Ring Of Ligand Research Articles

Synthesis, structural characterization, water ad‐/de‐sorption isotherm, and CO2 uptakes of a 2D Cu(I) metal organic framework with 1,3,5‐tris(4‐pyridylethynyl)benzene (L) and Tricyanomethanide (tcm−) ligands

AbstractA d10 Cu(I) two‐dimensional (2D) metal–organic framework (MOF) with chemical formulas, {[Cd(L)(tcm)(H2O)]⋅2H2O}n (1) (L = 1,3,5‐tris(4‐pyridylethynyl)benzene; tcm−1 = tricyanomethanide) was synthesized and structurally characterized by single crystal X‐ray diffraction method. In 1, the coordination geometry of Cu(I) ion is distorted tetrahedral coordinated to four N atoms from three L and one tcm− ligands. A 2D puckered honeycomb‐like layer is formed via the bridges of Cu(I) ions and L ligands with tris‐monodentate coordination mode. Two 2D layers are mutually interpenetrated via the π–π stacking interaction between benzene ring of L ligand and pyridyl ring of neighboring L ligand to form a two‐fold interpenetrated 2D net and then arranged orderly to construct its 3D supramolecular network. Thermal stability and in‐situ temperature‐dependent structural variations of 1 are performed by TG analysis associated with temperature‐dependent PXRD measurement. The water vapor ad‐/de‐sorption isotherm and CO2 adsorption isotherm of 1 are measured and discussed.

FK4H4-: Planar Tetracoordinate Fluorine Stabilized by Multicenter Ionic Bonding.

Planar tetracoordinate fluorine (ptF) species are very exotic and scarce due to high electronegativity of fluorine. Herein we report the ternary square ptF cluster, D4h FK4H4-, which is composed of a F center, a square K4 ring, and four outer H bridges. It is a true global minimum (GM) structure and possesses good dynamic stability. Bonding analyses indicate that there are four lone pairs for the central F atom, along with four K-H-K three-center two-electron (3c-2e) σ bonds for the peripheral K4H4 ligand ring. The stability of ptF is dominated by multicenter ionic bonds rather than the supposed σ aromaticity of the system. Excitingly, it is a pseudohalogen anion with the VDE 3.57 eV at the CCSD(T) level. The merge of ptF with pseudohalogen anion character makes the FK4H4- cluster an exotic species, which will motivate theoretical and experimental studies on novel ptF species as well as superhalogens.

The interplay between structural features and the efficiency of the energy transfer process in terbium complexes with triarylcyclopentadienyl ligands

Terbium and gadolinium complexes with triarylcyclopentadienyl ligands having electron-donating methoxy substituents in the ortho- (CpPh2Ar−o) and para- (CpPh2Ar−p) positions of one of the phenyl rings have been synthesized. Different structural types, including tetranuclear [{CpPh2Ar−oTb (THF)}2 (μ2-Cl)2(μ3-Cl)3K (THF)]2 (Tb1), [{CpPh2Ar−oTb}2 (μ2-Cl)2 (μ3-Cl)3K]2 (Tb3), [{(CpPh2Ar−oTb)2 (μ2-Cl)3}2 (μ2-Cl)2] (Tb5), [{CpPh2Ar−pTb (THF)}2 (μ2-Cl)2 (μ3-Cl)3K (THF)]2 (Tb6), binuclear [{CpPh2Ar−oTb (THF)Cl}2 (μ2-Cl)2] (Tb4), [{CpPh2Ar−pTb (THF)}2 (μ2-Cl)2 (μ3-Cl)3K (THF)]2 (Tb7), [CpPh2Ar−p2Tb (μ2-Cl) (μ3-Cl)K]2 (Tb8) and mononuclear [CpPh2Ar−o2TbCl] (Tb2) complexes have been obtained and confirmed by single crystal X-ray diffraction analysis. All designed terbium complexes exhibit high quantum yields of the photoluminescence (up to 65 %). The introduction of a methoxy group into one of the phenyl rings of the triarylcyclopentadienyl ligand leads to a more than twofold increase in the quantum yield of the terbium ion luminescence. The estimated values of radiative rate krad of the terbium ion vary in the range of 0.23–0.69 ms. The presence of the methoxy group as well as the mutual disposition of the phenyl rings promotes the appearance of an intraligand charge transfer states involved in the energy transfer process. Due to a lowering of the energy of the interconfigurational 4f −5d transitions caused by the relatively strong crystal field of the Cp ligand in bis(cyclopentadienyl) terbium complexes, the quantum yield of the photoluminescence is high at the short lifetimes of the 5D4 level of the terbium ion.

