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Three imidazole-modified Ag-polyoxovanadates frameworks (APFs) with a controllable molar ratio of Ag+ to polyoxovanadates (POVs) [Ag(IM)2]2V4O12∙2Ag(IM)2 (APF-1), [Ag2(1-eIM)4]2[Ag(1-eIM)2]3∙2Ag(1-eIM)2∙3(1-HeIM)[V10O28]2 (APF-2) and [Ag(1-pIM)2]3[HV10O28]∙2Ag(1-pIM)2∙2H2O (APF-3) (IM = imidazole; 1-eIM = 1-ethylimidazole and 1-pIM = 1-propylimidazole) have been successfully achieved by self-assembly of POVs, Ag+ cations, and three different imidazole derivatives. Interestingly, the molar ratios of Ag+ to POVs vary from 4:1, 4.5:1 to 5:1 by changing the vanadium resources and imidazole derivatives. Notably, the coordination environment of Ag+ cations and the structure of POVs in the APFs are also different. Specifically, for APF-1, the four Ag atoms adopt three-coordinated and four-coordinated geometries, respectively, and Ag-imidazole complexes and [V4O12]4− cluster form the one-dimensional polymeric chains. While Ag atoms in APF-2 and APF-3 exhibit two-, four- and five-coordinated geometries for APF-2, four-, five- and six-coordinated geometries for APF-3, respectively. These Ag+ cations and decavanadate clusters are assembled into the 2D supramolecular structure through the Ag-O bonds and Ag…Ag argentophilic interaction. Remarkably, thus-obtained APF-2 can serve as powerful efficient heterogeneous catalyst for construction of C-N bond and detoxification of simulant sulfur mustard (yields up to 99%), which enable successful recycling for three cycles with remained catalytic activities and structure stability.

A condition-controlled strategy for selectively synthesis of 2-acylbenzothiazoles and bibenzo[b][1,4]thiazines from aryl methyl ketones and disulfanediyldianilines was realized using I2/DMSO or I2/MeCN systems, respectively. The desired products were synthesized in only 15 min with moderate to excellent yields (50%-90%) under microwave-assisted, metal-free conditions. The strategy provides a great advantage for selective synthetic applications in the efficient synthesis of benzothiazoles and bibenzothiazines heterocycle compounds.

Summary γ-butyrolactone (γ-BL), serving as the monomer of biocompatible and recyclable poly(γ-butyrolactone) plastic, faces a giant challenge in ring-opening polymerization (ROP) due to its low strain energy. The ROP of γ-BL is generally achieved under harsh conditions (e.g., high-pressure or gas-protected atmosphere) and is mostly based on homogeneous systems. Here, we synthesize a series of lanthanum metal-organic framework-based porous nanospheres and successfully apply them as heterogeneous catalysts in efficient ROP of γ-BL under mild conditions. Specifically, NNU-mIM-3 presents a yield of 24.6% with low polydispersity distribution centered at 3.6 kDa and the obtained PγBL can be completely and quantitatively recycled into monomers by simple heat treatment. Besides, the ROP catalysis systems have been intensively explored with various imine-based additives, proven to exhibit largely improved performance with PγBL yield of ~50% and Mw of ~8 kDa. This work paves a new way to explore novel heterogeneous catalysts in producing biocompatible and degradable plastics.

An addition of H-phosphonates to aryl alkynes was realized under solvent- and metal-free conditions, affording Markovnikov-selective α-vinylphosphonates in moderate to good yields. A wide range of aryl alkynes could be applied for the reaction. A tentative mechanism of addition–substitution was proposed based on in situ 31P {1H} NMR studies.

A method for the synthesis of fused chromeno quinolines by the palladium/copper cocatalyzed C-H bond activation and C-C bond cleavage reaction has been developed. A variety of fused chromeno quinoline derivatives could be synthesized by coumarin derivatives and anilines through the C-C bond cleavage/C-H functionalization/C-C bond formation process. The MTT assay was used to evaluate the chromeno quinolines against the human cervix tumor cells (HeLa), 3c and 9c without coordination metals showed good inhibition effect.

