Advancing Pore-Space-Partitioned Metal-Organic Frameworks with Isoreticular Cluster Concept.

Trigonal planar M3(O/OH) trimers are among the most important clusters in inorganic chemistry and are the foundational features of multiple high-impact MOF platforms. Here we introduce a concept called isoreticular cluster series and demonstrate that M3(O/OH), as the first member of a supertrimer series, can be combined with a higher hierarchical member (double-deck trimer here) to advance isoreticular chemistry. We report here an isoreticular series of pore-space-partitioned MOFs called M3M6 pacs made from co-assembly between M3 single-deck trimer and M3x2 double-deck trimer. Important factors were identified on this multi-modular MOF platform to guide optimization of each module, which enables the phase selection of M3M6 pacs by overcoming the formation of previously-always-observed same-cluster phases. The new pacs materials exhibit high surface area and high uptake capacity for CO2 and small hydrocarbons, as well as selective adsorption properties relevant to separation of industrially important mixtures such as C2H2/CO2 and C2H2/C2H4. Furthermore, new M3M6 pacs materials show electrocatalytic properties with high activity.

Cyclobutanedicarboxylate Metal-Organic Frameworks as a Platform for Dramatic Amplification of Pore Partition Effect.

Ultrafine tuning of MOF structures at subangstrom or picometer levels can help improve separation selectivity for gases with subtle differences. However, for MOFs with a large enough pore size, the effect from ultrafine tuning on sorption can be muted. Here we show an integrative strategy that couples extreme pore compression with ultrafine pore tuning. This strategy is made possible by unique combination of two features of the partitioned acs (pacs) platform: multimodular framework and exceptional tolerance toward isoreticular replacement. Specifically, we use one module (ligand 1, L1) to shrink the pore size to an extreme minimum on pacs. A compression ratio of about 30% was achieved (based on the unit cell c/a ratio) from prototypical 1,4-benzenedicarboxylate-pacs to trans-1,3-cyclobutanedicarboxylate-pacs. This is followed by using another module (ligand 2, L2) for ultrafine pore tuning (<3% compression). This L1-L2 strategy increases the C2H2/CO2 selectivity from 2.6 to 20.8 and gives rise to an excellent experimental breakthrough performance. As the shortest cyclic dicarboxylate that mimics p-benzene-based moieties using a bioisosteric (BIS) strategy on pacs, trans-1,3-cyclobutanedicarboxylate offers new opportunities in MOF chemistry.

Simultaneous Control of Flexibility and Rigidity in Pore-Space-Partitioned Metal-Organic Frameworks.

Flexi-MOFs are typically limited to low-connected (<9) frameworks. Here we report a platform-wide approach capable of creating a family of high-connected materials (collectively called CPM-220) that integrate exceptional framework flexibility with high rigidity. We show that the multi-module nature of the pore-space-partitioned pacs (partitioned acs net) platform allows us to introduce flexibility as well as to simultaneously impose high rigidity in a tunable module-specific fashion. The inter-modular synergy has remarkable macro-morphological and sub-nanometer structural impacts. A prominent manifestation at both length scales is the retention of X-ray-quality single crystallinity despite huge hexagonal c-axial contraction (≈ 30%) and harsh sample treatment such as degassing and sorption cycles. CPM-220 sets multiple precedents and benchmarks on the pacs platform in both structural and sorption properties. They possess exceptionally high benzene/cyclohexane selectivity, unusual C3H6 and C3H8 isotherms, and promising separation performance for small gas molecules such as C2H2/CO2.

Multilevel-Regulated Metal-Organic Framework Platform Integrating Pore Space Partition and Open-Metal Sites for Enhanced CO2 Photoreduction to CO with Nearly 100% Selectivity.

