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The development of novel photocatalysts usually centers on features such as band structures, various nano-, micro-, or macro-forms, and composites in efforts to tune their light absorption and charge separation efficiency. In comparison, the selectivity of photocatalysts with respect to features of reactants such as size and charge has received much less attention, in part due to the difficulty in designing semiconducting photocatalysts with uniform pore size. Here, we use crystalline porous chalcogenides as a platform to probe reactant selectivity in photocatalytic processes. The 3-in-1 integration of high surface area, uniform porosity, and favorable band structures in such chalcogenides makes them excellent candidates for efficient and selective photocatalytic processes. We show that their photocatalytic activity and selectivity are closely related to their differing affinity and selectivity for different guest species. In particular, unlike common solid-state photocatalysts with neutral framework, the anionic nature of the porous chalcogenide framework used here endows them with a high degree of selectivity for cationic species in both guest exchange and closely coupled photocatalytic transformation of such guests. Another interesting discovery is the observation of an unusual ion exchange process involving a transient state of over-saturation of exchanged ions, which can be explained by a transition from an initially kinetically controlled process to a subsequent thermodynamically controlled one. This work is part of ongoing efforts to contribute to the development of a new generation of crystalline porous photocatalysts with custom-designed selectivity for various reactants or products. [ABSTRACT FROM AUTHOR]

Therare coexistence of the copper monomer and paddle-wheel dimerin the same crystal framework creates an apparent linear pseudocoppertrimer configuration that induces an unprecedented equalization ofpyridyl and carboxyl functionality in a heterofunctional pyridyl dicarboxylateligand, leading to an intriguing assembly into a highly symmetricalporous framework, despite the low symmetry of the ligand. The materialshows a total CO2uptake of 55 cm3/g at 1 atmand 273 K. [ABSTRACT FROM AUTHOR]

Abstract: Benzo[1,2-h: 5,4-h′]diquinoline(1a) represents a new family of tridentate NCN pincer ligand. We report the synthesis of the parent ligand (1a) and its derivatives (1b R = Me, 1c R = t-Butyl, 1d R = Phenyl). The ligands were characterized by 1H and 13C NMR, as well as mass spectral analysis, and X-ray structural determination. They readily undergo cyclometalation with LiPdCl4, Pd(OAc)2, and K2PtCl4 to form the cyclometalated Pd(NCN)Cl (2a–c, 3a), and Pt(NCN)Cl (4a) pincer complexes. These complexes have been characterized through NMR, and mass spectrometry. PdNCNCl (2a) structure was determined by single crystal X-ray diffraction. Complex 2a has shown to catalyze the Heck coupling reaction between bromobenzene and n-butylacyrlate in NMP at 140 °C, TON of 2506 were observed. [Copyright &y& Elsevier]

Abstract: Two new bimetallic sulfides, (Haep)2·Ga2Sb2S7 (1) and Mn2(phen)Sb2S5 (2), have been synthesized under solvothermal conditions, where aep=1-(2-aminoethyl)piperazine and phen=1,10-phenanthroline. The structure of 1 consists of GaS4 tetrahedra and SbS3 trigonal pyramids and has a layered structure with 8-membered-ring windows. Interestingly, the interlayer organic cations form helices through extensive hydrogen bonds. Compound 2 has a neutral layered structure containing infinite Mn–S sheets. The organic species are attached directly to Mn atoms within the layers by covalent bonds and protrude into the interlayer region. Both compounds 1 and 2 exhibit intense photoluminescence upon photoexcitation at 360nm. Magnetic susceptibility measurements demonstrate the existence of antiferromagnetic interactions in compound 2. Crystal data: 1, orthorhombic, P212121 (No. 19), a =9.9274(2)Å, b =12.9201(3)Å, c =21.2254(4)Å, V =2722.43(10)Å3, Z =4; 2, monoclinic, P21/c (No. 14), a =12.6385(3)Å, b =12.3998(3)Å, c =12.3670(3)Å, β =111.8240(10)°, V =1799.19(7)Å3, Z =4. [Copyright &y& Elsevier]

