controlling polymorphism mechanochemistry.J. 141: 19214-19220Crossref (29) Gianneschi, Farha, coworkers subsequently presented microporous scu-NU-906 mesoporous csq-NU-1008 driven dissolution-reprecipitation process.24Lyu Gong S.J. Gnanasekaran Wasson M.C. Bai Guo Gianneschi N.C. Phase directly monitored situ variable liquid-cell transmission electron microscopy diffraction.J. 142: 4609-4615Crossref (27) aforementioned accomplished complete nodes solution. does compromise crystallinity still unexplored consequence inevitable difficulties controlling location (regioselectivity) weakness crystal lattices. Monitoring snapshotting regioselectivity (SC-SC) manner sought after, yet, it never Zr-MOFs. show strain functionalities, realized state three sequential procedures: (1) linker deformation cleavage, (2) ordered elimination oriented (3) finally dimerization formation, unequivocally revealed SC crystallography. result transformation, (flu) efficient electron-deficient cationic dye methylene blue, enantiospecific large-sized ee. Moreover, serve extractant separate mixture achieving 4 h. To best our knowledge, second example successfully exploited extraction (SPE) technologies,25Navarro-Sánchez Argente-GarcÍa A.I. Moliner-MartÍnez Roca-Sanjuán CampÍns-Falcó MartÍ-Gastaldo Peptide enantioselective drugs.J. 4294-4297Crossref (152) enantioselectivity herein broad class stationary phases. spiro-derived functionalized tetracarboxylic S- R-4,4?,6,6?-tetrakis(4-benzoic acid)-[7,7?-(1,1?-Spirobiindano)]-1,4,7,10,13,16-hexaoxahexadecane (S-H4L R-H4L) (Figure 1A), prepared 56% yields starting enantiopure R-spinol, Solvothermal reactions ZrCl4 S-H4L R-H4L presence formic acid competing reagent N,N-dimethylformamide (DMF) afforded colorless triangular crystals [Zr6O4(?3-OH)4(?1-OH)(HCOO)(DMF)(H2O)2(L)2.5]. characterized both diffraction, latter confirming purity. analysis clearly Spiro-CE-1 crystallizes orthorhombic space group C2221, asymmetric unit containing whole formula unit. Zr6O8 core, six Zr atoms connected each other four ?3-O ?3-OH groups yielding D2d symmetry S1), ten fully deprotonated L4- coordinated monodentate fashion rest engaged bidentate coordination. secondary (SBU) completed one terminal ?1-OH, formate ligand, DMF molecule, 1A). contained narrow zig-zag channels necked junctions along c axis aperture measuring 0.8 nm, suffused disordered molecules. Spiro-CE-2 obtained exposing fresh-prepared air 3–5 min. Spiro-OH employing similar synthetic procedures Spiro-CE-1, except 4,4?,6,6?-tetrakis(4-benzoic acid)-1,1?-Spirobiindano-7,7?-diol used ligand. Changes cell parameters arising solvent effects uncommon high connectivity. Therefore, surprised observe distinct peak shift (PXRD) patterns bulk removal compared simulated pattern data S8). This phenomenon indicative solvent-evaporation-induced changes, prompted us further investigate materials. Fortunately, phase, denoted Spiro-CE-2, maintained crystallinity, allowing collect good determination. also C2221 group, half found decreased 31% resulted 27% shrinkage volume when Spiro-CE-1. Detailed showed edge-sharing ?2-OH generate new Zr12O8(?3-OH)8(?2-OH)2 SBU, reported even molecular complexes date 1C). novel SBUs eight them monodentately coordinated. remaining occupied ligands –OH/H2O give [Zr12O8(?3-OH)8(?2-OH)2(?1-OH)12(HCOO)2(H2O)14(L)2], 1.5 loss per close examination while keeping segments nearly undisturbed 1). massive significant contraction 47,325 Å3 (calculated density ?calc = 0.889 g cm?3) 34,475 (?calc 0.719 lead open large intercrossed edge length 1.8 nm distorted octahedral cavities approximate size × 2.9 nm3 (Figures 6A, 6B, S3, S4). Calculations PLATON26Spek A.L. Single-crystal validation program PLATON.J. Appl. Crystallogr. 2003; 36: 7-13Crossref (15734) probe radius Å had higher solvent-accessible than (69.4% 53.3%). From purely point view served 10-connected nodes, With combination, could now form simplified net symbol {417·624·84}2{45·6}2{46}3 1B). contrast, considering Zr12 8-connected 1C S2). alternatively described rare 4,5-connected binodal tcs S2), deconstructed interconnected nodes. It should noted flu generally recognized porous.27Zhang Bosch Gentle III, Z.U. Symmetry-guided topology.Angew. 53: 815-818Crossref (160) Scholar,28Tan Y.X. Yang B.B. Rational flu-type heterometallic cluster-based Zr-MOF.Chem. Commun.(Camb). 52: 13671-13674Crossref obtain detailed information regarding series carried out different First, rule possibility occurred solution before being taken system, initial solvothermal 1 week 393 unchanged PXRD indicated no during S9). freshly integrity after immersed month Second, removed solvents (DMF, acetone, CH2Cl2) conditions they completely effectively accelerated decelerated elevated cryogenic temperatures, Notably, proceeded smoothly 220 K, prohibited below freezing (212 K). Third, elucidated performing optical studies individual crystal. achieve steady slow rate, performed SC-XRD continuous shifts consecutive metastable intermediates 2A). Optical images apparent 2B, inset), accordance volume. gradually 64.585 44.637 60.169, 52.660, 48.352 Å, leading 12,850 Å3. Importantly, intermediate (denoted Spiro-CE-?) subsequent Spiro-CE-? Spiro-CE-?). Despite efforts Spiro-CE-?, unsuccessful structures, illustrated diffuse