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• W2991906522 abstract "•Controlled synthesis of Ti-MOF is achieved by post-synthetic and one-pot reactions•The chemical environment of the MOF pore was tuned following mixed-linker strategy•CO2 adsorption working capacity and selectivity over N2 could be adjusted•Ti8AF and MIP-207 feature facile green scalable preparations under mild conditions Rational design and synthesis of metal-organic frameworks (MOFs) is of particular interest in fine-tuning the crystalline structures for given targeting applications. Considerable advance of this topic has been achieved for MOFs built with a large number of metal species but not titanium. The complex and unpredictable titanium chemistry in solution not only leads to the difficulty of isolating crystalline Ti-MOFs via direct synthesis but also results in the challenge of maintaining control over ordered structures. We demonstrated a Ti-O cluster guided green scalable preparation of a Ti-MOF (MIP-207) in a controlled manner with both post-synthetic and one-pot reaction routes. The chemical environment and functionality of the MOF structural void could be easily tuned by adopting the mixed-linker strategy, which finally resulted in an adjustable performance in CO2 capture over N2. This provides a new avenue for the rational design of Ti-MOFs in energy- and environment-related applications. The complexity of Ti chemistry in solution not only leads to the difficulty of isolating crystalline titanium metal-organic frameworks (Ti-MOFs) but also brings the challenge of controlled assembly of the crystal structure. We report here the first example of a controlled synthesis of a Ti-MOF structure through a linker-exchange strategy directly from a preformed Ti-O cluster. A Ti8O8 cluster precursor with terminal formate and acetate ligands (Ti8AF) was reacted with trimesic acid (BTC) under green and mild conditions, generating a microporous Ti-MOF (MIP-207) while preserving the connection and configuration of the Ti8O8 core. In addition, due to the ditopic meta-positional connection mode of the linker, the chemical environment and functionality of the structural voids could be easily tuned by substituting trimesate moieties with isophthalate-type linkers via concise one-pot reactions. This finally resulted in an adjustable performance in CO2 capture over N2. The complexity of Ti chemistry in solution not only leads to the difficulty of isolating crystalline titanium metal-organic frameworks (Ti-MOFs) but also brings the challenge of controlled assembly of the crystal structure. We report here the first example of a controlled synthesis of a Ti-MOF structure through a linker-exchange strategy directly from a preformed Ti-O cluster. A Ti8O8 cluster precursor with terminal formate and acetate ligands (Ti8AF) was reacted with trimesic acid (BTC) under green and mild conditions, generating a microporous Ti-MOF (MIP-207) while preserving the connection and configuration of the Ti8O8 core. In addition, due to the ditopic meta-positional connection mode of the linker, the chemical environment and functionality of the structural voids could be easily tuned by substituting trimesate moieties with isophthalate-type linkers via concise one-pot reactions. This finally resulted in an adjustable performance in CO2 capture over N2. Titanium metal-organic frameworks (Ti-MOFs) have attracted considerable and continuous attention over the past decade, mainly due to the low toxicity and rich natural abundance of elemental Ti, the well-recognized specialty of Ti-MOFs in photocatalysis,1Zhu J.J. Li P.Z. Guo W.H. Zhao Y.L. Zou R.Q. Titanium-based metal-organic frameworks for photocatalytic applications.Coord. Chem. Rev. 2018; 359: 