Multipocket Cage Enables the Binding of High-Order Bulky and Drug Guests Uncovered by MS Methodology.

Achieving high guest loading and multiguest-binding capacity holds crucial significance for advancement in separation, catalysis, and drug delivery with synthetic receptors; however, it remains a challenging bottleneck in characterization of high-stoichiometry guest-binding events. Herein, we describe a large-sized coordination cage (MOC-70-Zn8Pd6) possessing 12 peripheral pockets capable of accommodating multiple guests and a high-resolution electrospray ionization mass spectrometry (HR-ESI-MS)-based method to understand the solution host-guest chemistry. A diverse range of bulky guests, varying from drug molecules to rigid fullerenes as well as flexible host molecules of crown ethers and calixarenes, could be loaded into open pockets with high capacities. Notably, these hollow cage pockets provide multisites to capture different guests, showing heteroguest coloading behavior to capture binary, ternary, or even quaternary guests. Moreover, a pair of commercially applied drugs for the combination therapy of chronic lymphocytic leukemia (CLL) has been tested, highlighting its potential in multidrug delivery for combined treatment.

Stereochemical Control of Redox CoII/CoIII-Cages with Switchable Cotton Effects Based on Labile-Static States.

The structural dynamics of artificial assemblies, in aspects such as molecular recognition and structural transformation, provide us with a blueprint to achieve bioinspired applications. Here, we describe the assembly of redox-switchable chiral metal-organic cages Λ8/Δ8-[Pd6(CoIIL3)8]28+ and Λ8/Δ8-[Pd6(CoIIIL3)8]36+. These isomeric cages demonstrate an on-off chirality logic gate controlled by their chemical and stereostructural dynamics tunable through redox transitions between the labile CoII-state and static CoIII-state with a distinct Cotton effect. The transition between different states is enabled by a reversible redox process and chiral recognition originating in the tris-chelate Co-centers. All cages in two states are thoroughly characterized by NMR, ESI-MS, CV, CD, and X-ray crystallographic analysis, which clarify their redox-switching behaviors upon chemical reduction/oxidation. The stereochemical lability of the CoII-center endows the Λ8/Δ8-CoII-cages with efficient chiral-induction by enantiomeric guests, leading to enantiomeric isomerization to switch between Λ8/Δ8-CoII-cages, which can be stabilized by oxidation to their chemically inert forms of Λ8/Δ8-CoIII-cages. Kinetic studies reveal that the isomerization rate of the Δ8-CoIII-cage is at least an order of magnitude slower than that of the Δ8-CoII-cage even at an elevated temperature, while its activation energy is 16 kcal mol-1 higher than that of the CoII-cage.

Linker-Guided Growth of Single-Crystal Covalent Organic Frameworks.

The core features of covalent organic frameworks (COFs) are crystallinity and porosity. However, the synthesis of single-crystal COFs with monomers of diverse reactivity and adjustment of their pore structures remain challenging. Here, we show that linkers that can react with a node to form single-crystal COFs can guide other linkers that form either COFs or amorphous polymers with the node to gain single-crystal COFs with mixed components, which are homogeneous on the unit cell scale with controlled ratios. With the linker-guided crystal growth method, we created nine types of single-crystal COFs with up to nine different components, which are more complex than any known crystal. The structure of the crystal adapted approximately to that of the main component, and its pore volume could be expanded up to 8.8%. Different components lead to complex and diverse pore structures and offer the possibilities to gain positive synergies, as exemplified by a bicomponent COF with 2200 and 733% SO2 uptake capacity of that of the two pure-component counterparts at 298 K and 0.002 bar. The selectivity for separation of SO2/CO2 ranges from 1230 to 4247 for flue gas based on ideal adsorbed solution theory, recording porous crystals. The bicomponent COF also exhibits a 1300% retention time of its pure-component counterparts for SO2 in a dynamic column breakthrough experiment for deep desulfurization.

Photocatalysis Meets Confinement: An Emerging Opportunity for Photoinduced Organic Transformations.

The self-assembled metal-organic cages (MOCs) have been evolved as a paradigm of enzyme-mimic catalysts since they are able to synergize multifunctionalities inherent in metal and organic components and constitute microenvironments characteristic of enzymatic spatial confinement and versatile host-guest interactions, thus facilitating unconventional organic transformations via unique driving-forces such as weak noncovalent binding and electron/energy transfer. Recently, MOC-based photoreactors emerged as a burgeoning platform of supramolecular photocatalysis, displaying anomalous reactivities and selectivities distinct from bulk solution. This perspective recaps two decades journey of the photoinduced radical reactions by using photoactive metal-organic cages (PMOCs) as artificial reactors, outlining how the cage-confined photocatalysis was evolved from stoichiometric photoreactions to photocatalytic turnover, from high-energy UV-irradiation to sustainable visible-light photoactivation, and from simple radical reactions to multi-level chemo- and stereoselectivities. We will focus on PMOCs that merge structural and functional biomimicry into a single-cage to behave as multi-role photoreactors, emphasizing their potentials in tackling current challenges in organic transformations through single-electron transfer (SET) or energy transfer (EnT) pathways in a simple, green while feasible manner.