In many areas of chemistry the synthesis of chiral compounds is a target of increasing importance. They play a vital role in biological function and in many areas of society and science, including biology, medicine, biotechnology, chemistry and agriculture. Many pharmaceutical molecules, like their biological targets, are chiral and it is therefore easy to understand the growing demand for efficient methods of producing enantiomerically pure compounds. This is equally true for the preparation of chiral solids, which have potential applications in asymmetric catalysis, chiral separations and the like. In this Review we will consider recent progress and future potential in the development of methods for the preparation of chirally pure solids, in particular where the building blocks of the structure are achiral themselves. We will discuss strategies for the synthesis of both inorganic (for example, zeolites) and inorganic–organic hybrid (for example, metal organic framework) chiral porous solids. [ABSTRACT FROM AUTHOR]

Five 4-connected zeolitic metal imidazolate frameworks have been synthesized by using complementary ligands in combination with fine-tuning of synthetic parameters such as solvent ratio. These materials exhibit four different tetrahedral topologies. In TIF-2 and TIF-3, the cubic double 4-ring units are assembled into two different topologies not previously found in metal imidazolates. TIF-2 possesses one-dimensional 12-ring channels and an unprecedented 4-connected topology. It exhibits permanent microporosity and high thermal stability. TIF-3 is the first known example of metal imidazolates with the zeolitic ACO topology. In TIF-4, TIF-5Zn, and TIF-5Co, two complementary ligands (one small and one large) control the framework topology in a cooperative manner with small ligands favoring small rings (such as 4-rings) and large ligands favoring large rings such as 6- and 8-rings, which highlights the significance of framework building units (i.e., cross-linking ligands) in the control of the framework topology, in distinct contrast with inorganic framework materials (e.g., zeolites) in which the framework topology is primarily controlled by extra-framework structure-directing agents. These new frameworks underline the rich synthetic and structural chemistry of metal-imidazolate-based porous frameworks. Solvothermal assembly between Zn2+ (or Co2+) and mixed imidazolate ligands complementary in size leads to several zeolite-like frameworks with interesting features such as double 4-rings, large pore size, and unprecedented topology. The strict ordering of two complementary ligands in the same framework demonstrates the cooperative structural templating effect. [ABSTRACT FROM AUTHOR]

Natural porous solids such as zeolites are invariably formed with inorganic cations such as Na+ and K+ (refs 1, 2). However, current research on new porous materials is mainly focused on the use of organic species as either structure-directing or structure-building units; purely inorganic systems have received relatively little attention in exploratory synthetic work. Here we report the synthesis of a series of three-dimensional sulphides and selenides containing highly mobile alkali metal cations as charge-balancing extra-framework cations. Such crystalline inorganic chalcogenides integrate zeolite-like architecture with high anionic framework polarizability and high concentrations of mobile cations. Such structural features are particularly desirable for the development of fast-ion conductors. These materials demonstrate high ionic conductivity (up to 1.8 × 10-2?ohm-1?cm-1) at room temperature and moderate to high humidity. This synthetic methodology, together with novel structural, physical and chemical properties, may lead to the development of new microporous and open-framework materials with potential applications in areas such as batteries, fuel cells, electrochemical sensors and photocatalysis. [ABSTRACT FROM AUTHOR]

Crystalline semiconducting sulfide and selenide zeolite analogs were synthesized that possess four-connected, three-dimensional tetrahedral networks built from tetravalent (M[sup4+] = Ge[sup4+] or Sn[sup4+], where M = meta) and trivalent (M³ = Ga³ or In³) cations. Microporous materials were obtained in all four combinations of M[sup4+] and N³, and some of them were thermally stable up to at least 380°C. These materials exhibit framework topologies with pore size ranging from 12 to 24 tetrahedral atoms, high surface area, high framework charge density and ion exchange capacity, and tunable electronic and optical properties. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Elaborates a study which reported a novel class of germanate zeolite structures prepared with inorganic cations or organic amines as structure-directing agents. Materials and methods of the study; Evaluation of germanium and gallium ratio; Discussion of structural correspondence between classes of body-centered cubic zeolite-type structures.

Reports on a family of zeolite-type materials that possess two independent sets of three-dimensional cross-linked helical pores, separated by a gyroid periodic minimal surface. Stimulation of research into the preparation of heterogeneous chiral catalysts of separation media that combine both shape selectivity and enantinoselectivity, by the increasing demand for enantimerically pure chemicals; Findings.