A series of microporous Ln(III)-based metal–organic frameworks (1-Ln) have been hydrothermally synthesized using 4,4′,4′′-nitrilotribenzoic acid (H3NTB). Single crystal X-ray diffraction analyses show that 1-Ln are isostructural and have 3D porous frameworks with remarkable stability and permanent porosity for Ar and CO2 adsorption. In addition, 1-Ln exhibit diverse photoluminescence emissions depending on the nature of lanthanide ions. More importantly, 1-Ln are further studied in the Knoevenagel reactions of benzaldehyde derivatives and malononitrile under solvent-free conditions, and it is found that 1-Tb shows the best catalytic activities (yields up to 99%), providing a unique example to differentiate the roles of Ln ions within the frameworks in catalyzing Knoevenagel reactions.

We reported an economic and practical ball-milling method for the synthesis of tetrahydroquinoline derivatives via a ‘one-pot’ three-component Diels-Alder reaction of anilines, aldehydes and alkenes catalyzed by phosphotungstic acid at room temperature. For this reaction, a simple “one-pot” ball-milling operation was conducted, readily available starting materials were employed, ‘one-pot’ conditions were applied, and the most important was to use inexpensive and environmentally friendly catalyst phosphotungstic acid. Various tetrahydroquinolines, which might be potentially applicable in the pharmaceutical and biochemical areas, were conveniently synthesized in moderate to excellent yields.

One bonded- and one discreted-Lindqvist hexatungstate-based copper hybrids (Cu-POMs) ([Cu2(O)OH(phen)2]2[W6O19]·6H2O (1) and [Cu2(phen)4Cl] [HW6O19]·2H2O (2) (phen = 1,10-phenanthroline)) were controllably synthesized and routinely characterized. Cu-POMs 1–2 consisted of identical [W6O19] unit and similar copper–phen complexes, the two units are bonded via four Cu–O chemical bonds in compound 1; however, compound 2 is discreted and stabilized by intermolecular electrostatic interactions. Importantly, these Cu-POMs catalysts were first applied in the novel reaction for the preparation of 2-phenylquinoxalines via the one-pot coupling and oxidation reactions of 2-haloanilines with vinyl azides or 3-phenyl-2H-azirines under mild conditions, and Cu-POMs 1 showed higher catalytic performance in good yields (79–84%). The reactions exhibit some functional group tolerance and allow for the preparation of a number of 2-phenylquinoxalines.

By rationally controlling hydrothermal conditions, three new inorganic–organic hybrid polyoxovanadates (POVs) [Ni2(1-vIM)7H2O][V4O12]·H2O (1), [Cu2(1-vIM)8][V4O12]·H2O (2) and [Co(1-vIM)H2O][VO3]2 (3) (1-vIM = 1-vinylimidazole) have been synthesized and thoroughly characterized by single X-ray diffraction (SXRD), powder X-ray diffraction (PXRD), infrared spectroscopy (FT-IR), and elemental analyses (EA). Interestingly, complexes 1 and 2 have similar structures including [V4O12]4− clusters; complex 3, however, was isolated as a structure by including the [VO3]22− cluster under a different synthetic condition compared with those of 1 and 2. Both complexes 1 and 2 display an interesting 3D supramolecular structure, and complex 3 shows a 2D two parallel networks supramolecular structure linked by a [Co2O2] unit due to the different coordination environments of the central metals. Three inorganic–organic hybrid POVs as heterogeneous catalysts are active in the selective oxidation of sulfides to produce sulfoxides or sulfones with high conversion and high selectivity (up to 99.5% for sulfoxides and 98.5% for sulfones respectively catalyzed by 1). Complex 1 is also used as catalyst in the oxidative CEES (2-chloroethyl ethyl sulfide, a sulfur mustard simulant) abatement with high activity and selectivity toward the corresponding sulfoxide. Moreover, complex 1 can be reused at least three times in sulfoxidation reactions without losing its activity.

Polyester plastics such as poly(ethylene terephthalate) (PET) are utilized commonly in everyday life, yet only a small portion of these plastics are recycled, and typically, the recycling procedure...