Anion Modulation of Ag-Imidazole Cuboctahedral Cage Microenvironments for Efficient Electrocatalytic CO2 Reduction.

How to achieve CO2 electroreduction in high efficiency is a current challenge with the mechanism not well understood yet. The metal-organic cages with multiple metal sites, tunable active centers, and well-defined microenvironments may provide a promising catalyst model. Here, we report self-assembly of Ag4L4 type cuboctahedral cages from coordination dynamic Ag+ ion and triangular imidazolyl ligand 1,3,5-tris(1-benzylbenzimidazol-2-yl) benzene (Ag-MOC-X, X=NO3, ClO4, BF4) via anion template effect. Notably, Ag-MOC-NO3 achieves the highest CO faradaic efficiency in pH-universal electrolytes of 86.1 % (acidic), 94.1 % (neutral) and 95.3 % (alkaline), much higher than those of Ag-MOC-ClO4 and Ag-MOC-BF4 with just different counter anions. In situ attenuated total reflection Fourier transform infrared spectroscopy observes formation of vital intermediate *COOH for CO2-to-CO conversion. The density functional theory calculations suggest that the adsorption of CO2 on unsaturated Ag-site is stabilized by C-H⋅⋅⋅O hydrogen-bonding of CO2 in a microenvironment surrounded by three benzimidazole rings, and the activation of CO2 is dependent on the coordination dynamics of Ag-centers modulated by the hosted anions through Ag⋅⋅⋅X interactions. This work offers a supramolecular electrocatalytic strategy based on Ag-coordination geometry and host-guest interaction regulation of MOCs as high-efficient electrocatalysts for CO2 reduction to CO which is a key intermediate in chemical industry process.

Sequential radical and cationic reactivity at separated sites within one molecule in solution.

Distonic radical cations (DRCs) with spatially separated charge and radical sites are expected to show both radical and cationic reactivity at different sites within one molecule. However, such "dual" reactivity has rarely been observed in the condensed phase. Herein we report the isolation of crystalline 1λ2,3λ2-1-phosphonia-3-phosphinyl-cyclohex-4-enes 2a,b˙+, which can be considered delocalized DRCs and were completely characterized by crystallographic, spectroscopic, and computational methods. These DRCs contain a radical and cationic site with seven and six valence electrons, respectively, which are both stabilized via conjugation, yet remain spatially separated. They exhibit reactivity that differs from that of conventional radical cations (CRCs); specifically they show sequential radical and cationic reactivity at separated sites within one molecule in solution.

Thermal control over phosphorescence or thermally activated delayed fluorescence in a metal-organic framework.

By integrating a tailor-made donor-acceptor (D-A) ligand in a metal-organic framework (MOF), a material with unprecedented features emerges. The ligand combines a pair of cyano groups as acceptors with four sulfanylphenyls as donors, which expose each a carboxylic acid as coordination sites. Upon treatment with zinc nitrate in a solvothermal synthesis, the MOF is obtained. The new material combines temperature-assisted reverse intersystem crossing (RISC) and intersystem crossing (ISC). As these two mechanisms are active in different temperature windows, thermal switching between their characteristic emission wavelengths is observed for this material. The two mechanisms can be activated by both, one-photon absorption (OPA) and two-photon absorption (TPA) resulting in a large excitement window ranging from ultraviolet (UV) over visible light (VL) to near infrared (NIR). Furthermore, the emission features of the material are pH sensitive, such that its application potential is demonstrated in a first ammonia sensor.

Microporous Fluorinated MOF with Multiple Adsorption Sites for Efficient Recovery of C2H6 and C3H8 from Natural Gas.

Purifying C2H6/C3H8 from a ternary natural gas mixture through adsorption separation is an important but challenging process in the petrochemical industry. To address this challenge, the industry is exploring effective strategies for designing high-performance adsorbents. In this study, we present two metal-organic frameworks (MOFs), DMOF-TF and DMOF-(CF3)2, which have fluorinated pores obtained by substituting linker ligands in the host material. This pore engineering strategy not only provides suitable pore confinement but also enhances the adsorption capacities for C2H6/C3H8 by providing additional binding sites. Theoretical calculations and transient breakthrough experiments show that the introduction of F atoms not only improves the efficiency of natural gas separation but also provides multiple adsorption sites for C2H6/C3H8-framework interactions.