Rational design and regulation of atomically precise photocatalysts are essential for constructing efficient photocatalytic systems tunable at both the atomic and molecular levels. Herein, we propose a platform-based strategy capable of integrating both pore space partition (PSP) and open-metal sites (OMSs) as foundational features for constructing high-performance photocatalysts. We demonstrate the first structural prototype obtained from this strategy: pore-partitioned NiTCPE-pstp (TCPE = 1,1,2,2-tetra(4-carboxylphenyl)ethylene, pstp = partitioned stp topology). Nonpartitioned NiTCPE-stp is constructed from six-connected [Ni3(µ3-OH)(COO)6] trimer and TCPE linker to form 1D hexagonal channels with six coplanar OMSs directed at channel centers. After introducing triangular pore-partitioning ligands, half of the OMSs were retained, while the other half were used for PSP, leading to unprecedented microenvironment regulation of the pore structure. The resulting material integrates multiple advanced properties, including robustness, wider absorption range, enhanced electronic conductivity, and high CO2 adsorption, all of which are highly desirable for photocatalytic applications. Remarkably, NiTCPE-pstp exhibits excellent CO2 photoreduction activity with a high CO generation rate of 3353.6 µmol g-1 h-1 and nearly 100% selectivity. Theoretical and experimental studies show that the introduction of partitioning ligands not only optimizes the electronic structure to promote the separation and transfer of photogenerated carriers but also reduces the energy barrier for the formation of *COOH intermediates while promoting CO2 activation and CO desorption. This work is believed to be the first example to integrate PSP strategies and OMSs within metal-organic framework (MOF) photocatalysts, which provides new insight as well as new structural prototype for the design and performance optimization of MOF-based photocatalysts.

Developing Water-Stable Pore-Partitioned Metal-Organic Frameworks with Multi-Level Symmetry for High-Performance Sorption Applications.

A new perspective is proposed in the design of pore-space-partitioned MOFs that is focused on ligand symmetry properties sub-divided here into three hierarchical levels: 1) overall ligand, 2) ligand substructure such as backbone or core, and 3) the substituent groups. Different combinations of the above symmetry properties exist. Given the close correlation between nature of chemical moiety and its symmetry, such a unique perspective into ligand symmetry and sub-symmetry in MOF design translates into the influences on MOF properties. Five new MOFs have been prepared that exhibit excellent hydrothermal stability and high-performance adsorption properties with potential applications such as C3 H6 /C2 H4 and C2 H2 /CO2 selective adsorption. The combination of high stability with high benzene/cyclohexane selectivity of ≈13.7 is also of particular interest.

Multi-Modular Design of Stable Pore-Space-Partitioned Metal-Organic Frameworks for Gas Separation Applications.

Pore space partition (PSP) is an effective materials design method for developing high-performance small-pore materials for storage and separation of gas molecules. The continued success of PSP depends on broad availability and judicious choice of pore-partition ligands and better understanding of each structural module on stability and sorption properties. Here, by using substructural bioisosteric strategy (sub-BIS), a dramatic expansion of pore-partitioned materials is targeted by using ditopic dipyridyl ligands with non-aromatic cores or extenders, as well as by expanding heterometallic clusters to uncommon nickel-vanadium and nickel-indium clusters rarely known before in porous materials. The dual-module iterative refinement of pore-partition ligands and trimers leads to remarkable enhancement of chemical stability and porosity. Here a family of 23 pore-partitioned materials synthesized from five pore-partition ligands and seven types of trimeric clusters is reported. New materials with such compositionally and structurally diverse framework modules reveal key factors that dictate stability, porosity, and gas separation properties. Among these, materials based on heterometallic vanadium-nickel trimeric clusters give rise to the highest long-term hydrolytic stability and remarkable uptake capacity for CO2 , C2 H2 /C2 H4 /C2 H6 , and C3 H6 /C3 H8 hydrocarbon gases. The breakthrough experiment shows the potential application of new materials for separating gas mixtures such as C2 H2 /CO2 .

Concurrent Enhancement of Acetylene Uptake Capacity and Selectivity by Progressive Core Expansion and Extra-Framework Anions in Pore-Space-Partitioned Metal-Organic Frameworks.