The indenyl effect on d0 organotransition metal complex LMCT luminescence: Synthesis, structural characterization, cyclic voltammetry, spectroscopic studies, and TD-DFT computations on (η5-permethylindenyl)tetrachlorotantalum(V), and comparison to (η5-pentamethylcyclopentadienyl)tetrachlorotantalum(V)

The new organotantalum(V) chloride (η5-permethylindenyl)tetrachlorotantalum, Ind*TaCl4, was prepared by addition of previously-unreported Ind*SnBu3 to TaCl5 in toluene at 70° in 53 % isolated yield. The solid-state four-legged piano-stool structure, consistent with solution multinuclear NMR spectroscopies, demonstrated that tantalum is bonded to all carbons of the five-membered ring of the permethylindenyl ligand, with little deviation in the Ta-C distances. The permethylindenyl ring torsional angles for the three independent molecules in the unit cell vary from 2.46(17)° to 5.10(17)°. The cyclic voltammogram of Ind*TaCl4 in tetrahydrofuran showed one reversible reduction feature at −1.24 V [Ta(V)/Ta(IV)] and one quasi-reversible reduction feature at −1.65 V [Ta(IV)/Ta(III)] vs. Fc/Fc+. The UV/vis LMCT absorption λmax at 593 nm (ε = 2000 M−1 cm−1) in toluene is remarkably red-shifted from that of the known η5-pentamethylcyclopentadienyl analog, luminescent-yellow Cp*TaCl4. TD-DFT calculations were used to explain the comparative UV/vis absorption spectra.

A Theoretical Study on the Influence of Five- and Six-Membered N-Heterocyclic Ring Side Chains of the N-Donor Extractants on Am(III)/Eu(III) Extraction and Separation.

According to the green development requirements of carbon neutrality and carbon peaking, the effective separation of lanthanides and actinides is one of the key factors for nuclear energy to become a sustainable energy source. In recent years, o-phenanthroline-based ligands have been proven to be effective in the separation of lanthanides and actinides. In this work, based on 5,9b-dihydro-4aH-cyclopenta[1,2-b:5,4-b']dipyridines, we designed six N-heterocyclic ring ligands and theoretically studied their extraction capacity and separation selectivity for the Am(III) and Eu(III) ions. Various theoretical methods were used to analyze the properties of the ligands and study the bonding nature of the ligands with the metal ions. Thermodynamic parameters were calculated to measure the extraction ability of the ligands to the metal ions and to explore the separation capacity of the ligand for the Am(III) and Eu(III) ions. The calculated results show that the five- and six-membered N-heterocyclic ring side chains of the ligands and the distribution of the N atoms on the side chain rings have obvious effects on the bonding of the ligands to metal ions and on the extraction and separation properties of the ligands for the metal ions. It was found that the extractants with six-membered ring side chains possess an extraction ability slightly better than that of the ligands with five-membered ring side chains and that the ligands with a pair of adjacent N atoms on the side chains have a stronger separation selectivity for the Am(III)/Eu(III) ions. The theoretical research in this work will help to understand the details of binding and extraction properties of similar ligands and provide insights for the future design of five- and six-membered heterocyclic ligands.

