ACS Combinatorial Science最新文献

{"title":"Metastable Oxygen-Induced Light-Enhanced Doping in Mixed Sn–Pb Halide Perovskites","authors":"Jasmeen Nespoli,&nbsp;Matthijs Mugge,&nbsp;Lara M. van der Poll,&nbsp;Snigdha Lal,&nbsp;Bahiya Ibrahim,&nbsp;Bart Boshuizen,&nbsp;Valentina M. Caselli,&nbsp;Arjan J. Houtepen,&nbsp;Lars J. Bannenberg and Tom J. Savenije*,&nbsp;","doi":"10.1021/jacs.4c0892410.1021/jacs.4c08924","DOIUrl":"https://doi.org/10.1021/jacs.4c08924https://doi.org/10.1021/jacs.4c08924","url":null,"abstract":"<p >Mixed Sn–Pb halide perovskites are promising absorber materials for solar cells due to the possibility of tuning the bandgap energy down to 1.2–1.3 eV. However, tin-containing perovskites are susceptible to oxidation affecting the optoelectronic properties. In this work, we investigated qualitatively and quantitatively metastable oxygen-induced doping in isolated ASn_<i>x</i>Pb_1–<i>x</i>I₃ (where A is methylammonium or a mixture of formamidinium and cesium) perovskite thin films by means of microwave conductivity, structural and optical characterization techniques. We observe that longer oxygen exposure times lead to progressively higher dark conductivities, which slowly decay back to their original levels over days. Here oxygen acts as an electron acceptor, leading to tin oxidation from Sn²⁺ to Sn⁴⁺ and creation of free holes. The metastable oxygen-induced doping is enhanced by exposing the perovskite simultaneously to oxygen and light. Next, we show that doping not only leads to the reduction in the photoconductivity signal but also induces long-term effects even after loss of doping, which is thought to derive from consecutive oxidation reactions leading to the formation of defect states. On prolonged exposure to oxygen and light, optical and structural changes can be observed and related to the formation of SnO_<i>x</i> and loss of iodide near the surface. Our work highlights that even a short-term exposure to oxygen immediately impairs the charge carrier dynamics of the perovskite, while structural perovskite degradation is only noticeable upon long-term exposure and accumulation of oxidation products. Hence, for efficient solar cells, exposure of mixed Sn–Pb perovskites to oxygen during production and operation should be rigorously blocked.</p>","PeriodicalId":14,"journal":{"name":"ACS Combinatorial Science","volume":"146 45","pages":"30860–30870 30860–30870"},"PeriodicalIF":14.4,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/jacs.4c08924","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142608153","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Ligand-Based Radical Reactivity of Metal Thiosemicarbazones Prompts the Identification of Platinum(II)-Based Cytoprotectants","authors":"Michael N. Donohoe,&nbsp;Aditya Upadhyay and Derek A. Pratt*,&nbsp;","doi":"10.1021/jacs.4c1271310.1021/jacs.4c12713","DOIUrl":"https://doi.org/10.1021/jacs.4c12713https://doi.org/10.1021/jacs.4c12713","url":null,"abstract":"<p >CuATSM, a copper(II) complex of a bis(thiosemicarbazone) of diacetyl, prevents oxidative cell death and acts as a neuroprotectant <i>in vivo</i>, prompting its evaluation to treat amyotrophic lateral sclerosis and other neurodegenerative conditions in the clinic. We recently demonstrated that CuATSM functions as a potent radical-trapping antioxidant (RTA), inhibiting lipid peroxidation and associated ferroptotic cell death by a noncanonical mechanism based on radical addition to the ligand backbone. Herein we report our investigations of the generality of this reactivity, which include studies of corresponding complexes of various other metals, including Co, Ru, Ni, Pd, Pt, and Au. Inhibited autoxidations of styrene and dioxane reveal that most of these complexes exhibit RTA activity, consistent with ligand-based reactivity, but the identity of the metal atom nevertheless plays a role. In particular, analyses of the electronic structures of the complexes of metals within the same group (i.e., the group 10 metals Ni, Pd and Pt) highlight how the metal atom can modulate the ligand-based reactivity by enabling spin delocalization to the other thiosemicarbazone moiety. The RTA activity determined in organic solution largely translates to phospholipid bilayers and mammalian cells, where most complexes inhibited lipid peroxidation and associated ferroptotic cell death. A preliminary structure–activity study revealed Pt complexes with potencies eclipsing those of archetype ferroptosis inhibitors ferrostatin-1 and liproxstatin-1, suggesting that Pt (and to a lesser extent Ni) bis(thiosemicarbazone)s may be better suited to optimization for therapeutic development than those based on Cu.