The synthesis of two sulfur-decorated perylene diimides, the five-membered S-heterocyclic annulated perylene diimide (1) and 1-propanethiol- N,N′-dicyclohexylperylene-3,4,9,10-tetracarboxylic diimide (2), and a novel sulfoxide-containing perylene diimide, 1-propyl sulfoxide- N,N′-dicyclohexylperylene-3,4,9,10-tetracarboxylic diimide (3), are reported. The photophysical, electrochemical, aggregation, and thermal properties of these compounds are investigated by ultraviolet visible absorption, fluorescence, cyclic voltammetric, X-ray diffraction, and thermogravimetric analysis techniques. The geometries of the compounds are optimized at the 6-31G* level of theory using density functional theory, and their potentials are correlated with molecular orbitals. The prepared perylene diimide derivatives exhibit narrow the highest occupied molecular orbitals and the lowest unoccupied molecular orbitals band gaps, and they have quite different absorptions and emissions in dichloromethane solutions, which are in agreement with the density functional theory–calculated results.

A sulfur-decorated perylene derivative, 1-propanethiol-N,N′-dicyclohexyl perylene-3,4,9,10 tetracarboxylic diimide (PTPDI), was synthesized and fully characterized by 1H NMR, 13C NMR, FTIR, HRMS, UV–vis absorption, fluorescence, fluorescence lifetime, fluorescence quantum yield, cyclic voltammetry, and thermogravimetric techniques. The optical, fluorescence, and scanning electron microscopies were employed to study its self-assembly process. The photophysical properties were affected strongly by modifying the propanethiol unit linking to the perylene core. Furthermore, the chromophore showed two irreversible oxidations and two quasi-reversible reductions in dichloromethane at modest potential. The optical properties of PTPDI in various conditions and complementary density functional theory calculations were reported. Due to steric hindrance of the bulky n-propyl mercaptan substituent, PTPDI molecules are arranged in slipped face-to-face fashion to form J-aggregates. Thus, the intermolecular π–π actions of the molecule are weak, causing its high luminescence efficiency. In the meantime, the space between perylene cores is very short (3.45 Å), which is favorable for the hopping transportation of charge carrier from one molecule to an adjacent one. PTPDI could be a candidate material for acquiring a well-defined organic nanostructure with excellent charge-transporting and light-emitting capabilities.

Four new mixed-valence manganese complexes, [Mn(II)Mn(III)2(S-L1)2(OAc)4]·2H2O(1), [Mn(II)Mn(III)2(R-L1)2(OAc)4]·2H2O (2), [Mn(II)Mn(III)2(2H2O)(S-L2)2(OAc)4] (3), [Mn(II)Mn(III)2(2H2O)(R-L2)2(OAc)4] (4) [H2L1 derived from (R)/(S)-2-amino-1-butanol and 2-hydroxy-5-chlorobenzaldehyde, H2L2 derived from (R)/(S)-2-amino-3-phenyl-1-propanol and 2-hydroxy-4-methoxybenzaldehyde], were synthesized and fully characterized by elemental analysis, IR spectroscopy and single crystal X-ray diffraction. Complexes 1–4 are mixed-valence trinuclear manganese compounds with six-coordinated. The linear MnIII–MnII–MnIII cores are triply bridged by acetate, phenolate and alkoxy groups. The vitro cytotoxicity test revealed that all complexes have substantial cytotoxic activity against three cancer cell lines (HepG2, MDA-MB-231 and A549). DNA-binding properties of 1–4 were investigated by UV–Vis, fluorescence spectroscopy, viscosity and thermal denaturation. All complexes bound to calf thymus DNA (CT-DNA) via an intercalative mode, and that derived from (S)-Schiff base ligands exhibited stronger interaction with DNA than (R)-isomers. Furthermore, the interactions of 1–4 with bovine serum albumins (BSA) in a static mode were also studied using absorption emission spectral techniques and molecular docking analysis. The chirality and structure of ligands showed to a large influence on the DNA/BSA binding ability and cytotoxicity of manganese complexes. The geometry optimization results are in agreement with experimental observations.

A highly efficient and reusable catalyst QA-HPMV was successfully prepared by the reaction of quinoline-2-formic acid (QA) with molybdovanadophosphoric heteropolyacid (H4PMo11VO40, HPMV) for the nitration of benzene. The physical and chemical properties of the sample was characterized by X-ray diffraction analysis (XRD), Fourier transform infrared spectroscopy (FTIR), UV-Vis and thermogravimetric analysis (TG). The characterization results showed that the formed QA-HPMV retained the Keggin structure of HPMV. As a catalyst for benzene nitration, QA-HPMV showed good catalytic performance and the yield of nitrobenzene was 82.5% under the optimized reaction conditions. As a heterogeneous catalyst, QA-HPMV can be easily recycled from the reaction medium by filtering and remained highly catalytic performance even after five runs of recycling.