Impact of ring size on the C[sbnd]H activation reactivity of iron(IV)–oxo complexes: A computational study with TMC macrocycles

Here, a DFT investigation has been presented to demonstrate the relevance of the macrocyclic ligand ring size of the high-valent Fe(IV)O complex-catalyzed CH activation process. A nonheme iron-oxo compound bound with extensively studied macrocycle tetramethylcyclam (TMC) with varying ring size measures in terms of n = 12, 13, 14, 15, and 16 in [Fe(IV)O(n-TMC)(CH3CN)]2+ has been considered as the oxidant and dihydroanthracene as the general substrate. Counterions, as always, have been considered to avoid the self-interaction error in these DFT calculations. Computations were carried out to determine the effect of the axial ligand, acetonitrile, on the CH activation reactivity. It has been discovered that the complexes without axial ligands turned out to be more reactive compared to their axially coordinated counterparts. The most intriguing finding, however, has been that reactivity increased steadily with ring size increments, giving us the trend 12 < 13 < 14 < 15 < 16. Behind this typical pattern of reactivity, several factors played a role, including the energy of the electron acceptor orbital, which sequentially decreases, and the distortion energy to achieve the transition state, which also decreases as we move on from n = 12 to 16. The triplet-quintet energy difference of the oxidants also has a part to play, as it decreases with increased ring size, with the quintet becoming more and more dominant. The current studies have also been able to corroborate the experimental data that was published regarding Fe(IV)O(13-TMC) (without axial syn form) having a higher CH activation reactivity than Fe(IV)O(14-TMC) (with axial anti form). On the whole, this computational exploration gives us a reactivity pattern based on the ring size commutes and can lead to successful experimental results if pursued based on this reaction.

InnTl4-nH+ (n = 0∼4): Tetracoordinate Hydrogen in a Planar Fashion?

The recent report of planar tetracoordinate hydrogen (ptH) in In4H+ is very intriguing in planar hypercoordinate chemistry. Our high-level CCSD(T) calculations revealed that the proposed D4h-symmetric ptH In4H+ is a first-order saddle point with an imaginary frequency in the out-of-plane mode of the hydrogen atom. In fact, at the CCSD(T)/aug-cc-pV5Z/aug-cc-pV5Z-PP level, the C4v isomer, with the H atom located 0.70 Å above the In4 plane, is 0.5 kcal/mol more stable than the D4h isomer. However, given the small perturbation from planarity and essentially barrierless C4v ↔ D4h ↔ C4v transition, the vibrationally averaged structure can still be considered as a planar. Extending our exploration to the InnTl4-nH+ (n = 0-3) systems, we found all these ptH structures, except for In2Tl2H+, to be the putative global minimum. The single σ-delocalized interaction between the central hydrogen atom and InnTl4-n ligand rings proves pivotal in establishing planarity and aromaticity and conferring substantial stability upon these rule-breaking ptH species.

Effect of Metal-Organic Frameworks with Different Ligand Structures (ZIF-11 & ZIF-23) on the Optoelectronic Performance of Perovskite Photodetectors.

Crystal engineering using passivation to reduce perovskite defects is crucial to improving the quality of perovskite crystals and optoelectronic properties. Because of their unique properties, metal-organic framework materials have been used as an emerging and effective passivator for perovskite materials and optoelectronic devices. This paper focuses on the differences in the optoelectronic properties of zeolite imidazolium ester framework materials (ZIF-11 & ZIF-23) doped with different conjugated ring ligands for perovskite photodetectors. This paper proposes a simple and effective method to dope zeolite imidazolium ester framework nanoparticles (ZIF-11 & ZIF-23) into organic-inorganic perovskite MAPbI3 films. The crystalline quality of the perovskite films was improved after doping with ZIF-11 and ZIF-23. Meanwhile, the performance of the planar photoconductive devices was significantly improved. The photoresponsivity of the photodetector doped with ZIF-23 was 0.185A/W, and the detectivity was 4.22 × 1012 Jones. The photoresponsivity of the photodetector doped with ZIF-23 was 0.164 A/W, and the detectivity was 3.27 × 1012 Jones. The devices maintained long-time operational stability, operating without significant degradation for 480 s under the 1.2 V bias voltage operating condition. In addition, we observed a significant suppression of the ion migration process in ZIF-23 for a voltage-controlled ion migration process. The potential application of perovskite and MOF heterojunction materials for image information acquisition and storage is demonstrated.