</p>","PeriodicalId":14,"journal":{"name":"ACS Combinatorial Science","volume":"146 45","pages":"31307–31320 31307–31320"},"PeriodicalIF":14.4,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142608011","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Self-Assembly of Chiral Ligands on 2D Semiconductor Nanoplatelets for High Circular Dichroism","authors":"Henri Lehouelleur,&nbsp;Hong Po,&nbsp;Lina Makké,&nbsp;Ningyuan Fu,&nbsp;Leonardo Curti,&nbsp;Corentin Dabard,&nbsp;Céline Roux-Byl,&nbsp;Benoit Baptiste,&nbsp;Nathan J. Van Zee,&nbsp;Thomas Pons,&nbsp;Emmanuel Lhuillier,&nbsp;Jing Li and Sandrine Ithurria*,&nbsp;","doi":"10.1021/jacs.4c0898110.1021/jacs.4c08981","DOIUrl":"https://doi.org/10.1021/jacs.4c08981https://doi.org/10.1021/jacs.4c08981","url":null,"abstract":"<p >Group II–VI semiconductor nanoplatelets (NPLs) with atomically defined thicknesses and extended atomically flat (001) facets are used for ligand binding and chiro-optical effects. In this study, we demonstrate that tartrate ligands, anchored by two carboxylate groups, chelate the (001) facets of NPLs at an average ratio of one tartrate molecule to two cadmium (Cd) surface atoms. This assembly of chiral molecules on inorganic nanocrystals generates a circular dichroism <i>g</i>-factor as high as 1.3 × 10^–2 at the first excitonic transition wavelength of NPLs. Tartrate ligands induce an orthorhombic distortion of the initially “cubic” crystal structure, classifying the NPLs within the 222-point group. Unlike spherical nanocrystals, where it is difficult to discern whether chiral ligands affect only the surface atoms or the entire crystal structure, our findings unequivocally show that the crystal structure of NPLs is modified due to their thinness and atomically precise thickness. The in-plane lattice parameters experience compressive and tensile stresses, significantly splitting the heavy-hole and light-hole bands. Additionally, tartrate ligands adopt different conformations on the NPL surface over time, resulting in dynamic changes in the circular dichroism signal, including an inversion of its sign.</p>","PeriodicalId":14,"journal":{"name":"ACS Combinatorial Science","volume":"146 45","pages":"30871–30882 30871–30882"},"PeriodicalIF":14.4,"publicationDate":"2024-11-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142608610","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis and Stability of Biomolecules in C–H–O–N Fluids under Earth’s Upper Mantle Conditions","authors":"Tao Li,&nbsp;Nore Stolte,&nbsp;Renbiao Tao,&nbsp;Dimitri A. Sverjensky,&nbsp;Isabelle Daniel and Ding Pan*,&nbsp;","doi":"10.1021/jacs.4c1168010.1021/jacs.4c11680","DOIUrl":"https://doi.org/10.1021/jacs.4c11680https://doi.org/10.1021/jacs.4c11680","url":null,"abstract":"<p >How life started on Earth is an unsolved mystery. There are various hypotheses for the location ranging from outer space to the seafloor, subseafloor, or potentially deeper. Here, we applied extensive ab initio molecular dynamics simulations to study chemical reactions between NH₃, H₂O, H₂, and CO at pressures (<i>P</i>) and temperatures (<i>T</i>) approximating the conditions of Earth’s upper mantle (i.e., 10–13 GPa, 1000–1400 K). Contrary to the previous assumptions that large organic molecules might readily disintegrate in aqueous solutions at extreme <i>P</i>–<i>T</i> conditions, we found that many organic compounds formed without any catalysts and persisted in C–H–O–N fluids under these extreme conditions, including glycine, ribose, urea, and uracil-like molecules. Particularly, our free-energy calculations showed that the C–N bond is thermodynamically stable at 10 GPa and 1400 K. Moreover, while the pyranose (six-membered ring) form of ribose is more stable than the furanose (five-membered ring) form at ambient conditions, we found that the formation of the five-membered-ring form of ribose is thermodynamically more favored at extreme conditions, which is consistent with the exclusive incorporation of β-<span>d</span>-ribofuranose in RNA. We have uncovered a previously unexplored pathway through which the crucial biomolecules could be abiotically synthesized from geofluids in the deep interior of Earth and other planets, and these formed biomolecules could potentially contribute to the early stage of the emergence of life.