In Situ MOF-74-Pyrolysis-Generated Porous Carbon Supporting Spinel Cu0.15Co2.85O4/C Boosts Ammonium Perchlorate Accelerating Decomposition: Precise Cu Doping Modulating Oxygen Vacancy Concentration.

As one of the main components of solid propellant, ammonium perchlorate (AP) shows slow sluggish decomposition kinetics with unconcentrated heat release. To achieve efficient catalytical decomposition, it is a significant challenge to design reasonable catalyst structure and explore the interaction between catalyst and AP. Herein, a series of porous carbon supported spinel-typed homogeneous heterometallic composites CuxCo3-xO4/C via pyrolysis of MOF-74-Co doped Cu. On basis of precise electronic-structure-tuning through modulating Cu/Co ratio in MOF-74, Cu0.15Co2.85O4/C with 5% Cu-doping featuring oxygen vacancy concentration of 26.25% exhibits the decrease to 261.5 °C with heat release up to 1222.1 J g-1 (456.9 °C and 669.2 J g-1 for pure AP). The detail process of AP accelerated decomposition is approved by TG-DSC-FTIR-MS technique. Density functional theory calculation revealed that in the Cu0.15Co2.85O4/C, the distinctive ability for NH3 catalyzed oxidation assisted with absorption performance of active porous C boosts accelerating AP decomposition. The findings would provide an insight for perceiving and understanding AP catalytic decomposition.

Heterointerface Connection with Multiple Hydrogen-Bonding in Z-Scheme Heterojunction SiW9Co3@UiO-67-NH2 Deciding High Stability and Photocatalytic CO2 Reduction Performance.

Merging metal-organic frameworks (MOFs) and polyoxometalates (POMs) into heterogeneous heterojunction photocatalysts through in situ encapsulation is an effective approach to suppress the leachability of POMs and enhance their electron supply. The heterointerfacial connection in POMs@MOFs directly determines the performance of stability and charge separation, and the suited interaction between MOFs and POMs for POMs@MOFs heterojunctions photocatalyst is of vital importance. Here, a distinctive Keggin-type POM [(n-C4H9)N]10[SiW9Co3 (H2O)3O37]·17H2O (SiW9Co3) with near-total visible region absorption, narrow band gap of 2.23 eV, and powerful electron supply activity was prepared and tightly immobilized in the cavities of UiO-67-NH2 and UiO-68-NH2 to construct two Z-scheme heterojunctions SiW9Co3@UiO-67-NH2 and SiW9Co3@UiO-68-NH2, which were used for photocatalytic reduction of CO2 to CO. Their compositions, structures, and energy band features were fully characterized by a series of tests including XRD, FT-IR, SEM, XPS, UV-vis-DRS, UPS, and so forth. SiW9Co3@UiO-67-NH2 showed optimal photocatalytic performance with an excellent CO yield of 153.3 µmol-1·g-1·h-1 and a selectivity of 100%, which is 3.3-fold higher than that of SiW9Co3@UiO-68-NH2 and far superior to most reported POM-based heterojunctions. Comprehensive investigations with extensive photoelectric characterizations and microcalorimetric experiments demonstrated that the exceptional photocatalytic performances of SiW9Co3@UiO-67-NH2 could be attributed to the fact that (i) strong host-guest interactions were formed due to the well-matched dimensions between SiW9Co3 cluster and MOF cavity, which generated an intimate heterointerface to effectively accelerate interface electron transfer; (ii) the intimate heterointerface promoted SiW9Co3 to yield multielectron supply for efficient interfacial carrier neutralization owing to its donor-acceptor structure and narrow band gap. Additionally, the excellent durability of SiW9Co3@UiO-67-NH2 was also supported by the solidly locked SiW9Co3 and a stable MOF framework.

In situ growth of copper-based energetic complexes on GO and an MXene to synergistically promote the thermal decomposition of ammonium perchlorate.