80-101Crossref Scopus (186) Google Scholar, 2Dolgopolova E.A. Rice A.M. Martin C.R. Shustova N.B. Photochemistry and photophysics of MOFs: steps towards MOF-based sensing enhancements.Chem. Soc. Rev. 2018; 47: 4710-4728Crossref PubMed Google Scholar, 3Horiuchi Y. Toyao T. Saito M. Mochizuki K. Iwata M. Higashimura H. Anpo M. Matsuoka M. Visible-light-promoted photocatalytic hydrogen production by using an amino-functionalized Ti(IV) metal-organic framework.J. Phys. Chem. C. 2012; 116: 20848-20853Crossref Scopus (478) Google Scholar, 4Fu Y. Sun D. Chen Y. Huang R. Ding Z. Fu X. Li Z. An amine-functionalized titanium metal-organic framework photocatalyst with visible-light-induced activity for CO2 reduction.Angew. Chem. Int. Ed. 2012; 51: 3364-3367Crossref PubMed Scopus (1201) Google Scholar and their great promise in gas separation.5Benoit V. Pillai R.S. Orsi A. Normand P. Jobic H. Nouar F. Billemont P. Bloch E. Bourrelly S. Devic T. et al.MIL-91(Ti), a small pore metal-organic framework which fulfils several criteria: an upscaled green synthesis, excellent water stability, high CO2 selectivity and fast CO2 transport.J. Mater. Chem. A. 2016; 4: 1383-1389Crossref Google Scholar,6Sun Y. Liu Y. Caro J. Guo X. Song C. Liu Y. In-plane epitaxial growth of highly c-oriented NH2-MIL-125(Ti) membranes with superior H2/CO2 selectivity.Angew. Chem. Int. Ed. 2018; 57: 16088-16093Crossref PubMed Scopus (84) Google Scholar However, the complexity of Ti chemistry in solution has led so far to notable difficulties in controlling the Ti-MOF structures. For all the published Ti-MOFs obtained from direct synthesis using simple Ti precursors, including MIL-91,7Serre C. Groves J.A. Lightfoot P. Slawin A.M.Z. Wright P.A. Stock N. Bein T. Haouas M. Taulelle F. Férey G. Synthesis, structure and properties of related microporous N,N′-piperazinebismethylenephosphonates of aluminum and titanium.Chem. Mater. 2006; 18: 1451-1457Crossref Scopus (148) Google Scholar MIL-125,8Dan-Hardi M. Serre C. Frot T. Rozes L. Maurin G. Sanchez C. Férey G. A new photoactive crystalline highly porous titanium(IV) dicarboxylate.J. Am. Chem. Soc. 2009; 131: 10857-10859Crossref PubMed Scopus (923) Google Scholar NTU-9,9Gao J. Miao J. Li P.-Z. Teng W.Y. Yang L. Zhao Y. Liu B. Zhang Q. A p-type Ti(iv)-based metal-organic framework with visible-light photo-response.Chem. Commun. (Camb.). 2014; 50: 3786-3788Crossref PubMed Google Scholar MIL-101,10Mason J.A. Darago L.E. Lukens Jr., W.W. Long J.R. Synthesis and O2 reactivity of a titanium(III) metal-organic framework.Inorg. Chem. 2015; 54: 10096-10104Crossref PubMed Scopus (63) Google Scholar COK-69,11Bueken B. Vermoortele F. Vanpoucke D.E. Reinsch H. Tsou C.C. Valvekens P. De Baerdemaeker T. Ameloot R. Kirschhock C.E. Van Speybroeck V. et al.A flexible photoactive titanium metal-organic framework based on a [Ti(IV)3(mu3-O)(O)2(COO)6] cluster.Angew. Chem. Int. Ed. 2015; 54: 13912-13917Crossref PubMed Scopus (82) Google Scholar Ti-CAT-5,12Nguyen N.T. Furukawa H. Gandara F. Trickett C.A. Jeong H.M. Cordova K.E. Yaghi O.M. Three-dimensional metal-catecholate frameworks and their ultrahigh proton conductivity.J. Am. Chem. Soc. 2015; 137: 15394-15397Crossref PubMed Scopus (227) Google Scholar MIL-167,13Assi H. Pardo Perez L.C. Mouchaham G. Ragon F. Nasalevich M. Guillou N. Martineau C. Chevreau H. Kapteijn F. Gascon J. et al.Investigating the case of titanium(IV) carboxyphenolate photoactive coordination polymers.Inorg. Chem. 2016; 55: 7192-7199Crossref PubMed Scopus (57) Google Scholar MIP-177,14Wang S. Kitao T. Guillou N. Wahiduzzaman M. Martineau-Corcos C. Nouar F. Tissot A. Binet L. Ramsahye N. Devautour-Vinot S. et al.A phase transformable ultrastable titanium-carboxylate framework for photoconduction.Nat. Commun. 