Crystal structure of catena-poly[[methanoldioxidouranium(VI)]-μ-2-[5-(2-oxidophen-yl)-1H-1,2,4-triazol-3-yl]acetato-κ2 O:O'

In the title complex, [U(C10H7N3O3)O2(CH3OH)] n , the UVI cation has a typical penta-gonal-bipyramidal environment with the equatorial plane defined by one N and two O atoms of one doubly deprotonated 2-[5-(2-hy-droxy-phen-yl)-1H-1,2,4-triazol-3-yl]acetic acid ligand, a carboxyl-ate O atom of the symmetry-related ligand and the O atom of the methanol mol-ecule [U-N/Oeq 2.256 (4)-2.504 (5) Å]. The axial positions are occupied by two oxide O atoms. The equatorial atoms are almost coplanar, with the largest deviation from the mean plane being 0.121 Å for one of the O atoms. The benzene and triazole rings of the tetra-dentate chelating-bridging ligand are twisted by approximately 21.6 (2)° with respect to each other. The carboxyl-ate group of the ligand bridges two uranyl cations, forming a neutral zigzag chain reinforced by a strong O-H⋯O hydrogen bond. In the crystal, adjacent chains are linked into two-dimensional sheets parallel to the ac plane by C/N-H⋯N/O hydrogen bonding and π-π inter-actions. Further weak C-H⋯O contacts consolidate the three-dimensional supra-molecular architecture. In the solid state, the compound shows a broad medium intensity LMCT transition centred around 463 nm, which is responsible for its red colour.

Synthesis and Structure of Copper(I) Halide Complexes with Halogen-Functionalized Isocyanide Ligands

Eleven copper(I) halide complexes [CuX(CNR)3] (X = Cl, Br; R = C6H3-2,6-Cl2, C6H3-2-Cl-6-Me, C6H3-2,6-Br2, C6H3-2-Br-6-Me; X = I, R = C6H3-2,6-Cl2, C6H3-2-Cl-6-Me, C6H3-2-Br-6-Me) bearing halogen-functionalized aromatic isocyanide ligands were synthesized. The compounds were characterized by atomic emission spectroscopy (Cu), IR, 1H NMR spectroscopy and high-resolution mass spectrometry. The structure of nine compounds was determined by X-ray diffraction. Structural studies allow to reveal that the supramolecular structure of the complexes is based on weak C–H···X (X = Cl, Br, I) interactions and π-stacking of the aromatic rings of isocyanide ligands.

Structural Effects of FeN4 Active Sites Surrounded by Fourteen-Membered Ring Ligands on Oxygen Reduction Reaction Activity and Durability

Structural Effects of FeN₄ Active Sites Surrounded by Fourteen-Membered Ring Ligands on Oxygen Reduction Reaction Activity and Durability

Orientation‐Driven Large Magnetic Hysteresis of Er(III) Cyclooctatetraenide‐Based Single‐Ion Magnets Adsorbed on Ag(100)