Presents the hydrothermal syntheses, X-ray crystal structures and magnetic properties of chiral tetrahedral cobalt phosphates. Description of framework structures; Use of systematic chemical variation; Control of solution acidity values; Factors that affect framework transition; Magnetic susceptibility measurements.

Studies the synthesis and structural characterization of several ruthenium porphyrin nitrosyl complexes. Experimental procedure used; Results of the study.

Presents research which synthesized zeolite type structures with large cages interconnected by multidimensional 12-ring channels. Over a dozen large-pore materials created in three different topologies; Specific discussion of tetragonal UCSB-8, rhombohedral UCSB-10 and hexagonal UCSB-6.

Presents the results of research which determined that concentrations of transition-metal atoms in frameworks can be controlled by varying the charge and geometry of the structure-directing amine molecules. Use of zeolite analogs; Generalized synthesis method for generating transition-metal-rich zeolite-type structures; Use of method; Overview of synthesis and products; New analogs and structures; Data.

A new super-supertetrahedral cluster, resembling a coreless supertetrahedral T6 cluster, was made as a tin oxyselenide by integrating hard and soft Lewis bases (O2− and Se2−) into the tetravalent system. Its hierarchical architecture, built from supertetrahedral T3-[Sn10O4Se20] and Sn2Se6 clusters, represents a new level of complexity in the cluster-based construction. Compared to pure tin selenides, the new tin oxyselenide material in this work shows much enhanced stability and size-dependent band energy level. [ABSTRACT FROM AUTHOR]

Metal chalcogenide supertetrahedral clusters (MCSCs) are of significance for developing crystalline porous framework materials and atomically precise cluster chemistry. Early research interest focused on the synthetic and structural chemistry of MCSC-based porous semiconductor materials with different cluster sizes/compositions and their applications in adsorption-based separation and optoelectronics. More recently, focus has shifted to the cluster chemistry of MCSCs to establish atomically precise structure–composition–property relationships, which are critical for regulating the properties and expanding the applications of MCSCs. Importantly, MCSCs are similar to II–VI or I–III–VI semiconductor nanocrystals (also called quantum dots, QDs) but avoid their inherent size polydispersity and structural ambiguity. Thus, discrete MCSCs, especially those that are solution-processable, could provide models for understanding various issues that cannot be easily clarified using QDs. This review covers three decades of efforts on MCSCs, including advancements in MCSC-based open frameworks (reticular chemistry), the precise structure–property relationships of MCSCs (cluster chemistry), and the functionalization and applications of MCSC-based microcrystals. An outlook on remaining problems to be solved and future trends is also presented. [ABSTRACT FROM AUTHOR]

We report a family of carbon materials (denoted SFZ8C) prepared from templated carbonization of zeolitic imidazolate framework-8 (ZIF-8) in NaCl–ZnCl 2 eutectic salt. The hard-templating effect of the salt is utilized to sustain the framework and maximize the porosity during carbonization. In addition to rich surface nitrogen and oxygen species, SFZ8Cs have large specific surface area. These combined features give rise to excellent adsorption properties for light hydrocarbon gases. SFZ8Cs have both C 2 H 2 /CO 2 selective and C 3 /C 2 selective adsorption, as well as the ability to selectively remove impurities from methane. Particularly noteworthy is the excellent C 3 /C 2 selective adsorption performance by SFZ8C-900. Its propane/ethane selectivity (7.68) is on par with the best value (7.72) reported so far, yet SFZ8C-900 excels in propane uptake capacity. The multifunctional properties together with the ease for the mass production make SFZ8Cs promising for a number of important applications. Multifunctional Selective Adsorption: Using environmentally friendly solvent-free synthesized ZIF-8 as carbon precursors and NaCl–ZnCl 2 eutectic salt as hard template, porous carbon materials with rich nitrogen sites were obtained. They exhibit strong performance for multiple separation processes such as acetylene/carbon dioxide, three-carbon/two-carbon (C 3 /C 2), and impurity/methane. [Display omitted] [ABSTRACT FROM AUTHOR]