2018; 9: 1660Crossref PubMed Scopus (100) Google Scholar MIL-100,15Castells-Gil J. M Padial N. Almora-Barrios N. da Silva I. Mateo D. Albero J. García H. Martí-Gastaldo C. De novo synthesis of mesoporous photoactive titanium(IV)-organic frameworks with MIL-100 topology.Chem. Sci. 2019; 10: 4313-4321Crossref PubMed Scopus (47) Google Scholar Ti-TBP,16Lan G. Ni K. Veroneau S.S. Feng X. Nash G.T. Luo T. Xu Z. Lin W. Titanium-based nanoscale metal-organic framework for type I photodynamic therapy.J. Am. Chem. Soc. 2019; 141: 4204-4208Crossref PubMed Scopus (193) Google Scholar and ZSTUs,17Li C. Xu H. Gao J. Du W. Shangguan L. Zhang X. Lin R. Wu H. Zhou W. Liu X. et al.Tunable titanium metal-organic frameworks with infinite 1D Ti-O rods for efficient visible-light-driven photocatalytic H2 evolution.J. Mater. Chem. A. 2019; 7: 11928-11933Crossref Google Scholar their inorganic building units range from discrete Ti-O clusters to infinite chains, showing the highly unpredictable feature of Ti reaction. In this regard, only post-synthetic cation exchange between MOFs built with various metal centers of known secondary building units (SBUs) and Ti ions has led to Ti-MOFs in a structurally controlled manner.18Kim M. Cahill J.F. Fei H. Prather K.A. Cohen S.M. Postsynthetic ligand and cation exchange in robust metal-organic frameworks.J. Am. Chem. Soc. 2012; 134: 18082-18088Crossref PubMed Scopus (613) Google Scholar, 19Brozek C.K. Dinca M. Ti(3+)-, V(2+/3+)-, Cr(2+/3+)-, Mn(2+)-, and Fe(2+)-substituted MOF-5 and redox reactivity in Cr- and Fe-MOF-5.J. Am. Chem. Soc. 2013; 135: 12886-12891Crossref PubMed Scopus (332) Google Scholar, 20Zou L. Feng D. Liu T.-F. Chen Y.-P. Yuan S. Wang K. Wang X. Fordham S. Zhou H.C. A versatile synthetic route for the preparation of titanium metal-organic frameworks.Chem. Sci. 2016; 7: 1063-1069Crossref PubMed Google Scholar To achieve a better structure control of the resulting MOF during direct synthesis, Zhou and co-workers firstly tried to prepare PCN-22 in N,N-diethylformamide (DEF)/benzoic acid under solvothermal conditions involving a preformed Ti6 cluster compound as precursor, which efficiently slowed down the crystallization and thus gave rise to a single-crystal product.21Yuan S. Liu T.-F. Feng D. Tian J. Wang K. Qin J. Zhang Q. Chen Y.P. Bosch M. Zou L. et al.A single crystalline porphyrinic titanium metal-organic framework.Chem. Sci. 2015; 6: 3926-3930Crossref PubMed Google Scholar Nonetheless, a break of the pristine Ti6 cluster and its reorganization into a Ti7 one was revealed by single-crystal structure analysis. Later, using the same Ti6 cluster complex in methanol, an exciting progress in synthesizing Ti-MOF while under control was achieved by Yaghi and co-workers by applying a combined MOF and covalent-organic framework (COF) strategy. MOF-901 was successfully assembled via the imine formation from the amino group of the Ti6 cluster-protecting ligand and the aldehyde groups of the organic spacer, during which the connection of the Ti6 cluster core was not disturbed.22Nguyen H.L. Gándara F. Furukawa H. Doan T.L.H. Cordova K.E. Yaghi O.M. A titanium-organic framework as an exemplar of combining the chemistry of metal- and covalent-organic frameworks.J. Am. Chem. Soc. 2016; 138: 4330-4333Crossref PubMed Scopus (195) Google Scholar This method was proven to tolerate other dialdehyde spacers by the preparation of MOF-902, which represents the first example of reticular chemistry in Ti-MOFs.23Nguyen H.L. Vu T.T. Le D. Doan T.L.H. Nguyen V.Q. Phan N.T.S. A titanium-organic framework: engineering of the band-gap energy for photocatalytic property enhancement.ACS Catal. 