A multi-stage core-expansion method is proposed here as one component of the integrative binding-site/extender/core-expansion (BEC) strategy. The conceptual deconstruction of the partitioning ligand into three editable parts draws our focus onto progressive core expansion and allows the optimization of both acetylene uptake and selectivity. The effectiveness of this strategy is shown through a family of eight cationic pore-partitioned materials containing three different partitioning ligands and various counter anions. The optimized structure, Co3 -cpt-tph-Cl (Hcpt=4-(p-carboxyphenyl)-1,2,4-triazole, H-tph=(2,5,8-tri-(4-pyridyl)-1,3,4,6,7,9-hexaazaphenalene) with the largest surface area and highest C2 H2 uptake capacity (200 cm3 /g at 298 K), also exhibits (desirably) the lowest CO2 uptake and hence the highest C2 H2 /CO2 selectivity. The successful boost in both C2 H2 capacity and IAST selectivity allows Co3 -cpt-tph-Cl to rank among the best crystalline porous materials, ionic MOFs in particular, for C2 H2 uptake and C2 H2 /CO2 experimental breakthrough separation.

Solvent-free Synthesis of Multi-Module Pore-Space-Partitioned Metal-Organic Frameworks for Gas Separation.

Multi-module design of framework materials with multiple distinct building blocks has attracted much attention because such materials are more amenable to compositional and geometrical tuning and thus offer more opportunities for property optimization. Few examples are known that use environmentally friendly and cost-effective solvent-free method to synthesize such materials. Here, we report the use of solvent-free method (also modulator-free) to synthesize a series of multi-module MOFs with high stability and separation property for C2 H2 /CO2 . The synthesis only requires simple mixing of reactants and short reaction time (2 h). Highly porous and stable materials can be made without any post-synthetic activation. The success of solvent-free synthesis of multi-module MOFs reflects the synergy between different modules, resulting in stable pore-partitioned materials, despite the fact that other competitive crystallization pathways with simpler framework compositions also exist.

De-Linker-Enabled Exceptional Volumetric Acetylene Storage Capacity and Benchmark C2 H2 /C2 H4 and C2 H2 /CO2 Separations in Metal-Organic Frameworks.

An ideal adsorbent for separation requires optimizing both storage capacity and selectivity, but maximizing both or achieving a desired balance remain challenging. Herein, a de-linker strategy is proposed to address this issue for metal-organic frameworks (MOFs). Broadly speaking, the de-linker idea targets a class of materials that may be viewed as being intermediate between zeolites and MOFs. Its feasibility is shown here by a series of ultra-microporous MOFs (SNNU-98-M, M=Mn, Co, Ni, Zn). SNNU-98 exhibit high volumetric C2 H2 uptake capacity under low and ambient pressures (175.3 cm3 cm-3 @ 0.1 bar, 222.9 cm3 cm-3 @ 1 bar, 298 K), as well as extraordinary selectivity (2405.7 for C2 H2 /C2 H4 , 22.7 for C2 H2 /CO2 ). Remarkably, SNNU-98-Mn can efficiently separate C2 H2 from C2 H2 /CO2 and C2 H2 /C2 H4 mixtures with a benchmark C2 H2 /C2 H4 (1/99) breakthrough time of 2325 min g-1 , and produce 99.9999 % C2 H4 with a productivity up to 64.6 mmol g-1 , surpassing values of reported MOF adsorbents.

Optimization of Pore-Space-Partitioned Metal-Organic Frameworks Using the Bioisosteric Concept.

Pore space partitioning (PSP) is methodically suited for dramatically increasing the density of guest binding sites, leading to the partitioned acs (pacs) platform capable of record-high uptake for CO2 and small hydrocarbons such as C2Hx. For gas separation, achieving high selectivity amid PSP-enabled high uptake offers an enticing prospect. Here we aim for high selectivity by introducing the bioisosteric (BIS) concept, a widely used drug design strategy, into the realm of pore-space-partitioned MOFs. New pacs materials have high C2H2/CO2 selectivity of up to 29, high C2H2 uptake of up to 144 cm3/g (298 K, 1 atm), and high separation potential of up to 5.3 mmol/g, leading to excellent experimental breakthrough performance. These metrics, coupled with exceptional tunability, high stability, and low regeneration energy, demonstrate the broad potential of the BIS-PSP strategy.