In this work, using tri(5-aminotetrazolium)triazine (H3TATT) as an energetic ligand, two new energetic complexes (ECs), Cu(HTATT)(H2O)2 (EC-Cu1) and [Cu3(TATT)2(H2O)2]n (EC-Cu2), have been synthesized under hydrothermal conditions. Their crystal structures, thermal decomposition behaviors and specific heat capacities were determined respectively. In addition, two ECs were combined with GO (graphene oxide) and an MXene (Ti3C2TX) respectively by an in situ growth strategy to obtain four carbon nanomaterials/EC composites, which were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The effects of two ECs and four composites on the thermal decomposition of AP were studied by differential scanning calorimetry (DSC). Among them, the sample containing 8 wt% composite (GO/EC-Cu2) has the best promoting effect on AP, causing the high temperature decomposition peak to overlap with the low temperature decomposition peak of AP, reducing the decomposition peak temperature of AP from 443.6 °C to 308.9 °C, and the heat release is up to 4875 J g-1. Compared with ECs acting solely on AP, composite materials have stronger synergistic and promoting effects. This study provides a new example of the synthesis of carbon nanomaterial/EC composites and the improvement of the performance of AP-based solid propellants.

High-definition and robust visualization of latent fingerprints utilizing ultrabright aggregation-induced emission of iridium developer.

Creation of AIEgens with high brightness is compactly related to acquiring optimum AIE capabilities and still faces challenges. This study proposes an ingenious structurally regulative approach for preparing ultrabright AIEgens, taking iridium complexes as the model. The incremental rotational activity of substituents obtained by fine adjustment of the stereoscopic configuration efficaciously activates the AIE of iridium complexes and synchronously imparts high-brightness luminescence. Subsequently, benefitting from the ultrabright AIE, high-resolution visualization of latent fingerprints (LFPs) is achieved on diverse substrates by transient immersion in a solution of the AIE-active iridium complex (Ir3) for 60 s. The LFPs stained by Ir3 are integral and distinct enough to possess level 1-3 detail features, which allow precisely realizing personal identification. The LFP photograph emerges inconspicuous attenuation of contrast when aged under ambient light for 10 days and then being continuously irradiated with high-power ultraviolet light for 1 h, reflecting extraordinary aging resistance. Notably, the ultrabright AIE of Ir3 with room-temperature phosphorescence feature successfully achieves enhanced visualization of local fingerprint details with ultrahigh contrast. This LFP visualization protocol based on the ultrabright AIEgens is practical and provides a reliable solution for forensic investigations in actual scenarios.

A Stable Triphenylamine-Based Zn(II)-MOF for Photocatalytic H2 Evolution and Photooxidative Carbon-Carbon Coupling Reaction.

Efficient charge transfer has always been a challenge in heterogeneous MOF-based photoredox catalysis due to the poor electrical conductivity of the MOF photocatalyst, the toilless electron-hole recombination, and the uncontrollable host-guest interactions. Herein, a propeller-like tris(3'-carboxybiphenyl)amine (H3TCBA) ligand was synthesized to fabricate a 3D Zn3O cluster-based Zn(II)-MOF photocatalyst, Zn3(TCBA)2(µ3-H2O)H2O (Zn-TCBA), which was applied to efficient photoreductive H2 evolution and photooxidative aerobic cross-dehydrogenation coupling reactions of N-aryl-tetrahydroisoquinolines and nitromethane. In Zn-TCBA, the ingenious introduction of the meta-position benzene carboxylates on the triphenylamine motif not only promotes Zn-TCBA to exhibit a broad visible-light absorption with a maximum absorption edge of 480 nm but also causes special phenyl plane twists with dihedral angles of 27.8-45.8° through the coordination to Zn nodes. The semiconductor-like Zn clusters and the twisted TCBA3- antenna with multidimensional π interaction sites facilitate photoinduced electron transfer to render Zn-TCBA a good photocatalytic H2 evolution efficiency of 27.104 mmol·g-1·h-1 in the presence of [Co(bpy)3]Cl2 under visible-light illumination, surpassing many non-noble-metal MOF systems. Moreover, the positive enough excited-state potential of 2.03 V and the semiconductor-like characteristics of Zn-TCBA endow Zn-TCBA with double oxygen activation ability for photocatalytic oxidation of N-aryl-tetrahydroisoquinoline substrates with a yield up to 98.7% over 6 h. The durability of Zn-TCBA and the possible catalytic mechanisms were also investigated by a series of experiments including PXRD, IR, EPR, and fluorescence analyses.