2017; 7: 338-342Crossref Scopus (92) Google Scholar The challenge remaining is to realize the controlled formation of Ti-MOF by modulating the Ti-O coordination bond of the cluster instead of the organic covalent bonds from the protective ligand, as in the cases reported previously for the other metal-based MOFs such as Fe24Surblé S. Serre C. Mellot-Draznieks C. Millange F. Férey G. A new isoreticular class of metal-organic-frameworks with the MIL-88 topology.Chem. Commun. (Camb.). 2006; 21: 284-286Crossref Google Scholar, 25Dybtsev D.N. Sapianik A.A. Fedin V.P. Pre-synthesized secondary building units in the rational synthesis of porous coordination polymers.Mendeleev Commun. 2017; 27: 321-331Crossref Scopus (40) Google Scholar, 26Peng L. Asgari M. Mieville P. Schouwink P. Bulut S. Sun D.T. Zhou Z. Pattison P. van Beek W. Queen W.L. Using predefined M3(μ3-O) clusters as building blocks for an isostructural series of metal-organic frameworks.ACS Appl. Mater. Interfaces. 2017; 9: 23957-23966Crossref PubMed Scopus (32) Google Scholar and Zr27DeStefano M.R. Islamoglu T. Garibay S.J. Hupp J.T. Farha O.K. Room-temperature synthesis of UiO-66 and thermal modulation of densities of defect sites.Chem. Mater. 2017; 29: 1357-1361Crossref Scopus (248) Google Scholar, 28Noh H. Kung C.-W. Islamoglu T. Peters A.W. Liao Y. Li P. Garibay S.J. Zhang X. DeStefano M.R. Hupp J.T. et al.Room temperature synthesis of an 8-connected Zr-based metal-organic framework for top-down nanoparticle encapsulation.Chem. Mater. 2018; 30: 2193-2197Crossref Scopus (61) Google Scholar, 29Guillerm V. Gross S. Serre C. Devic T. Bauer M. Férey G. A zirconium methacrylate oxocluster as precursor for the low-temperature synthesis of porous zirconium(IV) dicarboxylates.Chem. Commun. (Camb.). 2010; 46: 767-769Crossref PubMed Google Scholar MOFs. Recently, Park and co-workers reported DGIST-1, which displays an infinite Ti-O chain inorganic building block resulting from the reorganization of the pristine Ti6 or Ti8 clusters in the DEF/benzoic acid reaction system.30Keum Y. Park S. Chen Y.-P. Park J. Titanium-carboxylate metal-organic framework based on an unprecedented Ti-oxo chain cluster.Angew. Chem. Int. Ed. 2018; 57: 14852-14856Crossref PubMed Scopus (89) Google Scholar Similarly, Lin and co-workers found that a Ti3 building unit was generated in N,N-dimethylformamide (DMF)/acetic acid mixture when the same Ti6 cluster precursor reacted with a 4,4-biphenyl-dicarboxylic acid (BPDC) linker.31Feng X. Song Y. Chen J.S. Li Z. Chen E.Y. Kaufmann M. Wang C. Lin W. Cobalt-bridged secondary building units in a titanium metal-organic framework catalyze cascade reduction of N-heteroarenes.Chem. Sci. 2019; 10: 2193-2198Crossref PubMed Scopus (29) Google Scholar It further supported that alternative solvent systems other than the conventional one, i.e., DEF or DMF with modulators, could be an important factor in helping the preservation of the original connectivity in the Ti-O cluster precursor during reactions. In addition, the configuration of the Ti-O cluster precursor, such as the chemical component and connection mode, could represent another essential determinant for the linker-exchange process during the MOF formation. All the aforementioned Ti-O clusters reported so far feature large terminal monocarboxylate ligands with bulky aromatic moieties in a densely arranged configuration, which could possibly impede the effective bonding exchange between the protective species and the targeting linker for MOF formation. In this case, Ti-O connections of the cluster have to be reorganized to preferentially facilitate the linker exchange. Therefore, selection of a Ti-O cluster precursor with adequate space flexibility, particularly protected by small and appropriate terminal ligands such as formate or acetate, could