Metal-Mediated Directional Capping of Rod-Packing Metal-Organic Frameworks.

Two new rod-packing metal-organic frameworks (RPMOF) are constructed by regulating the in situ formation of the capping agent. In CPM-s7, carboxylate linkers extend 1D manganese-oxide chains in four additional directions, forming 3D RPMOF. The substitution of Mn2+ with a stronger Lewis acidic Co2+ , leads to an acceleration of the hydrolysis-prone sulfonate linker, resulting in presence of sulfate ions to reduce two out of the four carboxylate-extending directions, and thus forming a new 2D rod-packing CPM-s8. Density functional theory calculations and magnetization measurements reveal ferrimagnetic ordering of CPM-s8, signifying the potential of exploring 2D RPMOF for effective low-dimensional magnetic materials.

Simultaneous Control of Pore-Space Partition and Charge Distribution in Multi-Modular Metal-Organic Frameworks.

We report here a strategy for making anionic pacs type porous materials by combining pore space partition with charge reallocation. The method uses the first negatively charged pore partition ligand (2,5,8-tri-(4-pyridyl)-1,3,4,6,7,9-hexaazaphenalene, H-tph) that simultaneously enables pore partition and charge reallocation. Over two dozen anionic pacs materials have been made to demonstrate their excellent chemical stability and a high degree of tunability. Notably, Ni3 -bdt-tph (bdt=1,4-benzeneditetrazolate) exhibits month-long water stability, while CoV-bdt-tph sets a new benchmark for C2 H2 storage capacity under ambient conditions for ionic MOFs. In addition to tunable in-framework modules, we show feasibility to tune the type and concentration of extra-framework counter cations and their influence on both stability and capability to separate industrial C3 H8 /C3 H6 and C6 H6 /C6 H12 mixtures.

Ultrastable High-Connected Chromium Metal-Organic Frameworks.

State-of-the-art MOFs are generally known for chemical stability at one end of the pH scale (i.e., pH < 0 or pH > 14). Herein, we report new Cr-MOFs capable of withstanding extreme pH conditions across approximately 16 pH units from pH < 0 to pH > 14, likely the largest observed pH range for MOFs. The integration of multiple stability-enhancing factors including nonlabile Cr3+, mixed Cr-N and Cr-O cross-links, and the highest possible connectivity by Cr3O trimers enables extraordinary chemical stability confirmed by both PXRD and gas adsorption. Notably, the base stability is much higher than literature Cr-MOFs, thereby revitalizing Cr-MOF's viability in the pursuit for the most chemically stable MOFs. Among known cationic MOFs, the chemical stability of these new Cr-MOFs is unmatchable, to our knowledge. These Cr-MOFs can be developed into multiseries of isoreticular MOFs with a rich potential for functionalization, pore size, and pore geometry engineering and applications.

Tunable Metal-Organic Frameworks Based on 8-Connected Metal Trimers for High Ethane Uptake.

Metal trimers [M3 (O/OH)](OOCR)6 are among the most important structural building blocks. From these trimers, a great success has been achieved in the design of 6- or 9-connected framework materials with various topological features and outstanding gas-sorption properties. In comparison, 8-connected trimer-based metal-organic frameworks (MOFs) are rare. Given multiple competitive pathways for the formation of 6- or 9-connected frameworks, it remains challenging to identify synthetic or structural parameters that can be used to direct the self-assembly process toward trimer-based 8-connected materials. Here, a viable strategy called angle bending modulation is revealed for creating a prototypical MOF type based on 8-connected M3 (OH)(OOCR)5 (Py-R)3 trimers (M = Zn, Co, Fe). As a proof of concept, six members in this family are synthesized using three types of ligands (CPM-80, -81, and -82). These materials do not possess open-metal sites and show excellent uptake capacity for various hydrocarbon gas molecules and inverse C2 H6 /C2 H4 selectivity. CPM-81-Co, made from 2,5-furandicarboxylate and isonicotinate, features selectivity of 1.80 with high uptake capacity for ethane (123 cm3 g-1 ) and ethylene (113 cm3 g-1 ) at 298 K and 1 bar.