</p>","PeriodicalId":14,"journal":{"name":"ACS Combinatorial Science","volume":"146 45","pages":"31240–31250 31240–31250"},"PeriodicalIF":14.4,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142608019","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The Reaction Mechanism and Rates at Ru Single-Atom Catalysts for Hydrogenation of Biomass BHMF to Produce BHMTHF for Renewable Polymers","authors":"Liyuan Huai,&nbsp;Jian Zhang* and William A. Goddard III*,&nbsp;","doi":"10.1021/jacs.4c1155110.1021/jacs.4c11551","DOIUrl":"https://doi.org/10.1021/jacs.4c11551https://doi.org/10.1021/jacs.4c11551","url":null,"abstract":"<p >Realizing high selectivity for producing biodegradable 2,5-bis(hydroxymethyl)tetrahydrofuran (BHMTHF) for renewable polymers from 5-hydroxymethylfurfural (HMF) biomass through ring hydrogenation on single-atom catalysts poses a considerable challenge due to the complexity of HMF functional groups and the difficulty of H₂ dissociation. We developed a detailed reaction mechanism based on <i>ab initio</i> molecular dynamics (AIMD) and quantum mechanics (QM) to find that Ru single-atom catalysts can simultaneously dissociate H₂ and perform the ring hydrogenation of biomass-derived 2,5-bis(hydroxymethyl)furan (BHMF) to produce biodegradable BHMTHF, with a free energy barrier of 0.82 eV. The unique property of Ru single-atom sites enables H₂ to dissociate easily on a single active site of Ru to participate directly in the reaction without diffusion. Furthermore, our predicted reaction rate from microkinetic analysis indicates that ring hydrogenation and side-chain hydrogenolysis are much faster than ring-opening hydrogenation over the range of 300–550 K. The product BHMTHF dominates with a selectivity of 98.9% at 300 and 78.4% at 550 K (the second product is 5-methylfurfural (5-MFA)). This study underscores the unique effectiveness of Ru single atoms in ring hydrogenation reactions using H₂ as the hydrogen source, offering insights for the design of single-atom catalysts for other biomass reactions.</p>","PeriodicalId":14,"journal":{"name":"ACS Combinatorial Science","volume":"146 45","pages":"31251–31263 31251–31263"},"PeriodicalIF":14.4,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142608140","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Programmable Piperazine Synthesis via Organic Photoredox Catalysis","authors":"Alexander J. Boley,&nbsp;Jason C. Genova and David A. Nicewicz*,&nbsp;","doi":"10.1021/jacs.4c1202810.1021/jacs.4c12028","DOIUrl":"https://doi.org/10.1021/jacs.4c12028https://doi.org/10.1021/jacs.4c12028","url":null,"abstract":"<p >Piperazine cores have long been identified as privileged scaffolds in the development of pharmaceutical compounds. Despite this, the facile synthesis of diverse C-substituted piperazines remains a challenge without prefunctionalized substrates/cores. Herein, we describe a programmable approach to highly diversifiable piperazine cores, which circumvents the typical need for radical precursors. The use of organic photoredox catalysis renders this method operationally simple, as direct substrate oxidation followed by 6-<i>endo-trig</i> radical cyclization with in situ generated imines may furnish the product. Additionally, the photoredox-catalyzed anti-Markovnikov hydroamination of readily accessible ene-carbamates provides a modular approach to functionalized diamine starting materials which are shown to generate more complex piperazine cores. A wide range of both carbonyl and amine condensation partners were shown to be compatible with this system in good to excellent yield.