be a feasible solution. However, to our knowledge, controlled synthesis of Ti-MOF starting from such Ti-O clusters with adapted reactivity and directly via linker exchange has never been achieved to date. Here, we report a controlled preparation of a microporous Ti-MOF, denoted MIP-207 (MIP stands for the Materials of the Institute of porous materials from Paris), via direct ligand exchange between the small terminal monocarboxylate species of a Ti8O8 cluster (Ti8-acetate-formate, Ti8AF) and the targeting trimesic acid (BTC) for MOF fabrication. MIP-207 can be synthesized not only under solvothermal conditions by using the preformed Ti8 cluster as precursor, but also in reflux reaction under ambient pressure by the assembly of the in situ generated Ti8O8 cluster and BTC, which is concise and facile for scale-up preparation. The BTC linker in the structure adopts a meta-connection mode leaving the free carboxylic group pointing toward the pore, which allows a successful partial substitution of trimesate linker by different isophthalates with diverse functional groups, so that the chemical environment of the MOF pore can be tuned. It is noteworthy that the Ti8AF cluster features an appropriate reactivity and a green scalable production, which makes it a suitable precursor for rational design and direct synthesis of Ti-MOFs. Furthermore, MIP-207 displays good water stability at room temperature (RT) and a promising adsorptive selectivity of carbon dioxide (CO2) over nitrogen, suitable for future CO2 working adsorption processes. Considerable progress in crystalline Ti-O clusters has been achieved during the past few decades, leading to diverse structures with different numbers of Ti centers.32Steunou N. Robert F. Boubekeur K. Ribot F. Sanchez C. Synthesis through an in situ esterification process and characterization of oxo isopropoxo titanium clusters.Inorg. Chim. Acta. 1998; 279: 144-151Crossref Scopus (66) Google Scholar, 33Rozes L. Sanchez C. Titanium oxo-clusters: precursors for a Lego-like construction of nanostructured hybrid materials.Chem. Soc. Rev. 2011; 40: 1006-1030Crossref PubMed Scopus (286) Google Scholar, 34Assi H. Mouchaham G. Steunou N. Devic T. Serre C. Titanium coordination compounds: from discrete metal complexes to metal-organic frameworks.Chem. Soc. Rev. 2017; 46: 3431-3452Crossref PubMed Google Scholar, 35Fang W.-H. Zhang L. Zhang J. Synthetic strategies, diverse structures and tuneable properties of polyoxo-titanium clusters.Chem. Soc. Rev. 2018; 47: 404-421Crossref PubMed Google Scholar, 36Chakraborty B. Weinstock I.A. Water-soluble titanium-oxides: complexes, clusters and nanocrystals.Coord. Chem. Rev. 2019; 382: 85-102Crossref Scopus (45) Google Scholar In most cases, the syntheses of Ti-O clusters require hydrolysis of Ti precursor under solvothermal conditions, which is always limited by long reaction time, low reaction yield, and small scale for further applications. In contrast, the Ti8AF cluster was prepared under reflux conditions with ambient pressure for a short duration, simply by heating the mixture of Ti(iPrO)4, formic acid, and acetic anhydride in a round-bottomed flask in contact with air. This facile process allows easy scale-up preparation. The crystal structure of the Ti8(μ2-O)8(acetate)12(formate)4 (Ti8AF) cluster was solved ab initio from high-resolution powder X-ray diffraction (PXRD) data (Figures S1 and S2; Tables S1 and S2). As shown in Figure 1, different from the reported Ti8 clusters, the protective ligands of the Ti8AF cluster are bridging formates and acetates, which are of much less steric hindrance or weaker bonding interactions with the Ti(IV) ions in comparison with those reported, such as 4-aminobenzoic acid, terephthalic