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 C2H2/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. [ABSTRACT FROM AUTHOR]

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 C2H2/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. [ABSTRACT FROM AUTHOR]

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 C2H2 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 C2H2/C2H4, 22.7 for C2H2/CO2). Remarkably, SNNU‐98‐Mn can efficiently separate C2H2 from C2H2/CO2 and C2H2/C2H4 mixtures with a benchmark C2H2/C2H4 (1/99) breakthrough time of 2325 min g−1, and produce 99.9999 % C2H4 with a productivity up to 64.6 mmol g−1, surpassing values of reported MOF adsorbents. [ABSTRACT FROM AUTHOR]

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 C2H2 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 C2H2/C2H4, 22.7 for C2H2/CO2). Remarkably, SNNU‐98‐Mn can efficiently separate C2H2 from C2H2/CO2 and C2H2/C2H4 mixtures with a benchmark C2H2/C2H4 (1/99) breakthrough time of 2325 min g−1, and produce 99.9999 % C2H4 with a productivity up to 64.6 mmol g−1, surpassing values of reported MOF adsorbents. [ABSTRACT FROM AUTHOR]

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 C2H2 uptake capacity (200 cm3/g at 298 K), also exhibits (desirably) the lowest CO2 uptake and hence the highest C2H2/CO2 selectivity. The successful boost in both C2H2 capacity and IAST selectivity allows Co3‐cpt‐tph‐Cl to rank among the best crystalline porous materials, ionic MOFs in particular, for C2H2 uptake and C2H2/CO2 experimental breakthrough separation. [ABSTRACT FROM AUTHOR]

We report here a one‐step method for synthesizing multi‐component and in‐situ‐formed homochiral spiroborate‐ester‐based metal‐organic framework CPM‐B1. This unique material successfully integrates COF fragment spiroborate ester within the MOF and simultaneously incorporate homochirality and helicity. In addition, CPM‐B1 is a rare example of framework materials that results from the cooperative assembly of three charge‐complementary cations: +1 (lithium), +2 (cobalt), and +3 (boron). The sophistication of the co‐assembly is further highlighted by the three structural roles of lithium ions. This unique structure contributes to its multi‐functional properties such as ionic conductivity and catalytic activity for oxygen reduction reaction (by CPM‐B1 carbonized material) and provides a new path to develop MOF materials with complex secondary building units and multi‐functional applications. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Nonprecious transition metal‐organic frameworks (MOFs) are one of the most promising precursors for developing electrocatalysts with high porosity and structural rigidity. This study reports the synthesis of high efficiency electrocatalysts based on S‐doped NiFeP. MOF‐derived S‐doped NiFeP structure is synthesized by a one‐step phosphorization process with using S‐doped MOFs as the precursor, which is more convenient and environment friendly, and also helps retain the samples' framework. The oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) performance of the NiFeP catalysts can be improved after partially replacing P by S due to the tunable electronic structure. The optimized CCS‐NiFeP‐10 reaches a current density of 10 mA cm–2 for OER with an overpotential of 201 mV and outperforms most NiFe‐based catalysts. The S doping plays an important role in tuning the ΔG values for intermediates formation in Ni atoms to a suitable value and exhibits a pronouncedly improved the OER performance. CCS‐NiFeP‐20 sample presents excellent HER performance due to the d‐band center downshifting from the Fermi level. When the voltage of the electrolytic cell is 1.50 V, a current density of 10 mA cm–2 can be obtained. This strategy paves the way for designing highly active none‐noble metal catalysts. [ABSTRACT FROM AUTHOR]

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 C2H2 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 C3H8/C3H6 and C6H6/C6H12 mixtures. [ABSTRACT FROM AUTHOR]

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 C2H2 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 C3H8/C3H6 and C6H6/C6H12 mixtures. [ABSTRACT FROM AUTHOR]