Dynamic Metal-Iodide Bonds in a Tetracoordinated Cadmium-Based Metal-Organic Framework Boosting Efficient CO2 Cycloaddition under Solvent- and Cocatalyst-Free Conditions.

Due to the inherent thermodynamic stability and kinetic inertness of CO2, heterogeneous catalytic conversion of CO2 to cyclic carbonates often requires harsh operating conditions, high temperature and high pressure, and the addition of cocatalysts. Therefore, the development of efficient heterogeneous catalysts under cocatalyst-free and mild conditions for CO2 conversion has always been a challenge. Herein, an infrequent tetracoordinated Cd-MOF was synthesized and used to catalyze CO2 cycloaddition reactions efficiently without the addition of any cocatalyst, and its catalytic mechanism was systematically investigated through a series of experiments, including fluorescence analysis, X-ray photoelectron spectroscopy, microcalorimetry, and density functional theory (DFT) calculation. Cd-MOF features a 3D supermolecule structure with 1D 11.6 × 7.7 Å2 channels, and the abundant Lewis acid/base and I- sites located in the confined channel boost efficient CO2 conversion with a maximum yield of 98.2% and a turnover number value of 1080.11 at 60 °C and 0.5 MPa, far surpassing most pristine MOF-based catalytic systems. A combined experimental and DFT calculation demonstrates that the exposed Cd(II) Lewis acid sites rapidly participate in coordination to activate the epoxides, and the resulting large steric hindrance facilitates leaving of the coordinated iodide ions in a reversibly dynamic fashion convenient for the rate-determining step ring-opening as a strong nucleophile. Such a pristine MOF catalyst with self-independent catalytic ring-opening overcomes the complicated operation limitation of the traditional cocatalyst-free MOF systems based on encapsulating/postmodifying cocatalysts, providing a whole new strategy for the development of simple, green, and efficient heterogeneous catalysts for CO2 cycloaddition.

Tailoring Electronic Structure and Size of Ultrastable Metalated Metal-Organic Frameworks with Enhanced Electroconductivity for High-Performance Supercapacitors.

Utilization of metal-organic frameworks (MOFs) as electrodes for energy storage/conversion is challenging because of the low chemical stability and poor electrical conductivity of MOFs in electrolytes. A nanoscale MOF, Co0.24 Ni0.76 -bpa-200, possessing ultrahigh stability with uncommon semiconductor behavior (σ=4.2×10-3  S m-1 ) was fabricated. The MOF comprises a robust hydrophobic paddlewheel and an optimized Co/Ni ratio, with consequent control over MOF size and the degree of conjugation of the coligand. A DFT study revealed that appropriate Ni2+ doping reduces the activation energy of the system, thus providing a higher carrier concentration, and the strongly delocalized N-donor ligand notably increases the metal-ligand orbital overlap to achieve efficient charge migration, leading to continuous through-bond (-CoNi-N-CoNi-)∞ conduction paths. These structural features endow the MOF with a good cycling stability of 86.5 % (10 000 cycles) and a high specific capacitance of 1927.14 F g-1 among pristine MOF-based electrodes.

High temperature quantum tunnelling of magnetization and thousand kelvin anisotropy barrier in a Dy2 single-molecule magnet.

We report here a dinuclear DyIII iodine-bridged single-molecule magnet self-assembled by cis/trans coordination chemistry that displays a large anisotropy barrier of ca. 1300 K and a hysteresis opening temperature of 16 K. High temperature quantum tunnelling of magnetization is observed up to 56 K in zero-field and explained by the combination of the large anisotropy barrier and the local transverse field at the trans site. The results provide a model for thorough understanding of the effect of electronic structure on the magnetic behavior of lanthanide complexes.