The molecular self‐assembly and the magnetic properties of two cyclooctatetraenide (COT)‐based single‐ion magnets (SIM) adsorbed on Ag(100) in the sub‐monolayer (ML) range are reported. Our study combines scanning‐tunneling microscopy, X‐ray photoemission spectroscopy and polarized X‐ray absorption spectroscopy to show that Cp*ErCOT (Cp* = 1,2,3,4,5‐pentamethylcyclopentadienide anion) SIMs self‐assemble as alternating compact parallel rows including standing‐up and lying‐down conformations, following the main crystallographic directions of the substrate. Conversely, K[Er(COT)2], obtained from subliming the [K(18‐c‐6)][Er(COT)2]·2THF salt, forms uniaxially ordered domains with the (COT)2− rings perpendicular to the substrate plane. The polarization‐dependent X‐ray absorption spectra reproduced by the multiX simulations suggest that the strong in‐plane magnetic anisotropy of K[Er(COT)2]/Ag(100) and the weak out‐of‐plane anisotropy of Cp*ErCOT/Ag(100) can be attributed to the strikingly different surface ordering of these two complexes. Compared to the bulk phase, surface‐supported K[Er(COT)2] exhibits a similarly large hysteresis opening, while the Cp*ErCOT shows a rather small opening. This result reveals that despite structural similarities, the two organometallic SMMs have strongly different magnetic properties when adsorbed on the metal substrate, attributed to the different orientations and the resulting interactions of the ligand rings with the surface.

Enzyme-Inspired Ligand Engineering of Gold Nanoclusters for Electrocatalytic Microenvironment Manipulation.

Natural enzymes intricately regulate substrate accessibility through specific amino acid sequences and folded structures at their active sites. Achieving such precise control over the microenvironment has proven to be challenging in nanocatalysis, especially in the realm of ligand-stabilized metal nanoparticles. Here, we use atomically precise metal nanoclusters (NCs) as model catalysts to demonstrate an effective ligand engineering strategy to control the local concentration of CO2 on the surface of gold (Au) NCs during electrocatalytic CO2 reduction reactions (CO2RR). The precise incorporation of two 2-thiouracil-5-carboxylic acid (TCA) ligands within the pocket-like cavity of [Au25(pMBA)18]- NCs (pMBA = para-mercaptobenzoic acid) leads to a substantial acceleration in the reaction kinetics of CO2RR. This enhancement is attributed to a more favorable microenvironment in proximity to the active site for CO2, facilitated by supramolecular interactions between the nucleophilic Nδ- of the pyrimidine ring of the TCA ligand and the electrophilic Cδ+ of CO2. A comprehensive investigation employing absorption spectroscopy, mass spectrometry, isotopic labeling measurements, electrochemical analyses, and quantum chemical computation highlights the pivotal role of local CO2 enrichment in enhancing the activity and selectivity of TCA-modified Au25 NCs for CO2RR. Notably, a high Faradaic efficiency of 98.6% toward CO has been achieved. The surface engineering approach and catalytic fundamentals elucidated in this study provide a systematic foundation for the molecular-level design of metal-based electrocatalysts.

Elucidation of the Pyridine Ring-Opening Mechanism of 2,2'-Bipyridine or 1,10-Phenanthroline Ligands at Re(I) Carbonyl Complexes.

The cleavage of the C-N bonds of aromatic heterocycles, such as pyridines or quinolines, is a crucial step in the hydrodenitrogenation (HDN) industrial processes of fuels in order to minimize the emission of nitrogen oxides into the atmosphere. Due to the harsh conditions under which these reactions take place (high temperature and H2 pressure), the mechanism by which they occur is only partially understood, and any study at the molecular level that reveals new mechanistic possibilities in this area is of great interest. Herein, we unravel the pyridine ring-opening mechanism of 2,2'-bipyridine (bipy) and 1,10-phenanthroline (phen) ligands coordinated to the cis-{Re(CO)2(N-RIm)(PMe3)} (N-RIm= N-alkylimidazole) fragment under mild conditions. Computational calculations show that deprotonation of the pyridine ring, once dearomatized, is crucial to induce ring contraction, triggering extrusion of the nitrogen atom from the ring and cleavage of the C-N bond. It is noteworthy that different products (regioisomers) are obtained depending on whether the ligand used is bipy or phen due to the additional rigidity and stability conferred by the central ring of the phen ligand, an issue also addressed and clarified computationally. Strong support for the proposed mechanism is provided by the characterization and isolation, including three single-crystal X-ray diffraction structures, of several of the proposed reaction intermediates.

