Rotor proliferation promotes high-brightness AIE of iridium emitter accomplishing high-contrast luminous imaging of latent fingerprints to level 3 details.

Luminous imaging of latent fingerprints (LFPs) necessitates the possession of high-brightness aggregation-state luminescence by developers to ensure sufficient imaging contrast and resolution. A novel strategy involving incremental rotor modification is presented for AIE activation of the iridium developer. The rotor proliferation prominently improves the rotational activity of groups and facilitates high-efficiency RIM, thereby prompting the AIE activation of iridium developer with high luminous efficiency.

Stable Hierarchical Porous Heterostructure NiP/NC@CoNiS Fabricated via the NiCo-LDH Template Strategy for High-Performance Supercapacitors.

Transition metal phosphide/sulfide (TMP/TMS) heterostructures are attractive supercapacitor electrode materials due to their rapid redox reaction kinetics. However, the limited active sites and weak interfacial interactions result in undesirable electrochemical performance. Herein, based on constructing the NiCo-LDH template on Ni-MOF-derived NiP/NC, NiP/NC@CoNiS with a porous heterostructure is fabricated by sulfurizing the intermediate and is used for supercapacitors.

In Situ MOF-74-Pyrolysis-Generated Porous Carbon Supporting Spinel CuCoO/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 CuCoO/C via pyrolysis of MOF-74-Co doped Cu.

Heterointerface Connection with Multiple Hydrogen-Bonding in Z-Scheme Heterojunction SiWCo@UiO-67-NH Deciding High Stability and Photocatalytic CO 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 [(-CH)N][SiWCo (HO)O]·17HO (SiWCo) with near-total visible region absorption, narrow band gap of 2.

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 (HTATT) as an energetic ligand, two new energetic complexes (ECs), Cu(HTATT)(HO) (EC-Cu1) and [Cu(TATT)(HO)] (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 (TiCT) respectively by an 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).

Photostable and high-brightness aggregation-induced emission of iridium luminogen achieving reliable and sensitive continuous luminescent quantification of molecular oxygen.

Online continuous luminescent oxygen quantification requires both high-brightness luminescence and superior photobleaching resistance of luminogens to afford the requisite level of sensitivity and operational stability, which remains a challenge. Herein, a fluorine-free design strategy of incremental rotors for preparing iridium luminogens with excellent photobleaching resistance and high-brightness aggregation-induced emission (AIE) is presented. The incremental rotors gradually improve the rotational activity of substituents, efficaciously activating the AIE with synchronously improved aggregation-state luminescence efficiency, which is theoretically confirmed by the variations of dipole moments and experimentally verified by the luminescent lifetimes.

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.

A Stable Triphenylamine-Based Zn(II)-MOF for Photocatalytic H 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 () ligand was synthesized to fabricate a 3D ZnO cluster-based Zn(II)-MOF photocatalyst, Zn(TCBA)(μ-HO)HO (), which was applied to efficient photoreductive H evolution and photooxidative aerobic cross-dehydrogenation coupling reactions of -aryl-tetrahydroisoquinolines and nitromethane. In , the ingenious introduction of the meta-position benzene carboxylates on the triphenylamine motif not only promotes 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.

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

Due to the inherent thermodynamic stability and kinetic inertness of CO, heterogeneous catalytic conversion of CO 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 CO conversion has always been a challenge. Herein, an infrequent tetracoordinated was synthesized and used to catalyze CO 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.

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, Co Ni -bpa-200, possessing ultrahigh stability with uncommon semiconductor behavior (σ=4.2×10  S m ) was fabricated.

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)(HO)] () (HBTI = 4,5-bistetrazole-imidazole), was synthesized by a hydrothermal method. Due to the existence of coordination water molecules in , however, its energy density was limited, which led to the insufficient detonation performance. To further improve its detonation performance, [Cu(HBTI)(NO)] () was then obtained by substituting the coordinated water molecule in with nitrate through the coordination substitution reaction under acidic conditions.

High temperature quantum tunnelling of magnetization and thousand kelvin anisotropy barrier in a Dy 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.