Improved Detonation Performance Via Coordination Substitution: Synthesis and Characterization of Two New Green Energetic Coordination Polymers.

In this work, a new energetic coordination polymer (ECP), [Cu(HBTI)(H2O)]n (1) (H3BTI = 4,5-bistetrazole-imidazole), was synthesized by a hydrothermal method. Due to the existence of coordination water molecules in 1, however, its energy density was limited, which led to the insufficient detonation performance. To further improve its detonation performance, [Cu(H2BTI)(NO3)]n (2) was then obtained by substituting the coordinated water molecule in 1 with nitrate through the coordination substitution reaction under acidic conditions. The structures of two ECPs were respectively characterized using X-ray single-crystal diffraction, and the theoretical density of 2 (2.227 g·cm-3) was greater than 1 (1.851 g·cm-3). Thermogravimetric analyses showed that 2 has a one-step rapid weight loss process compared with the two-step slow weight loss process of 1. The theoretical calculations indicated that the detonation performances of 2 were better than those of 1. Moreover, the promotion effects of two ECPs on the combustion decomposition of ammonium perchlorate were studied using a differential scanning calorimetry method.

An Inconspicuous Six-Coordinate Neutral DyIII Single-Ion Magnet with Remarkable Magnetic Anisotropy and Stability.

It is a crucial challenge to address both magnetic anisotropy and stability for single-molecule magnets (SMMs) used in next-generation nanodevices. Highly axial lanthanide SMMs with neutral charge and moderate coordination numbers represent promising magnetic materials. Here, using iodide ions with large volume and low surface charge density as weak donors, we report a six-coordinate neutral dysprosium SMM [Dy(Cy3PO)2I3(CH3CN)] with a certain degree of stability exhibiting a huge thermal barrier of 1062 K and hysteresis loops open up to 9 K. Through the elaborate reduction of ligand field strength, an apparent strongly axial crystal field is provided which elicits prominent crystal-field splitting and high axiality with the thermally activated relaxation via the third-excited Kramers' doublet. Moreover, the profound influence of strong equatorial ligand substitution on the electronic structure and relaxation pathway is clearly explored in DyIII analogues. The result suggests the great potential of the reducing the transverse ligand field in the improvement of SMMs performance.

A Luminescent Mg-Metal-Organic Framework for Sustained Release of 5-Fluorouracil: Appropriate Host-Guest Interaction and Satisfied Acid-Base Resistance.

It is important to achieve a moderate sustained release rate for drug delivery, so it is critical to regulate the host-guest interactions for the rational design of a carrier. In this work, a nano-sized biocompatible metal-organic framework (MOF), Mg(H2TBAPy)(H2O)3·C4H8O2 (TDL-Mg), was constructed by employing π-conjugated 1,3,6,8-tetrakis(p-benzoic acid)pyrene (H4TBAPy) as a ligand and used for 5-fluorouracil (5-FU) loading (28.2 wt %) and sustained slow release. TDL-Mg exhibits a 3D supramolecular architecture featuring a 1D rectangle channel with a size of 6.2 × 8.1 Å2 and a Brunauer-Emmett-Teller surface area of 627 m2·g-1. Channel microenvironment analysis shows that the rigid H2TBAPy2- ligand adopts special torsion to stabilize the channels and offer rich π-binding sites; the partially deprotonated carboxyls not only participate in the formation of strong hydrogen bonds but also create a mild pH buffer environment for biological applications. Suitable host-guest interactions are generated by the synergistic effect of polydirectional hydrogen bonds, multiple π-interactions, and confined channels, which allow 5-FU@TDL-Mg to release 76% of load in 72 h, a medically reasonable rate. Microcalorimetry was used to directly quantify these host-guest interactions with a moderate enthalpy of 22.3 kJ·mol-1, which provides a distinctive thermodynamic interpretation for understanding the relationship between the MOF design and the drug release rate. Additionally, the nano-sized 5-FU@TDL-Mg can be taken up by mouse breast cancer cells (4T1 cells) for imaging based on the dramatic fluorescence change during the release of 5-FU, exhibiting potential applications in biological systems.