High gas‐uptake capacity is desirable for many reasons such as gas storage and sequestration. Moreover, ultrahigh capacity can enable a practical separation process by mitigating the selectivity factor that sometimes compromises separation efficiency. Herein, a single‐walled nickel–organic framework with an exceptionally high gas capture capability is reported. For example, C2H4 and C2H6 uptake capacities are at record‐setting levels of 224 and 289 cm3 g−1 at 273 K and 1 bar (169 and 110 cm3 g−1 at 298 K and 1 bar), respectively. Such ultrahigh capacities for both gases give rise to an excellent separation performance, as shown for C2H6/C2H4 with breakthrough times of 100, 60 and 30 min at 273, 283 and 298 K and under 1 atm. This new material is also shown to readily remove ethylene released from fruits, and once again, its ultrahigh capacity plays a key role in the extraordinary length of time achieved in the preservation of the fruit freshness. [ABSTRACT FROM AUTHOR]

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 M3O 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. [ABSTRACT FROM AUTHOR]

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 M3O 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. [ABSTRACT FROM AUTHOR]

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 Co2V‐pacs MOFs exhibit near or at record high uptake capacities for C2H2, C2H4, C2H6, and CO2 among MOFs. The storage capacity of C2H2 is 234 cm3 g−1 (298 K) and 330 cm3 g−1 (273 K) at 1 atm for CPM‐733‐dps (the Co2V‐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 C2H2 adsorption capacity following multiple adsorption–desorption cycles. [ABSTRACT FROM AUTHOR]

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 Co2V‐pacs MOFs exhibit near or at record high uptake capacities for C2H2, C2H4, C2H6, and CO2 among MOFs. The storage capacity of C2H2 is 234 cm3 g−1 (298 K) and 330 cm3 g−1 (273 K) at 1 atm for CPM‐733‐dps (the Co2V‐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 C2H2 adsorption capacity following multiple adsorption–desorption cycles. [ABSTRACT FROM AUTHOR]

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 (H3OBDC) ligand. Interestingly, each metal site in CPM‐76 binds one solvent molecule, leading to a high density of solvent binding sites. [ABSTRACT FROM AUTHOR]

A novel discrete neutral Cd17 sulfide cluster (denoted CMM-9) with seven corners has been synthesized by slow diffusion of methanol into a mixed solution (DMF/CS2 = 1:1, weight ratio) containing an ionic starting material CMM-4. The structures of CMM-4 and CMM-9 are determined from single crystal X-ray diffraction data collected at 150 K. The structure of the new Cd17 cluster is distinctly different from the well-known C1 cluster that also has 17 Cd sites. The UV/Vis spectrum of the new cluster CMM-9 revealed a maximum absorption at 305 nm in DMF solution, which is slightly red-shifted compared to the regular C1 cluster (C1, [Cd17S4(SPh)28]2-, with a maximum absorption at 296 nm). [ABSTRACT FROM AUTHOR]

Reported here are two 4-connected 3D frameworks based on monomeric lithium nodes, which are synthesized through a mixed ligand route. By combining a negatively charged imidazole ligand and a neutral bis(imidazolyl)methane ligand (or one of its derivatives), neutral frameworks adopting chiral quartz-dual and diamond topologies have been obtained. These materials have low framework density and can reversibly adsorb hydrogen gas. [ABSTRACT FROM AUTHOR]

Reported here is a rare example of enantioselective processes between organic racemic ligands (dl-camphorates) with in situ formed chiral metal complexes. Such enantioselectivity leads to a double spontaneous resolution of two pairs of distinctly different racemates [the ΛΔ-Zn(Htea) units and the dl-camphorate ligands] into two chiral three-dimensional frameworks containing only one enantiommeric form from each racemate. This work demonstrates unique enantioselectivity in the self-assembly of metal−organic frameworks containing multiple chiral features, which points to a new avenue for the preparation of chiral framework materials and for the resolution of racemates. This work reports an interesting example that shows that multiple chiral features in metal−organic framework (MOF) building blocks can interact with each other to produce new structural and chiral phenomena. Specifically, organic racemic ligands and in situ formed chiral metal complexes undergo enantioselective recognition, leading to double spontaneous resolution of both organic dl-racemates and ΔΛ-complexes during the self-assembly of three-dimensional MOFs. [ABSTRACT FROM AUTHOR]