An Inconspicuous Six-Coordinate Neutral Dy 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(CyPO)I(CHCN)] with a certain degree of stability exhibiting a huge thermal barrier of 1062 K and hysteresis loops open up to 9 K.

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(HTBAPy)(HO)·CHO (), was constructed by employing π-conjugated 1,3,6,8-tetrakis(-benzoic acid)pyrene () as a ligand and used for 5-fluorouracil (5-FU) loading (28.2 wt %) and sustained slow release.

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

A series of binuclear dysprosium compounds, namely, [Dy(api)] (1), [Dy(api)]·2CHCl (2), [Dy(Clapi)]·2CHO (3), and [Dy(Clapi)]·2CHO (4) (Hapi = 2-(2-hydroxyphenyl)-1,3-bis[4-(2-hydroxyphenyl)-3-azabut-3-enyl]-1,3-imidazoline; HClapi = 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 Hapi/HClapi with DyCl·6HO in different solvent systems. Structural analysis reveals that each salen-type ligand provides a heptadentate coordination pocket (NO) to encapsulate a Dy ion and all of the Dy centers in 1-4 adopt a distorted square antiprism geometry with symmetry. Magnetic studies showed that compound 1 did not exhibit single-molecule magnetic (SMMs) behavior.

A Tetra-amido-Protected Ge-Spiropentadiene.

The first isolable Ge-spiropentadiene was synthesized via the reduction of (PrSi)NGeCl () with potassium. The crystal structure of reveals a spirocyclic Ge skeleton containing two Ge-Ge double bonds (avg. 2.

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 (HO)[ZnL(HO)]·3NMP·6HO (1), constructed with eco-friendly Zn and the multicarboxylate intraligand (LH) 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 ( up to 11.

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

We report the first bromine-bridged dinuclear [Dy(CyPO)(μ-Br)(Br)]·2CH single-molecule magnet with an effective energy barrier of 684 K and magnetic hysteresis below 3 K. The asymmetric Dy centres present two unique stereoisomeric octahedral coordination environments depending on the cis/trans disposition of the CyPO 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) Dy SMMs, with formulas [Dy(Hbpen)(Cl)] (1), [Dy(Hbpen)Cl(OPhBrNO)] (2), [Dy(Hbpen)(OPhClNO)] (3) and [Dy(Mbpen)(Cl)] (1CH), were controllably prepared based on a H-substituted amine-based ligand N,N'-bis(2-pyridylmethyl)-ethylenediamine (Hbpen) or a CH-substituted amine-based ligand N,N'-dimethyl-N,N'-bis(2-pyridylmethyl)-ethylenediamine (Mbpen) and are compared with the reported imine-based Dy 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.

A Robust Tb-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)(HO)]·DMF [HTCBA = tris(3'-carboxybiphenyl)amine; Ln = Tb (1), Eu (2), and Gd (3); DMF = dimethylformamide] was synthesized and characterized, in which the propeller-like TCBA 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 D 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.

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.

Modifying electron transfer between photoredox and organocatalytic units via framework interpenetration for β-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 β-enaminyl radicals before the intermediates couple with other active species, achieving β-functionalized carbonyl products.

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.

2-(5-Amino-2H-tetra-zol-2-yl)acetic acid.

In the title mol-ecule, C(3)H(5)N(5)O(2), the tetra-zole ring and carboxyl group form a dihedral angle of 82.25 (14)°. In the crystal, adjacent mol-ecules are linked through O-H⋯N, N-H⋯O and N-H⋯N hydrogen bonds into layers parallel to the bc plane.

A new polymorph of 5,5'-(ethane-1,2-di-yl)bis-(1H-tetra-zole).

The asymmetric unit of the title compound, C(4)H(6)N(8), contains a quarter of the mol-ecule, which possesses a crystallographically imposed centre of symmetry with all non-H atoms situated on a mirror plane. The crystal packing exhibits inter-molecular N-H⋯N hydrogen bonds and π-π stacking inter-actions between the tetra-zole rings of adjacent mol-ecules [centroid-centroid distance = 3.4402 (10) Å].