acid, isobutyric acid, and sulfate, to name a few. It not only provides adequate space and freedom for the surrounding coordination but also possesses appropriate coordination strength between the ligands and Ti-O core, as it is well demonstrated that both formate and acetate are good modulators for MOF synthesis and are thus replaced smoothly by multitopic carboxylate linkers.37Wu H. Chua Y.S. Krungleviciute V. Tyagi M. Chen P. Yildirim T. Zhou W. Unusual and highly tunable missing-linker defects in zirconium metal-organic framework UiO-66 and their important effects on gas adsorption.J. Am. Chem. Soc. 2013; 135: 10525-10532Crossref PubMed Scopus (941) Google Scholar, 38Schaate A. Roy P. Godt A. Lippke J. Waltz F. Wiebcke M. Behrens P. Modulated synthesis of Zr-based metal-organic frameworks: from nano to single crystals.Chemistry. 2011; 17: 6643-6651Crossref PubMed Scopus (1130) Google Scholar, 39Bai Y. Dou Y. Xie L.H. Rutledge W. Li J.R. Zhou H.C. Zr-based metal-organic frameworks: design, synthesis, structure, and applications.Chem. Soc. Rev. 2016; 45: 2327-2367Crossref PubMed Google Scholar Hence, a much easier installation of the MOF linker molecule can be promoted via an efficient linkage exchange when the Ti8AF cluster is used as precursor (see Figures S6–S9 for the detailed characterizations). With the Ti8AF cluster in hand, controlled synthesis of Ti-MOF using it as precursor was carried out. Based on the influence of the reported solvent systems, acetic anhydride was selected because it is a widely used solvent in organic synthesis and has been proven to be efficient for MOF preparation.40Wang S. Lee J.S. Wahiduzzaman M. Park J. Muschi M. Martineau-Corcos C. Tissot A. Cho K.H. Marrot J. Shepard W. et al.A robust large-pore zirconium carboxylate metal-organic framework for energy-efficient water-sorption-driven refrigeration.Nat. Energy. 2018; 3: 985-993Crossref Scopus (144) Google Scholar A highly crystalline Ti-MOF of chemical formula Ti8(μ2-O)8(acetate)8(BTC)4, named MIP-207, was obtained in the solvent mixture of formic acid and acetic anhydride under solvothermal conditions (Figure S10). The crystal structure was initially solved from PXRD data and further refined with the geometry optimization performed at the density functional theory (Tables S3 and S4; Figures S3–S5). This reveals that the MIP-207 structure crystallizes in a tetragonal P4/nbm space group with unit-cell parameters of a = b = 24.2224(15) Å, c = 7.8291(5) Å, and V = 4,593.5(6) Å3. As shown in Figure 2A, the entire arrangement and configuration of the Ti8 cluster core is maintained in the SBU of MIP-207. A thorough ligand exchange was observed for all of the terminal formates. Eight carboxylate groups from the BTC molecules occupy the adjacent positions of formates and acetates in an up-and-down mode above and below the symmetrical plane of the cluster core, which could be due to the steric hindrance repulsion effect. Each Ti8 cluster is interconnected with neighboring four SBUs by using a meta-position carboxylate group of the BTC linker, forming a two-dimensional (2D) layer with a large amount of free carboxylic acid groups facing the voids (Figure 2B). The presence of both acetate and BTC moieties is confirmed by the 13C solid-state nuclear magnetic resonance (NMR) spectrum (Figures S13 and S14), in which all carboxylic carbon atoms are clearly distinguished. The presence of the free carboxylic groups is validated by the 1H solid-state NMR spectrum that displays a characteristic acidic proton at 13.3 ppm (Figure S13). Contiguous layers stack against each other in a strictly ordered fashion so that the channel of about 6 Å (Figure S12) inside the Ti8 cluster and between SBUs remains when viewed along the c axis of