Metal Chalcogenide Supertetrahedral Clusters: Synthetic Control over Assembly, Dispersibility, and Their Functional Applications.

ConspectusMetal chalcogenide supertetrahedral clusters (MCSCs) bear the closest structural resemblance to II-VI or I-III-VI semiconductor nanocrystals and can be considered as well-defined ultrasmall "quantum dots" (QDs). Compared to traditional colloidal QDs that are typically associated with size dispersity, irregular surface atomic structures, poorly defined core-ligand interfaces, and random defect/dopant sites, the nano- or subnano-sized MCSCs feature precise structural properties such as atomically uniform size, precise structure, and ordered dopant distribution, all of which offer ample opportunities for a broad and in-depth understanding of the correlation between the precise local structure and site- or size-dependent properties, which are critical to the exploitation of their functional applications. Our previous Account in 2005 provided a narrative on the efforts to expand the structural diversity of open-framework materials using different-sized and compositionally tunable clusters as building blocks with a primary objective of integrating the semiconducting properties with porosity in zeolite-type solids. Over the past 15 years, significant progress has been made, particularly in the synthetic control of discrete clusters, allowing the establishment of the composition-structure-property correlation of the MCSCs to guide the optimization of their properties for various applications. In the present Account, the recent progress in MCSC-based chemistry is reviewed from three aspects: (1) controllable synthesis of new members and types of MCSC models and the development of organic-ligand-directed hybrid assembly modes for MCSC-based open frameworks; (2) new synthetic strategies for the discretization of MCSCs in crystal lattice and their dispersibility in solvents, affording practical applications of pure inorganic MCSCs as nanomaterials; and (3) functionality of MCSC-based materials including photochemical and electrochemical properties triggered by precise dopant/defect sites, open-framework-related functional expansion via host-guest chemistry, and dispersed cluster-based composite materials with synergy from functional multimetallic components. All these advances show that MCSCs with well-defined structures and atomically precise dopant/defect sites are powerful model systems for establishing the precise structure-composition-property correlation and understanding the photophysical dynamic behaviors, both of which are difficult or impossible to achieve in the traditional QD system. Perspectives on their potential applications are presented in terms of the amorphous assemblies of monodispersed MCSCs, MCSC-based two-dimensional layered materials, and optical/electronic devices.

Selective Crystallization of Rare-Earth Ions into Cationic Metal-Organic Frameworks for Rare-Earth Separation.

For rare-earth separation, selective crystallization into metal-organic frameworks (MOFs) offers new opportunities. Especially important is the development of MOF platforms with high selectivity toward target ions. Here we report a MOF platform (CPM-66) with low-coordination-number environment for rare-earth ions. This platform is highly responsive to the size variation of rare-earth ions and shows exceptional ion-size selectivity during crystallization. CPM-66 family are based on M3 O trimers (M=6-coordinated Sc, In, Er-Lu) that are rare for lanthanides. We show that the size matching between urea-type solvents and metal ions is crucial for their successful synthesis. We further show that CPM-66 enables a dramatic multi-fold increase in separation efficiency over CPM-29 with 7-coordinated ions. This work provides some insights into methods to prepare low-coordinate MOFs from large ions and such MOFs could serve as high-efficiency platforms for lanthanide separation, as well as other applications.

Pore-Space-Partition-Enabled Exceptional Ethane Uptake and Ethane-Selective Ethane-Ethylene Separation.