scattering all collected image frames S12). Spiro-CE-? same bonded linkers. comparison bidentately Spiro-CE-?, corresponding showing severe dihedral angle spiro backbone 78.8° 89.7°, depicted Figures 3 S6. noteworthy movement evidently brings adjacent closer would conceivably induce domino-like dimerization. Given cannot evaporate low temperature, excludes evaporation temperatures needed liberate speculated main driving force system subtle 18-crown-ether-6 moieties may trigger providing sufficient energy drastic vibrations, resembling effect. verify deduction, carefully analyses, experiments, We began comparing remarkable deformations S5), implying intense vibration process. Next, rates same, regardless types pores, suggesting transition. addition experimental results, functional theory (DFT) calculations S21) 298 K generation SBU favorable, enthalpy (?rH) Gibbs free (?rG) ?103.4 ?20.7 kcal mol?1, Finally, role spiro-based 7.7?-positions modified hydroxyl S7). After assembly conditions, (Spiro-OH) crystallized less sterically hindered 4,12-connected framework, axial carboxylic Nonetheless, akin difference additional present additionally studied previously remained harsh confirmed measurements S7), suggests played crucial Inspired well-established affinity K+ ions,29Sam Simmons H.E. Crown ether chemistry. Substitution potassium halide hydroxide dicyclohexyl-18-crown-6.J. 1974; 96: 2252-2253Crossref (117) looked fix chelation, thereby restricting vibrational motion. optimizing host-guest adducts Spiro-CE-1-K immersing saturated methanol KBF4 333 24 Inductively coupled plasma emission spectrometry (ICP-OES) analyses gave K/Zr ratio 0.43, matched value 0.42 calculated formula. several sets post-synthetically synchrotron radiation, locating ions structure. activated Brunauer-Emmett-Teller (BET) area 450 m2 g?1 S16). results hand, set study room 373 S11), alluding importance motion MOF. Taking note propose associated initiators. shown Figure 4, behave rotors,30Conyard Addison Heisler I.A. Cnossen Browne W.R. Feringa B.L. Meech S.R. Ultrafast dynamics power stroke rotary motor.Nat. 4: 547-551Crossref (127) machines vibrate inside lattice. restricted solvated pores; accordingly, generated weak unable Once solvent, equilibrium ingress egress disrupted, greatly facilitating rotors. leads exclusion liberation pores accelerates reinforces Consequently, provides enough ultimately circular dichroism (CD) spectra made S R enantiomers H4L mirror other, MOF’s enantiomeric nature S13). N2 adsorption/desorption pretreated 77 type I isotherm 5D) 1,230 g-1, (1,440 g-1) accessible surface program.31Düren Millange Walton K.S. Calculating geometric areas characterization tool frameworks.J. Phys. 111: 15350-15356Crossref (440) Thermogravimetric (TGA) evacuated weight range 313–603 decomposition about 603 S14). examined thoroughly PXRD, sorption, treatment boiling water, 0.01 M NaOH (aq.) (RT), 8 HCl RT week. 5C, intact treatments, collapse occurred. Furthermore, permanent retained evidenced 5D). evaluate solution, experiments. Due ubiquitous distribution electron-rich chose blue (MB) (15.6 6.8 Å2) model S17). 6A; Table S7, adsorb 4.5 MB MeOH, 0.7 indicating ample interspaces accommodate Additionally, above-mentioned adsorbed 3.0/3.1/3.9 unit, respectively, integrity. recovered extra crystals, verified corroborated favored product S10).Figure 6Adsorption Behaviors Spiro-CE-2Show full caption(A) UV-vis curves treatments. Inset: Image color change (left) optimized (right).(B) adsorption, inset picture lansoprazole.(C) Cartoon illustration adsorptive S-Spiro-CE-2. yellow triangles S-Spiro-CE-2.(D) SPE R-Spiro-CE-2. R-Spiro-CE-2 R/S circles configuration molecule.View Large ViewerDownload Hi-res Download (PPT) (A) (right). (B) lansoprazole. (C) (D) molecule. advantages intrinsic chirality rich potential recognition sites, stability, foresaw utilized separation.32Corella-Ochoa M.N. Tapia J.B. Rubin H.N. Lillo González-Cobos Núñez-Rico J.L. Balestra S.R.G. Almora-Barrios Lledós Guell-Bara al.Homochiral separations liquid chromatography.J. 14306-14316Crossref (52) implement hypothesis, gastric ulcers,33Lai K.C. Lam S.K. Chu K.M. Wong B.C.Y. Hui Hu W.H.C. Lau G.K.K. Yuen M.F. Chan A.O.O. al.Lansoprazole prevention recurrences ulcer complications long-term low-dose aspirin use.N. Med. 2002; 346: 2033-2038Crossref (553) substrate (16.1 7.2 readily accommodated Spiro-CE-2. 6B S18, 3.7 MeOH fast kinetics. allowed precluding separation. evaluated careful optimization S-Spiro-CE-2 (94 mg, 0.025 mmol) mL dry 0.4 mmol 277 excess. dominated handedness sorbent, enantiomer over enantiomer. recycled least five times compromising S19) retaining 5C slight decrease runs ascribed residual washing. uniform morphology performance use (CSP) 6D, (50 13.3 packed polypropylene cartridge, (10 0.027 eluted 2 0.5 mL/h assistance syringe pump. High-performance chromatography (HPLC) resulting extract excess, ability preferentially trap enantiomers. inefficient packing crystals. cartridge reused S20). Thus, highlight application summary, conventionally moiety unique C2 symmetric linker. believed elimination. led network shows outstanding performances technologies. work probes limits maintaining microscopic macroscopic crystallographic but principles production crystalline