the structure (Figure 2C), resulting in a Brunauer-Emmett-Teller (BET) area of 570 m2 g−1 and a free pore volume of 0.34 cm3 g−1 deduced from the nitrogen porosimetry data collected at 77 K (Figure S11 and Table S5). There is a considerable amount of guest water molecules accommodated between layers, supplying intermolecular hydrogen bonding for guest-guest and guest-host interactions to further stabilize the crystal structure of MIP-207 (Figure 2D). Since the Ti8AF cluster and MIP-207 share the same solvent system for preparation, a direct synthesis using Ti(iPrO)4 as the Ti(IV) precursor was considered. As expected, MIP-207 was obtained from heating the mixture of Ti(iPrO)4 and BTC in the presence of formic acid and acetic anhydride under solvothermal conditions. A further attempt at performing the same reaction under reflux conditions worked as well, although with a slightly less crystalline product. Additionally, the absence of formate in the MIP-207 structure inspired us to replace formic acid by acetic acid, since acetic acid is much more cost-effective and of less risk when handled in large quantity in comparison with formic acid. To this end, a product of the same phase but with a slightly worse crystallinity was obtained by applying acetic acid instead of formic acid. Thus, the preparation of MIP-207 was improved to a green scalable chemistry level, which could be of remarkable benefit for its future applications on an industrial scale. Water stability is an important concern for MOFs when real application conditions are considered. Therefore, stability of MIP-207 in contact with water was checked (Figure S15). First, a long-duration (18 months) exposure of an MOF sample in open-air atmosphere was carried out. The PXRD pattern of the corresponding product did not show obvious change in comparison with that of the pristine compound, suggesting good stability of MIP-207 in air at RT. Similar observations were made when the MOF sample was soaked in water for 3 days at RT. Nevertheless, MIP-207 displays limited hydrothermal resistance, similar to other reported Ti-MOFs. Both hot water vapor (100°C) and hot liquid water (80°C) could destroy the long-range order of MIP-207 crystal structure within 24 h. Therefore, MIP-207 presents moderate water stability at the same level of NH2-MIL-125, which is adequate for applications involving water vapor at low temperatures.14Wang S. Kitao T. Guillou N. Wahiduzzaman M. Martineau-Corcos C. Nouar F. Tissot A. Binet L. Ramsahye N. Devautour-Vinot S. et al.A phase transformable ultrastable titanium-carboxylate framework for photoconduction.Nat. Commun. 2018; 9: 1660Crossref PubMed Scopus (100) Google Scholar,41Gordeeva L.G. Solovyeva M.V. Aristov Y.I. NH2-MIL-125 as a promising material for adsorptive heat transformation and storage.Energy. 2016; 100: 18-24Crossref Scopus (73) Google Scholar,42Permyakova A. Wang S. Courbon E. Nouar F. Heymans N. D'Ans P. Barrier N. Billemont P. De Weireld G. Steunou N. et al.Design of salt–metal organic framework composites for seasonal heat storage applications.J. Mater. Chem. A. 2017; 5: 12889-12898Crossref Google Scholar Thermal stability of MIP-207 was evaluated by a combined analysis of thermogravimetric data and temperature-dependent PXRD data (Figures S16 and S17). A continuous weight loss was observed from RT to 325°C in the thermogravimetric analysis (TGA) curve before the sharp drop, which could be ascribed to the gradual departure of guest solvent molecules and terminal acetates. The PXRD patterns confirm the successful maintenance of the long-range order of the MOF crystal structure up to 300°C, with slight alterations in relative intensity of some peaks. Further increase of heating temperature leads to a