A Tetra-amido-Protected Ge5-Spiropentadiene.

The first isolable Ge5-spiropentadiene 1 was synthesized via the reduction of (iPr3Si)2NGeCl (3) with potassium. The crystal structure of 1 reveals a spirocyclic Ge5 skeleton containing two Ge-Ge double bonds (avg. 2.34 Å), which are fettered in two Ge3 rings with a dihedral angle of 70.193°. The DFT calculations and orbital analysis show that the σ-delocalization of the Ge5 skeleton and the 2π-delocalized aromatic Ge3 rings enhance the stability of molecule 1.

Bromine-bridged Dy2 single-molecule magnet: magnetic anisotropy driven by cis/trans stereoisomers.

We report the first bromine-bridged dinuclear [Dy(Cy3PO)2(µ-Br)(Br)2]2·2C7H8 single-molecule magnet with an effective energy barrier of 684 K and magnetic hysteresis below 3 K. The asymmetric DyIII centres present two unique stereoisomeric octahedral coordination environments depending on the cis/trans disposition of the Cy3PO ligands, leading to the orthogonality of the easy magnetic axes that annihilates the dipolar interactions.

Fine-tuning the type of equatorial donor atom in pentagonal bipyramidal Dy(iii) complexes to enhance single-molecule magnet properties.

A family of new structurally manipulable pentagonal-bipyramidal (PBP) DyIII SMMs, with formulas [Dy(Hbpen)(Cl)3] (1), [Dy(Hbpen)Cl(OPhBr2NO2)2] (2), [Dy(Hbpen)(OPhCl2NO2)3] (3) and [Dy(Mbpen)(Cl)3] (1CH3), were controllably prepared based on a H-substituted amine-based ligand N,N'-bis(2-pyridylmethyl)-ethylenediamine (Hbpen) or a CH3-substituted amine-based ligand N,N'-dimethyl-N,N'-bis(2-pyridylmethyl)-ethylenediamine (Mbpen) and are compared with the reported imine-based DyIII analogues (1'-3'). Upon fine-modulating the type of nitrogen donor on the pentagon plane, the electronic effect is efficiently implemented to significantly modify the magnetic anisotropy and SMM behavior of PBP complexes. Notably, the amine-based 2 shows a three-fold improved energy barrier and an observable hysteresis opening up to 3 K. 1 and 1CH3 exhibit slower relaxation and enhanced anisotropy compared to the imine-based analogue, accompanied by the reorientation of magnetic easy axes. Conversely, poor magnetic properties are observed in 3 after the reduction of imine. The changes in SMM behavior and uniaxial anisotropies are rationalized by both experimental and theoretical studies. The H-substituted amine has formally a larger magnitude of negative charge than imine due to the polarized N-H σ bond. However the repulsion generated by the sp3 N of amine towards the DyIII ion is also affected by the orientation of lone pair electrons. The present work provides a feasible way to rationally optimize the SMM performance of DyIII complexes, highlighting the importance of the electronic properties of an equatorial donor in controlling the quantum tunneling and the magnetic relaxation of PBP DyIII-SMMs.

A Robust TbIII-MOF for Ultrasensitive Detection of Trinitrophenol: Matched Channel Dimensions and Strong Host-Guest Interactions.