Structure of the five-coordinate CoII complex (1H-imidazole){tris-[(1-benzyl-triazol-4-yl-κN3)meth-yl]amine-κN}cobalt(II) bis-(tetra-fluoro-borate).

The title compound, [Co(C3H4N2)(C30H30N10)](BF4)2, is a five-coordinate CoII complex based on the neutral ligands tris-[(1-benzyl-triazol-4-yl)meth-yl]amine (tbta) and imidazole. It exhibits a distorted trigonal bipyramidal geometry in which the equatorial positions are occupied by the three N-atom donors from the triazole rings of the tripodal tbta ligand. The apical amine N-atom donor of tbta and the N-atom donor of the imidazole ligand occupy the axial positions of the coordination sphere. Two tetra-fluoro-borate anions provide charge balance in the crystal.

On-Surface Synthesis of Organolanthanide Sandwich Complexes.

The synthesis of lanthanide-based organometallic sandwich compounds is very appealing regarding their potential for single-molecule magnetism. Here, it is exploited by on-surface synthesis to design unprecedented lanthanide-directed organometallic sandwich complexes on Au(111). The reported compounds consist of Dy or Er atoms sandwiched between partially deprotonated hexahydroxybenzene molecules, thus introducing a distinct family of homoleptic organometallic sandwiches based on six-membered ring ligands. Their structural, electronic, and magnetic properties are investigated by scanning tunneling microscopy and spectroscopy, X-ray absorption spectroscopy, X-ray linear and circular magnetic dichroism, and X-ray photoelectron spectroscopy, complemented by density functional theory-based calculations. Both lanthanide complexes self-assemble in close-packed islands featuring a hexagonal lattice. It is unveiled that, despite exhibiting analogous self-assembly, the erbium-based species is magnetically isotropic, whereas the dysprosium-based compound features an in-plane magnetization.

Supramolecular architecture of sodium heterocyclic dithiocarbamate salt: Insights from spectral analysis and bond valence sum characterization

The hydrated sodium salt of 1,2,3,4-tetrahydroquinolinedithiocarbamate (1) has been successfully synthesized and characterized using IR, NMR, and X-ray single crystal analysis. The υC–S and thioureide υC–N bands appeared at 1484 cm−1 and 968 cm−1, respectively, in Na(H2O)3+(thqdtc)– • H2O. The notable NCS2 carbon signal emerged at 212 ppm, credited to unique nitrogen and sulfur-induced deshielding effects. Compound 1 crystallizes in the monoclinic system, P21/c space group, with dimensions a = 14.4297(4) Å, b = 6.1534(2) Å, c = 17.6701(4) Å, β = 108.7340(10)°, V = 1485.83(7) Å3, and Z = 4. The structure of 1 exhibits a supramolecular architecture through secondary interactions, such as weak intermolecular interactions that link the molecules into a linear polymeric chain. The incorporation of heterocyclic rings in the dithiocarbamate ligands leads to the formation of an intriguing supramolecular architecture, as confirmed by BVS analysis results. The BVS value of sodium does not agree well with the formal oxidation state due to the interactions of anions, cations, coordinated and uncoordinated water molecules.