fast decomposition of the MOF structure, evidenced by a steep weight loss in TGA and a significant decrease of crystallinity in PXRD. Therefore, MIP-207 is among the best thermally stable Ti-MOFs reported so far. The BTC molecule in the MIP-207 structure uses two carboxylate groups at meta-positions on the benzene ring for the linkage of SBUs and leaves the third carboxylic acid group free from coordination, so it could be considered as an isophthalate-type linker. Thus, to make the chemical environment of the MOF cavity diverse and tunable, we can envisage partial or even entire replacement of the BTC by other functional linkers with similar molecular size and angles between the two connection sites as that of the isophthalic acid (IPA). Accordingly, various similar linkers have therefore been tested under the same reaction conditions (acetic acid/acetic anhydride solvent system, reflux), and the corresponding results are shown in Figure 3 and listed in Table 1.Table 1Summary of Secondary Linker Substitution and Corresponding Selective CO2 Sorption PerformanceEntrySubstitution LinkerRatioaThe ratio of the secondary linker was determined by the NMR data obtained with decomposed MOF product in D2O/KOH solution. (mol %)SBETbData obtained from the nitrogen adsorption isotherm collected at 77 K. (m2 g−1)SBETbData obtained from the nitrogen adsorption isotherm collected at 77 K. (m2 cm−3)CO2 Uptake 298 K, 0.15 bar (mmol g−1)CO2 Working Capacity 298 K (mmol g−1)CO2 Working Capacity 298 K (μmol g−1 m−2)IAST Selectivity CO2/N2 = 15:85, 298 K, 1 bar1––5908200.890.631.0752.825-tBu-IPA56809500.880.630.9345.235-OH-IPA75307400.690.520.9842.345-Me-IPA77501,0401.040.730.9755.555-NH2-IPA76308801.000.711.1348.46IPA86709300.820.600.9045.775-OMe-IPA97501,0401.010.710.9547.885-F-IPA125607800.860.611.0950.895-Br-IPA126208700.850.610.9848.6105-NO2-IPA137801,0900.810.590.7647.3115-SO3H-IPA174205900.520.431.0227.212PYDc3,5-Pyridine-dicarboxylic acid.186809301.210.841.2453.613PDAd3,5-Pyrazole-dicarboxylic acid.57301,0101.140.791.0860.714TDCe2,5-Thiophene-dicarboxylic acid.137701,0601.090.750.9758.315FDCf2,5-Furan-dicarboxylic acid.217501,0201.020.720.9649.216IPA56809400.960.691.0143.05-NO2-IPA5a The ratio of the secondary linker was determined by the NMR data obtained with decomposed MOF product in D2O/KOH solution.b Data obtained from the nitrogen adsorption isotherm collected at 77 K.c 3,5-Pyridine-dicarboxylic acid.d 3,5-Pyrazole-dicarboxylic acid.e 2,5-Thiophene-dicarboxylic acid.f 2,5-Furan-dicarboxylic acid. Open table in a new tab If no crystalline MOF comprising the pure isophthalate ligands could be obtained, a good tolerance toward a large range of functional groups of this substitution reaction was observed when partial substitution of trimesate by IPA derivatives was applied (Table 1, entries 2–12; Figures S18–S21). Interestingly, the electronic effect of the functional group plays an important role in determining the final ratio of the secondary linker included. Compared with the electron-withdrawing free carboxyl group in the pure MIP-207 structure, the electron-donating functions including H, Me, OH, NH2, OMe, and tBu on the IPA moiety all result in replacing ratios below 10% (Table 1, entries 2–7; Figure S22). In sharp contrast, electron-withdrawing functional groups, such as -NO2, -SO3H, -F, -Br, and pyridyl (Table 1, entries 8–12; Figure S23), give rise to elevated substitution proportions (i.e., 12–18 mol %). In particular, the higher replacing rates of the bulky -NO2 and -SO3H derivatives compared with the less hindered -H and -Me ones indeed highlight the key role of the influence of electronic effect. It is noteworthy that dicar" @default.
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