Host-Guest interaction is crucial to the sensitivity of heterogeneous sensors. Here, a series of isomorphic three-dimensional lanthanide metal-organic frameworks (Ln-MOFs), [Ln(TCBA)(H2O)2]2·DMF [H3TCBA = tris(3'-carboxybiphenyl)amine; Ln = Tb (1), Eu (2), and Gd (3); DMF = dimethylformamide] was synthesized and characterized, in which the propeller-like TCBA3- ligands adopt special torsional link between Tb(III) ions to form one-dimensional triangular channels. Optical experiments show that 1 exhibits bright green luminescence with an overall quantum yield of 26%, a 5D4 lifetime of 478 µs, and can act as an excellent heterogeneous fluorescent sensor to detect 2,4,6-trinitrophenol (TNP) explosive with an extremely low detection limit of 1.64 ppb. Because the confined channels within 1 exhibit matched dimensions toward TNP and feature multiple guest-response sites including rich π-conjugated groups, electron-donating N centers, and open metal nodes, strong host-guest interactions between 1 and TNP are captured and accurately determined by online microcalorimetry, which provides a distinctive thermodynamic perspective to understand the heterogeneous sensing behaviors. Additionally, the finely modulated heterometallic isomorphism [Tb0.816Eu0.184(TCBA)(H2O)2]2·DMF emits bright white light when excited at 380 nm and could potentially be used as single-phase white light-emitting diode phosphors materials.

Selective sensing and visualization of pesticides by ABW-type metal-organic framework based luminescent sensors.

A new ABW-type luminescent metal-organic framework (MOF) namely (H3O)[Zn2L(H2O)]·3NMP·6H2O (1), constructed with eco-friendly Zn2+ and the multicarboxylate intraligand (LH5) was designed, synthesized and fully characterized by X-ray single-crystal diffraction, steady-state absorption and emission spectroscopy, and SEM observations. The MOF-based suspension sensor 1 (NMP) demonstrated high sensitivity to low-concentration pesticides of chlorothalonil (CTL), nitrofen (NF), trifluralin (TFL), and 2,6-dichloro-4-nitroaniline (DCN), which was assigned to the synergistic effect of the photoinduced electron transfer and the fluorescence resonance energy transfer. With the highest luminescent detection efficiency (K SV up to 11.194 µmol-1 and LOD down to 2.93 ppm) to DCN, 1 (NMP) was successfully applied for the selective sensing of DCN. The MOF-based film sensor 1 (film) illustrated the selective visualization sensing of trace amounts of DCN. In addition, based on the high saturated vapor pressure of TFL and the unique bathochromic shift effect to the emission maxima of 1, the MOF-based luminescent vapor sensing device 1 (LED) successfully exhibited operability for sensing of TFL vapor. The results illustrated a feasible approach to construct new MOF-based luminescent sensors for selective sensing and visualization of pesticides.

Solvent-tuned magnetic exchange interactions in Dy2 systems ligated by a µ-phenolato heptadentate Schiff base.

A series of binuclear dysprosium compounds, namely, [Dy(api)]2 (1), [Dy(api)]2·2CH2Cl2 (2), [Dy(Clapi)]2·2C4H8O (3), and [Dy(Clapi)]2·2C3H6O (4) (H3api = 2-(2-hydroxyphenyl)-1,3-bis[4-(2-hydroxyphenyl)-3-azabut-3-enyl]-1,3-imidazoline; H3Clapi = 2-(2'-hydroxy-5'-chlorophenyl)-1,3-bis[3'-aza-4'-(2''-hydroxy-5''-chlorophenyl)prop-4'-en-1'-yl]-1,3-imidazolidine), have been isolated by the reactions of salen-type ligands H3api/H3Clapi with DyCl3·6H2O in different solvent systems. Structural analysis reveals that each salen-type ligand provides a heptadentate coordination pocket (N4O3) to encapsulate a DyIII ion and all of the DyIII centers in 1-4 adopt a distorted square antiprism geometry with D 4d symmetry. Magnetic studies showed that compound 1 did not exhibit single-molecule magnetic (SMMs) behavior. With the introduction of different lattice solvents, compounds 2-4 showed filed-induced slow magnetic relaxation with barriers U eff of 18.2 K (2), 28.0 K (3) and 16.4 K (4), respectively. Ab initio calculations were employed to interpret the magnetization behavior of 1-4. The combination of experimental and theoretical data reveal the importance of the weak exchange interaction between the DyIII ions in the observation of slow magnetic relaxation, and a relaxation mechanism has been developed to rationalize the observed difference in the U eff values. The different lattice solvents influence Dy-O-Dy bond angles and thus alter the torsion of the square antiprism geometry, consequently resulting in distinct magnetic interactions and the magnetic behavior.