Zeolitic imidazolate frameworks (ZIFs) are traditionally synthesized solvothermally by using cost‐ and waste‐incurring organic solvents. Here, a direct synthesis method is reported for ZIF‐8, ZIF‐67, and their heterometallic versions from solid precursors only. This solvent‐free crystallization method not only completely avoids organic solvents, but also provides an effective path for the synthesis of homogeneous mixed‐metal ZIFs. Furthermore, under templating by NaCl/ZnCl2 eutectic salt, carbonization of the ZIF materials gives rise to a series of N‐containing high‐surface‐area carbon materials with impressive catalytic properties for the oxygen reduction reaction. [ABSTRACT FROM AUTHOR]

A strategy called ultramicroporous building unit (UBU) is introduced. It allows the creation of hierarchical bi‐porous features that work in tandem to enhance gas uptake capacity and separation. Smaller pores from UBUs promote selectivity, while larger inter‐UBU packing pores increase uptake capacity. The effectiveness of this UBU strategy is shown with a cobalt MOF (denoted SNNU‐45) in which octahedral cages with 4.5 Å pore size serve as UBUs. The C2H2 uptake capacity at 1 atm reaches 193.0 cm3 g−1 (8.6 mmol g−1) at 273 K and 134.0 cm3 g−1 (6.0 mmol g−1) at 298 K. Such high uptake capacity is accompanied by a high C2H2/CO2 selectivity of up to 8.5 at 298 K. Dynamic breakthrough studies at room temperature and 1 atm show a C2H2/CO2 breakthrough time up to 79 min g−1, among top‐performing MOFs. Grand canonical Monte Carlo simulations agree that ultrahigh C2H2/CO2 selectivity is mainly from UBU ultramicropores, while packing pores promote C2H2 uptake capacity. [ABSTRACT FROM AUTHOR]

A strategy called ultramicroporous building unit (UBU) is introduced. It allows the creation of hierarchical bi‐porous features that work in tandem to enhance gas uptake capacity and separation. Smaller pores from UBUs promote selectivity, while larger inter‐UBU packing pores increase uptake capacity. The effectiveness of this UBU strategy is shown with a cobalt MOF (denoted SNNU‐45) in which octahedral cages with 4.5 Å pore size serve as UBUs. The C2H2 uptake capacity at 1 atm reaches 193.0 cm3 g−1 (8.6 mmol g−1) at 273 K and 134.0 cm3 g−1 (6.0 mmol g−1) at 298 K. Such high uptake capacity is accompanied by a high C2H2/CO2 selectivity of up to 8.5 at 298 K. Dynamic breakthrough studies at room temperature and 1 atm show a C2H2/CO2 breakthrough time up to 79 min g−1, among top‐performing MOFs. Grand canonical Monte Carlo simulations agree that ultrahigh C2H2/CO2 selectivity is mainly from UBU ultramicropores, while packing pores promote C2H2 uptake capacity. [ABSTRACT FROM AUTHOR]

Embedding cubane [M4(OH)4] (M=Ni, Co) clusters within the matrix of metal–organic frameworks (MOFs) is a strategy to develop materials with unprecedented synergistic properties. Herein, a new material type based on the pore‐space partition of the cubic primitive minimal‐surface net (MOF‐14‐type) has been realized. CTGU‐15 made from the [Ni4(OH)4] cluster not only has very high BET surface area (3537 m2 g−1), but also exhibits bi‐microporous features with well‐defined micropores at 0.86 nm and 1.51 nm. Furthermore, CTGU‐15 is stable even under high pH (0.1 m KOH), making it well suited for methanol oxidation in basic medium. The optimal hybrid catalyst KB&CTGU‐15 (1:2) made from ketjen black (KB) and CTGU‐15 exhibits an outstanding performance with a high mass specific peak current of 527 mA mg−1 and excellent peak current density (29.8 mA cm−2) at low potential (0.6 V). The isostructural cobalt structure (CTGU‐16) has also been synthesized, further expanding the application potential of this material type. [ABSTRACT FROM AUTHOR]