</p>","PeriodicalId":14,"journal":{"name":"ACS Combinatorial Science","volume":"146 45","pages":"31274–31280 31274–31280"},"PeriodicalIF":14.4,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142608020","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Activity Control of a Synthetic Transporter by Photodynamic Modulation of Membrane Mobility and Incorporation","authors":"Jasper E. Bos,&nbsp;Maxime A. Siegler and Sander J. Wezenberg*,&nbsp;","doi":"10.1021/jacs.4c1095210.1021/jacs.4c10952","DOIUrl":"https://doi.org/10.1021/jacs.4c10952https://doi.org/10.1021/jacs.4c10952","url":null,"abstract":"<p >Artificial transmembrane transport systems are receiving a great deal of attention for their potential therapeutic application. A major challenge is to switch their activity in response to environmental stimuli, which has been achieved mostly by modulating the binding affinity. We demonstrate here that the activity of a synthetic anion transporter can be controlled through changes in the membrane mobility and incorporation. The transporters─equipped with azobenzene photoswitches─poorly incorporate into the bilayer membrane as their thermally stable (<i>E</i>,<i>E</i>,<i>E</i>)-isomers, but incorporation is triggered by UV irradiation to give the (<i>Z</i>)-containing isomers. The latter isomers, however, are found to have a lower mobility and are therefore the least active transporters. This opposite effect of <i>E</i>-<i>Z</i> isomerization on transport capability offers unique photocontrol as is demonstrated by <i>in situ</i> irradiation studies during the used transport assays. These results help to understand the behavior of artificial transporters in a bilayer and are highly important to future designs, with new modes of biological activity and with the possibility to direct motion, which may be crucial toward achieving active transport.</p>","PeriodicalId":14,"journal":{"name":"ACS Combinatorial Science","volume":"146 45","pages":"31085–31093 31085–31093"},"PeriodicalIF":14.4,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/jacs.4c10952","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142608064","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Formation of Radical-like NH Ligand from NH3 at Ambient Conditions Mediated by Dialkyl Rare-Earth Complexes","authors":"Changjiang Wu,&nbsp;Yingzhuang Xu,&nbsp;Songyi Li,&nbsp;Yinshan Meng,&nbsp;Huayi Fang* and Chunhua Yan,&nbsp;","doi":"10.1021/jacs.4c0875210.1021/jacs.4c08752","DOIUrl":"https://doi.org/10.1021/jacs.4c08752https://doi.org/10.1021/jacs.4c08752","url":null,"abstract":"<p >Although intensive work on ammonia activation has been carried out in recent decades, generating nitrogen-centered radicals from NH₃ under ambient conditions remains quite challenging. In the presented research, the conversion of NH₃ to radical-like NH ligand has been achieved by the reactions of a series of dialkyl rare-earth (RE) complexes (<b>1-RE</b>, RE = Tb, Dy, Y, Ho, Er, Yb, and Lu) supported by β-diketiminate ligands with NH₃ in <i>n</i>-hexane at room temperature, resulting in the formations of the radical-like μ₃-NH ligands containing trinuclear RE complexes (<b>2-RE</b>). The radical-like feature of the μ₃-NH ligand was revealed by electron paramagnetic resonance and magnetic measurements, radical trapping experiments, and computational spin density analysis. In addition, H₂ was detected to form during the reaction of <b>1-RE</b> with NH₃, indicating that the radical-like μ₃-NH ligand was likely to be generated via N–H bond homolysis. Moreover, the solvents and coordination pattern of β-diketiminate ligands are crucial for the formation of the radical-like μ₃-NH ligand from NH₃. When toluene instead of <i>n</i>-hexane was used in the reaction of <b>1-RE</b> with NH₃, an array of octaamido tetranuclear RE complexes (<b>3-RE</b>) was obtained. The reaction of the dialkyl yttrium complex (<b>4-Y</b>) bearing a modified β-diketiminate ligand, in which the two mesityl substituents are replaced by a 2,6-diisopropylphenyl group and a 2-(dimethylamino)ethyl group, with NH₃ in both <i>n</i>-hexane and toluene only yielded a tetranuclear yttrium complex carrying the dianionic closed-shell μ₃-NH ligands (<b>5-Y</b>).