Coordinative Alignment of Chiral Molecules to Control over the Chirality Transfer in Spontaneous Resolution and Asymmetric Catalysis.

The production and availability of enantiomerically pure compounds that spurred the development of chiral technologies and materials are very important to the fine chemicals and pharmaceutical industries. By coordinative alignment of enantiopure guests in the metal‒organic frameworks, we reported an approach to control over the chirality of homochiral crystallization and asymmetric transformation. Synthesized by achiral triphenylamine derivatives, the chirality of silver frameworks was determined by the encapsulated enantiopure azomethine ylides, from which clear interaction patterns were observed to explore the chiral induction principles. With the changing of addition sequence of substrates, the enantioselectivity of asymmetric cycloaddition was controlled to verify the determinant on the chirality of the bulky MOF materials. The economical chirality amplification that merges a series of complicated self-inductions, bulk homochiral crystallization and enantioselective catalysis opens new avenues for enantiopure chemical synthesis and provides a promising path for the directional design and development of homochiral materials.

Modifying electron transfer between photoredox and organocatalytic units via framework interpenetration for ß-carbonyl functionalization.

Modifying electron transfer pathways is essential to controlling the regioselectivity of heterogeneous photochemical transformations relevant to saturated carbonyls, due to fixed catalytic sites. Here we show that the interpenetration of metal-organic frameworks that contain both photoredox and asymmetric catalytic units can adjust the separations and electron transfer process between them. The enforced close proximity between two active sites via framework interpenetration accelerates the electron transfer between the oxidized photosensitizer and enamine intermediate, enabling the generation of 5πe- ß-enaminyl radicals before the intermediates couple with other active species, achieving ß-functionalized carbonyl products. The enriched benzoate and iminium groups in the catalysts provide a suitable Lewis-acid/base environment to stabilize the active radicals, allowing the protocol described to advance the ß-functionalization of saturated cyclic ketones with aryl ketones to deliver γ-hydroxyketone motifs. The homochiral environment of the pores within the recyclable frameworks provides additional spatial constraints to enhance the regioselectivity and enantioselectivity.Metal organic frameworks are promising catalysts due to their porous structure and the possible incorporation of multiple active sites. Here, the authors show that interpenetrated metal-organic frameworks containing both a photocatalyst and an organocatalyst catalyse the ß-alkylation of carbonyl compounds.

Eu-MOFs with 2-(4-carboxyphenyl)imidazo[4,5-f]-1,10-phenanthroline and ditopic carboxylates as coligands: synthesis, structure, high thermostability, and luminescence properties.

Hydrothermal reactions of europium(III) salt with 2-(4-carboxyphenyl)imidazo[4,5-f]-1,10-phenanthroline and dicarboxylic acid as coligands-benzene-1,4-dicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 2,5-dibromoterephthalic acid, and naphthalene-1,4-dicarboxylic acid-lead to four europium fluorescent materials (1-4). Structural analyses reveal that 1-4 have binuclear 3D metal-organic frameworks with different channels, void volumes, and conjugated structures tuned by ditopic carboxylates. There are no latticed and coordinated water molecules occurring in 1-3, while the free water molecules fill in 1D channels of 4. 4' was readily obtained via water removal of 4. Thermal analyses of all compounds show the high thermal stability of the main framework up to 450 °C. Optical studies indicate that 1-4 and 4' show the characteristic red luminescence emission of the Eu(III) ion in the visible regions at room temperature. On the basis of emission spectra, their luminescence lifetimes were determined. In particular, compound 4' shows a longer lifetime (τ = 0.942 ms) and significantly enhanced quantum yield (39%) compared with those of 1 (11%, 0.770 ms), 2 (4%, 0.414 ms), 3 (18%, 0.807 ms), and 4 (26%, 0.858 ms).