Embedding cubane [M4(OH)4] (M=Ni, Co) clusters within the matrix of metal–organic frameworks (MOFs) is a strategy to develop materials with unprecedented synergistic properties. Herein, a new material type based on the pore‐space partition of the cubic primitive minimal‐surface net (MOF‐14‐type) has been realized. CTGU‐15 made from the [Ni4(OH)4] cluster not only has very high BET surface area (3537 m2 g−1), but also exhibits bi‐microporous features with well‐defined micropores at 0.86 nm and 1.51 nm. Furthermore, CTGU‐15 is stable even under high pH (0.1 m KOH), making it well suited for methanol oxidation in basic medium. The optimal hybrid catalyst KB&CTGU‐15 (1:2) made from ketjen black (KB) and CTGU‐15 exhibits an outstanding performance with a high mass specific peak current of 527 mA mg−1 and excellent peak current density (29.8 mA cm−2) at low potential (0.6 V). The isostructural cobalt structure (CTGU‐16) has also been synthesized, further expanding the application potential of this material type. [ABSTRACT FROM AUTHOR]

We report a new magnesium metal–organic framework (MOF) (CPM‐107) with a special interaction with CO2. CPM‐107 contains Mg2‐acetate chains crosslinked into a 3D net by terephthalate. It has an anionic framework encapsulating ordered extra‐framework cations and solvent molecules. The desolvated form is closed and unresponsive to common gasses, such as N2, H2, and CH4. Yet, with CO2 at 195 K, it abruptly opens and turns into a rigid porous form that is irreversible via desorption. Once opened by CO2, CPM‐107 remains in the stable porous state accessible to additional gas types over multiple cycles or CO2 itself at different temperatures. The porous phase can be re‐locked to return to the initial closed phase via re‐solvation and desolvation. Such peculiar properties of CPM‐107 are apparently linked to a convergence of factors related to both framework and extra‐framework features. The unusual CO2 effect is currently the only available path to porous CPM‐107 which shows efficient C2H2/CO2 separation. [ABSTRACT FROM AUTHOR]

We report a new magnesium metal–organic framework (MOF) (CPM‐107) with a special interaction with CO2. CPM‐107 contains Mg2‐acetate chains crosslinked into a 3D net by terephthalate. It has an anionic framework encapsulating ordered extra‐framework cations and solvent molecules. The desolvated form is closed and unresponsive to common gasses, such as N2, H2, and CH4. Yet, with CO2 at 195 K, it abruptly opens and turns into a rigid porous form that is irreversible via desorption. Once opened by CO2, CPM‐107 remains in the stable porous state accessible to additional gas types over multiple cycles or CO2 itself at different temperatures. The porous phase can be re‐locked to return to the initial closed phase via re‐solvation and desolvation. Such peculiar properties of CPM‐107 are apparently linked to a convergence of factors related to both framework and extra‐framework features. The unusual CO2 effect is currently the only available path to porous CPM‐107 which shows efficient C2H2/CO2 separation. [ABSTRACT FROM AUTHOR]

We report a new magnesium metal–organic framework (MOF) (CPM‐107) with a special interaction with CO2. CPM‐107 contains Mg2‐acetate chains crosslinked into a 3D net by terephthalate. It has an anionic framework encapsulating ordered extra‐framework cations and solvent molecules. The desolvated form is closed and unresponsive to common gasses, such as N2, H2, and CH4. Yet, with CO2 at 195 K, it abruptly opens and turns into a rigid porous form that is irreversible via desorption. Once opened by CO2, CPM‐107 remains in the stable porous state accessible to additional gas types over multiple cycles or CO2 itself at different temperatures. The porous phase can be re‐locked to return to the initial closed phase via re‐solvation and desolvation. Such peculiar properties of CPM‐107 are apparently linked to a convergence of factors related to both framework and extra‐framework features. The unusual CO2 effect is currently the only available path to porous CPM‐107 which shows efficient C2H2/CO2 separation. [ABSTRACT FROM AUTHOR]