</p>","PeriodicalId":14,"journal":{"name":"ACS Combinatorial Science","volume":"146 45","pages":"30824–30835 30824–30835"},"PeriodicalIF":14.4,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142608200","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Gene-Directed In Vitro Mining Uncovers the Insect-Repellent Constituent from Mugwort (Artemisia argyi)","authors":"Yao Zhi,&nbsp;Chong Dai,&nbsp;Xueting Fang,&nbsp;Xiaochun Xiao,&nbsp;Hui Lu,&nbsp;Fangfang Chen,&nbsp;Rong Chen,&nbsp;Weihua Ma,&nbsp;Zixin Deng,&nbsp;Li Lu* and Tiangang Liu*,&nbsp;","doi":"10.1021/jacs.4c0885710.1021/jacs.4c08857","DOIUrl":"https://doi.org/10.1021/jacs.4c08857https://doi.org/10.1021/jacs.4c08857","url":null,"abstract":"<p >Plants contain a vast array of natural products yet to be discovered, particularly those minor bioactive constituents. Identification of these constituents requires a significant amount of plant material, presenting considerable technical challenges. Mugwort (<i>Artemisia argyi</i>) is a widely recognized insect repellent herb, particularly renowned for its extensive usage during the Dragon Boat Festival in China, but the specific constituent responsible for its repellent activity remains unknown. Here, we employed a gene-directed in vitro mining approach to characterize mugwort terpene synthases (TPSs) systematically in a yeast expression system. Based on the establishment of “Terpene synthase-standard library”, we have successfully identified 54 terpene products, including a novel compound designated as cyclosantalol. Through activity screening, we have identified that (+)-intermedeol, which presents in trace amount in plants, exhibits significant repellent activity against mosquitoes and ticks. After establishing its safety and efficacy, we then achieved its biosynthetic production in a yeast chassis, with an initial yield of 2.34 g/L. The methodology employed in this study not only identified a highly effective, safe, and commercially viable insect repellent derived from mugwort but also holds promise for uncovering and producing other valuable plant natural products in future research endeavors.</p>","PeriodicalId":14,"journal":{"name":"ACS Combinatorial Science","volume":"146 45","pages":"30883–30892 30883–30892"},"PeriodicalIF":14.4,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142608201","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Integrating Compositional and Structural Diversity in Heterometallic Titanium Frameworks by Metal Exchange Methods","authors":"Eloy P. Gómez-Oliveira,&nbsp;Javier Castells-Gil,&nbsp;Clara Chinchilla-Garzón,&nbsp;Andrés Uscategui-Linares,&nbsp;Josep Albero,&nbsp;Neyvis Almora-Barrios,&nbsp;Sergio Tatay,&nbsp;Natalia M. Padial* and Carlos Martí-Gastaldo*,&nbsp;","doi":"10.1021/jacs.4c1044410.1021/jacs.4c10444","DOIUrl":"https://doi.org/10.1021/jacs.4c10444https://doi.org/10.1021/jacs.4c10444","url":null,"abstract":"<p >The increasing use of Metal–Organic Frameworks (MOFs) in separation, catalysis, or storage is linked to the targeted modification of their composition or porosity metrics. While modification of pore shape and size necessarily implies the assembly of alternative nets, compositional changes often rely on postsynthetic modification adapted to the functionalization or exchange of the organic linker or the modification of the inorganic cluster by metal exchange methods. We describe an alternative methodology that enables the integration of both types of modification, structural and compositional, in titanium MOFs by metal exchange reaction of the heterometallic cluster Ti₂Ca₂. A systematic analysis of this reactivity with MUV-10 is used to understand which experimental variables are crucial to enable replacement of calcium only or to integrate metal exchange with structural transformation. The isoreticular expanded framework, MUV-30, is next used to template the formation of MUV-301, a titanium framework not accessible by direct synthesis that displays the largest mesoporous cages reported to date. Given that the interest of Ti MOFs in photoredox applications often meets the limitations imposed by the challenges of titanium solution chemistry to design concrete candidates, this soft strategy based on preassembled frameworks will help integrate specific combinations of metals into high porosity architectures.</p>","PeriodicalId":14,"journal":{"name":"ACS Combinatorial Science","volume":"146 45","pages":"31021–31033 31021–31033"},"PeriodicalIF":14.4,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142608067","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}