Characterization of Four Complete Mitogenomes of Monolepta Species and Their Related Phylogenetic Implications.

Monolepta is one of the diverse genera in the subfamily Galerucinae, including 708 species and 6 sub-species worldwide. To explore the information on the mitogenome characteristics and phylogeny of the section "Monoleptites", especially the genus Monolepta, we obtained the newly completed mitochondrial genomes (mitogenomes) of four Monolepta species using high-throughput sequencing technology. The lengths of these four new mitochondrial genomes are 16,672 bp, 16,965 bp, 16,012 bp, and 15,866 bp in size, respectively. All four mitochondrial genomes include 22 transfer RNA genes (tRNAs), 13 protein-coding genes (PCGs), 2 ribosomal RNA genes (rRNAs), and one control region, which is consistent with other Coleoptera. The results of the nonsynonymous with synonymous substitution rates showed that ND6 had the highest evolution rate, while COI displayed the lowest evolution rate. The substitution saturation of three datasets (13 PCGs_codon1, 13 PCGs_codon2, 13 PCGs_codon3) showed that there was no saturation across all datasets. Phylogenetic analyses based on three datasets (ND1, 15 genes of mitogenomes, and 13 PCGs_AA) were carried out using maximum likelihood (ML) and Bayesian inference (BI) methods. The results showed that mitogenomes had a greater capacity to resolve the main clades than the ND1 gene at the suprageneric and species levels. The section "Monoleptites" was proven to be a monophyletic group, while Monolepta was a non-monophyletic group. Based on ND1 data, the newly sequenced species whose antennal segment 2 was shorter than 3 were split into several clades, while, based on the mitogenomic dataset, the four newly sequenced species had close relationships with Paleosepharia. The species whose antennal segment 2 was as long as 3 were split into two clades, which indicated that the characteristic of "antennal segment 2 as long as 3" of the true "Monolepta" evolved multiple times in several subgroups. Therefore, to explore the relationships among the true Monolepta, the most important thing is to perform a thorough revision of Monolepta and related genera in the future.

Capture Fluorocarbon and Chlorofluorocarbon from Air Using DUT-67 for Safety and Semi-Quantitative Analysis.

Fluoro- and chlorofluorocabons (FC/CFCs) are important refrigerants, solvents, and fluoropolymers in industry while being toxic and carrying high global warming potential. Detection and reclamation of FC/CFCs based on adsorption technology with highly selective adsorbents is important to labor safety and environmental protection. Herein, the study reports an integrated method to combine capture, separation, enrichment, and analysis of representative FC/CFCs (chlorodifluoromethane(R22) and 1,1,1,2-tetrafluoroethane (R134a)) by using the highly stable and porous Zr-MOF, DUT-67. Gas adsorption and breakthrough experiments demonstrate that DUT-67 has high R22/R134a uptake (124/116 cm3 g-1) and excellent R22/R134a/CO2 separation performance (IAST selectivities of R22/CO2 and R134a/CO2 ranging from 51.4 to 33.3, and 31.1 to 25.8), even in rather low concentration and humid conditions. A semi-quantitative analysis protocol is set up to analyze the low concentrations of R22/R134a based on the high selective R22/R134a adsorption ability, fast adsorption kinetics, water-resistant utility, facile regeneration, and excellent recyclability of DUT-67. In situ single-crystal X-ray diffraction, theoretical calculations, and in situ diffuse reflectance infrared Fourier transform spectra have been employed to understand the adsorption mechanism. This work may provide a potential adsorbent for purge and trap technique under room temperature, thus promoting the application of MOFs for VOCs sampling and quantitative analysis.

Anionic Ni-Based Metal-Organic Framework with Li(I) Cations in the Pores for Efficient C2H2/CO2 Separation.

Acetylene (C2H2) is widely used as a raw material for producing various downstream commodities in the petrochemical and electronic industry. Therefore, the acquisition of high-purity C2H2 from a C2H2/CO2 mixture produced by partial methane combustion or thermal hydrocarbon cracking is of great significance yet highly challenging due to their similar physical and chemical properties. Herein, we report an anionic metal-organic framework (MOF) named LIFM-210, which has Li+ cations in the pores and shows a higher adsorption affinity for C2H2 than CO2. LIFM-210 is constructed by a unique tetranuclear Ni(II) cluster acting as a 10-connected node and an organic ligand acting as a 5-connected node. Single-component adsorption and transient breakthrough experiments demonstrate the good C2H2 selective separation performance of LIFM-210. Theoretical calculations revealed that Li+ ions strongly prefer C2H2 to CO2 and are primary adsorption sites, playing vital roles in the selective separation of C2H2/CO2.