Heterometallic bridged Pt(II)‐Zn(II) complexes: Influence of the substituent in 4′‐position in inert terpy ligand on antigenotoxicity, potential antitumor activity and mechanism of interactions of the complexes with biomolecules

The synthesis and characterization of novel hetrometallic complexes [{cis‐PtCl(NH3)2(μ‐4,4′‐bipyridyl)ZnCl(terpy‐Cl)}](ClO4)2 (C1a), [{trans‐PtCl(NH3)2(μ‐4,4′‐bipyridyl)ZnCl(terpy)}](ClO4)2 (C2a), [{cis‐PtCl(NH3)2(μ‐pyrazine)ZnCl(terpy‐Cl)}](ClO4)2 (C3a) and [{trans‐PtCl(NH3)2(μ‐pyrazine)ZnCl(terpy‐Cl)}](ClO4)2 (C4a) (where terpy‐Cl = 4′‐chloro‐2,2′:6′,2′′‐terpyridine) was done. Acid–base titrations were performed by UV–Vis spectrophotometric method to evaluate the pKa values of corresponding aqua complexes. Interactions between complexes and important biomolecules, guanosine‐5′‐monophosphate (5′‐GMP) and glutathione (GSH) were examined by 1H NMR spectroscopy. The chloride substituent at the 4′ position on the middle pyridine ring of terpyridine ligand significantly affects the coordination of biomolecules, as well as overall stability of complexes. The complexes were evaluated in vitro for the antioxidant prevention of DNA damages. All tested novel complexes demonstrated a significant reduction in DNA damage against oxidative modifications of DNA caused by the hydroxyl and peroxyl radicals. Also, cytotoxicity evaluation showed that significant cytotoxicity occurs only after long‐term effect of C1a, C2a and C3a, complexes in HCT‐116 cells. Molecular docking studies predict results in agreement with experimental research.

Turn-on Near-Infrared Phosphorescent Recognition of Anion Based on Self-Assembly of Cyclometalated Platinum Complexes That Induce Oncosis and Monitor Living Cells.

The design of bio-responsive functional molecular materials that can undergo self-assembly to form nanostructures within cells in response to cellular endogenous stimuli and the clarification of their prospective reaction mechanisms are of paramount significance. This work aims to elucidate the spatiotemporal generation of subcellular nanostructures and their influence on cellular functionality. Three sets of cyclometalated platinum complexes have been designed and synthesized as near-infrared phosphorescent turn-on probes for specific anions based on dynamic self-assembly in aqueous solution. The augmentation of the quantity of aromatic rings in the NN bidentate ligand of the complex modifies both the intensity of the intermolecular Pt-Pt interaction and the capacity to generate self-assembled nanowires with near-infrared emission. Besides, we explored the impact of the CN ligand's substituent effect on anion recognition, which revealed that complexes with electron-absorbing F atom substitution exhibit superior selectivity for Br-. These complexes display vivid green turn-on luminescence upon interaction with cellular biomolecules, enabling dynamic monitoring of their subcellular distribution and their interaction on diverse conditions. Furthermore, our complexes were observed to induce oncosis in cancer cells, underscoring the potential of our work in facilitating in vitro diagnosis and developing effective theranostic agents for cancer therapy.

A stable 3D Sr-MOF as an efficient heterogeneous catalyst for the cycloadditions of CO2 and knoevenagel condensation reactions

The catalytic activity of MOF is determined not only by its unique structure but also by the active sites from metal sites and functional ligands. A sTable 3D strontium complex, {[Sr2(BTCB)Cl(H2O)2]}n (Sr-BTCB), was synthesized under solvothermal condition. It is assembled with an amide-functionalized tricarboxylic acid and a Sr(II)-based infinite chain, where Sr2 repeating units are arranged sequentially. Two such 3D structures are interwoven to create a two-folded interpenetrated structure. The interpenetrated structure is strengthened by π-π interstacking between the central phenyl rings of ligands from different 3D structures. After solvent exchange and vacuum drying, the surface of nanochannels in desolvated Sr-BTCB is modified by unsaturated Sr2+ions. Complex Sr-BTCB has abundant Lewis acidic metal sites and Lewis basic sites of amide groups, as well as 1D rhombic channels. It exhibits excellent stability and heterogeneous catalysis on CO2 fixation reactions into cyclic carbonates and Knoevenagel condensation reactions of aldehydes and malononitrile.