The creation of new cluster building blocks, as well as new ligand coordination modes, are among the most effective ways to develop new framework materials. Yet, large and chiral clusters are both difficult to create and relatively few. Here, by studying the competing coordination of different azolates against carboxylate and combined carboxylate/phenolate, it is shown that the impact of azolates in the MOF‐74 synthesis system differs dramatically, leading to the synthesis of MOF‐74, UTSA‐74, and CPM‐72 for 2‐methylimidazole, 1,2,4‐triazole, and 1,2,3‐triazole, respectively. The new CPM‐72 contains a novel chiral Zn12 triazolate cluster, which features a trigonal‐prismatic Zn6 core inside an octahedral Zn6 shell. In contrast with MOF‐74 with fully deprotonated and symmetrically bonded 2,5‐dihydroxyterephthalic acid (H4DOBDC), H4DOBDC adopts an unusual nonsymmetric bonding mode in CPM‐72 (carboxylate only at one end and carboxylate/phenolate at the other), resulting in a highly porous and intrinsically chiral 3D framework. The nonsymmetric bonding mode by H4DOBDC, apparently dictated by the chiral Zn12 cluster, can be replicated with 2‐hydroxyterephthalic acid (H3OBDC), leading to the synthesis of porous isoreticular CPM‐73. [ABSTRACT FROM AUTHOR]

The introduction of a symmetry‐ and size‐matching pore‐partitioning agent in the form of either a molecular ligand, such as 2,4,6‐tri(4‐pyridinyl)‐1,3,5‐triazine (tpt), or a metal‐complex cluster, into the hexagonal channels of MIL‐88/MOF‐235‐type (the acs net) to create pacs‐type (partitioned acs) crystalline porous materials is an effective strategy to develop high‐performance gas adsorbents. We have developed an integrated COF–MOF coassembly strategy as a new method for pore‐space partitioning through the coassembly of [(M3(OH)1−x(O)x(COO)6] MOF‐type and [B3O3(py)3] COF‐type trimers. With this strategy, the coordination‐driven assembly of the acs framework occurred concurrently and synergistically with the COF‐1‐type condensation of pyridine‐4‐boronic acid into a C3‐symmetric trimeric boroxine molecule. The resulting boroxine‐based pacs materials exhibited dramatically enhanced gas‐sorption properties as compared to nonpartitioned acs‐type materials and are among the most efficient NH3‐sorption materials. [ABSTRACT FROM AUTHOR]

The introduction of a symmetry‐ and size‐matching pore‐partitioning agent in the form of either a molecular ligand, such as 2,4,6‐tri(4‐pyridinyl)‐1,3,5‐triazine (tpt), or a metal‐complex cluster, into the hexagonal channels of MIL‐88/MOF‐235‐type (the acs net) to create pacs‐type (partitioned acs) crystalline porous materials is an effective strategy to develop high‐performance gas adsorbents. We have developed an integrated COF–MOF coassembly strategy as a new method for pore‐space partitioning through the coassembly of [(M3(OH)1−x(O)x(COO)6] MOF‐type and [B3O3(py)3] COF‐type trimers. With this strategy, the coordination‐driven assembly of the acs framework occurred concurrently and synergistically with the COF‐1‐type condensation of pyridine‐4‐boronic acid into a C3‐symmetric trimeric boroxine molecule. The resulting boroxine‐based pacs materials exhibited dramatically enhanced gas‐sorption properties as compared to nonpartitioned acs‐type materials and are among the most efficient NH3‐sorption materials. [ABSTRACT FROM AUTHOR]

The integration of heterometallic units and nanostructures into metal–organic frameworks (MOFs) used for the oxygen evolution reaction (OER) can enhance the electrocatalytic performance and help elucidate underlying mechanisms. We have synthesized a series of stable MOFs (CTGU‐10a1–d1) based on trinuclear metal carboxylate clusters and a hexadentate carboxylate ligand with a (6,6)‐connected nia net. We also present a strategy to synthesize hierarchical bimetallic MOF nanostructures (CTGU‐10a2–d2). Among these, CTGU‐10c2 is the best material for the OER, with an overpotential of 240 mV at a current density of 10 mA cm−2 and a Tafel slope of 58 mV dec−1. This is superior to RuO2 and confirms CTGU‐10c2 as one of the few known high‐performing pure‐phase MOF‐OER electrocatalysts. Notably, bimetallic CTGU‐10b2 and c2 show an improved OER activity over monometallic CTGU‐10a2 and d2. Both DFT and experiments show that the remarkable OER performance of CTGU‐10c2 is due to the presence of unsaturated metal sites, a hierarchical nanobelt architecture, and the Ni–Co coupling effect. [ABSTRACT FROM AUTHOR]