An ideal material for C2H6/C2H4 separation would simultaneously have the highest C2H6 uptake capacity and the highest C2H6/C2H4 selectivity. But such material is elusive. A benchmark material for ethane-selective C2H6/C2H4 separation is peroxo-functionalized MOF-74-Fe that exhibits the best known separation performance due to its high C2H6/C2H4 selectivity (4.4), although its C2H6 uptake capacity is moderate (74.3 cm3/g). Here, we report a family of pore-space-partitioned crystalline porous materials (CPMs) with exceptional C2H6 uptake capacity and C2H6/C2H4 separation potential (i.e., C2H4 recovered from the mixture) despite their moderate C2H6/C2H4 selectivity (up to 1.75). The ethane uptake capacity as high as 166.8 cm3/g at 1 atm and 298 K, more than twice that of peroxo-MOF-74-Fe, has been achieved even though the isosteric heat of adsorption (21.9-30.4 kJ/mol) for these CPMs is as low as about one-third of that for peroxo-MOF-74-Fe (66.8 kJ/mol). While the overall C2H6/C2H4 separation potentials have not yet surpassed peroxo-MOF-74-Fe, these robust CPMs exhibit outstanding properties including high thermal stability (up to 450 °C) and aqueous stability, low regeneration energy, and a high degree of chemical and geometrical tunability within the same isoreticular framework.

Bimetallic Rod-Packing Metal-Organic Framework Combining Two Charged Forms of 2-Hydroxyterephthalic Acid.

Although many rod-packing metal-organic frameworks are known, few are based on ordered heterometallic rod building unit. We show here the synthesis of CPM-76 based on an unprecedented Zn-Mg bimetallic rod with crystallographically distinguishable metal sites. The configuration of the rod offers two types of coordination site with trigonal bipyramidal and octahedral sites selectively occupied by Zn and Mg, respectively. Also unusual is the inter-connection mode between the rods, which is based on dual-charged forms (-3 and -2) of the 2-hydroxyterephthalic acid (H3 OBDC) ligand. Interestingly, each metal site in CPM-76 binds one solvent molecule, leading to a high density of solvent binding sites.

A Strategy for Constructing Pore-Space-Partitioned MOFs with High Uptake Capacity for C2 Hydrocarbons and CO2.

Introduction of pore partition agents into hexagonal channels of MIL-88 type (acs topology) endows materials with high tunability in gas sorption. Here, we report a strategy to partition acs framework into pacs (partitioned acs) crystalline porous materials (CPM). This strategy is based on insertion of in situ synthesized 4,4'-dipyridylsulfide (dps) ligands. One third of open metal sites in the acs net are retained in pacs MOFs; two thirds are used for pore-space partition. The Co2 V-pacs MOFs exhibit near or at record high uptake capacities for C2 H2 , C2 H4 , C2 H6 , and CO2 among MOFs. The storage capacity of C2 H2 is 234 cm3 g-1 (298 K) and 330 cm3 g-1 (273 K) at 1 atm for CPM-733-dps (the Co2 V-BDC form, BDC=1,4-benzenedicarboxylate). These high uptake capacities are accomplished with low heat of adsorption, a feature desirable for low-energy-cost adsorbent regeneration. CPM-733-dps is stable and shows no loss of C2 H2 adsorption capacity following multiple adsorption-desorption cycles.

Ligand Charge Separation To Build Highly Stable Quasi-Isomer of MOF-74-Zn.

Built from an unusual high-charge-density ligand 2,5-dioxido-1,4-benzenedicarboxylate (dobdc4-), MOF-74 M (M2dobdc) have unsurpassed gas uptake and separation properties. It is thus intriguing to mimic or replicate such ligand properties in other chemical systems. Here, we show a ligand charge separation (LCS) model that could offer one pathway toward this goal. Two new materials (CPM-74 and -75, corresponding to MOF-74 and IRMOF-74-II, respectively) are presented here to illustrate this concept and its feasibility. Specifically, the dobdc4- ligand in MOF-74 can be conceptually broken down into OH- and obdc3- (H3obdc = 2-hydroxyterephthalic acid), which leads to CPM-74, Zn2(OH)(obdc), that is nearly isomeric with MOF-74-Zn. Different from MOF-74, CPM-74 is made from homohelical rod packing. Moreover, CPM-74 has high hydrothermal and thermal stability uncommon for Zn-MOFs. It contains open Zn sites on 4-coordinated Zn2+ and its isosteric heat of adsorption for CO2 is 22% higher than that of MOF-74-Zn at low pressures.