Hydrophosphorylated fullerene derivatives were readily prepared in one step by treating C60 with Ph3– n PCl n (n = 1–3) and ROH (R = H, alkyl). The one-pot reaction could be performed under mild conditions with moderate to good yields. Dichlorophenylphosphine and alcohols exhibited unexpected reactivity towards C60. A possible reaction mechanism involving the formation of P(III)–OH in situ was proposed to explain the experimental results.

Three pyrazole-3-carboxylic acid (H 2 pca) complexes, Cr(Hpca) 3 ·2H 2 O ( 1 ), Ni 2 (pca) 2 (H 2 O) 6 ·2H 2 O ( 2 ) and [Pb 2 (Hpca) 4 ] n ( 3 ), have been synthesized and fully characterized. The single crystal X-ray diffraction indicate that the mononuclear Cr(III) cation in complex 1 and binuclear Ni(II) cations in complex 2 are coordinated by pyrazole-3-carboxylic acid ligands and water molecules in a distorted octahedral geometry and the binuclear Pb(II) cations in complex 3 presents a distorted seven-coordinated {PbN2O5} pentagonal-bipyramid geometry. Notably, these complexes as effective heterogeneous catalysts show efficient catalytic activities for Knoevenagel condensation (yield up to 97%) and the catalyst can be recycled without losing activity.

Two transition metal (Cu and Pd)-catalyzed C-S, C-N, and C-C bond cross-coupling reactions for the preparation of N-fused benzo[4,5]imidazo[2,1-b]thiazole derivatives were developed. A variety of 3-substituted and 2,3-disubstituted benzo[4,5]imidazo[2,1-b]thiazoles were efficiently and conveniently synthesized from the coupling reaction via trans-1,2-diiodoalkenes, 1H-benzo[d]imidazole-2-thiols, and halobenzenes in moderate to excellent yields.

A novel banana-shaped molecule using 2,8-Dimethyl-6H,12H-5,11-methanodibenzo [b,f] [1,5]diazocine (Tr&ouml, ger&rsquo, s base) as bent-core was synthesized via double Carbon-Carbon cross-coupling reaction. The double Sonogashira cross-coupling reaction was optimized by using Pd(PPh3)2Cl2 as catalyst, CuI as cocatalyst and diisopropylamine as base in place of triethylamine. The structure of this compound was confirmed by 1H-NMR, 13C-NMR, Fourier transform infrared (FT-IR) spectroscopy and mass spectrometry.

Reutilization of carbon dioxide (CO2) and destruction of chemical warfare agents (CWAs) at ambient conditions are deemed as two of the crucial challenges to steer toward a more sustainable future because they can cause great hazard to human beings and environment. Design of stable, selective and powerful catalysts for multi-functional catalysis is highly desirable yet largely unmet. In this work, a series of novel decavanadate-based transition metal clusters (POVs-TM, compounds 1–5) have been reported. Compounds 1–5 possess decavanadate-centered structures in which one decavanadate cluster bridged two bridged or free transition metal units. Decavanadate unit, serving as redox center can construct bifunctional catalysis platform with transition metal. Thus-obtained clusters can serve as powerful bifunctional catalysts in both cycloaddition of CO2 and degradation of sulfur mustard simulant. Specially, compound 1 presented high performance (conv. up to 99.4 %, sele. up to 99.5 %) in chemical fixation of CO2 into valuable cyclic carbonates with simulated flue gas as the gas resource. Besides, compound 3 performed superior efficiency (conv. 98.9 %, sele. 98.7 %) than other catalysts in the degradation of sulfur mustard simulant under ambient conditions. These dual-function validated POVs-TM clusters hold much promise in the exploration of novel catalysts for applications like continuous catalytic or flow bed reactions.

Two cobalt(ii) compounds, namely, {[Co(HL)(bpy)(H2O)2]·DMF}n (1), and {[Co(HL)(bpe)]·0.5bpe}n (2) (H3L = 1,3-bis(2-carboxylphenoxy)benzoic acid, bpy = 4,4'-bipyridine, bpe = 4,4'-vinylenedipyridine), have been synthesized using cobalt(ii) transition metal salt with phenolic carboxylic acid and different N-donor ligands. The compounds were fully characterized by elemental analysis, infrared spectroscopy (IR), single crystal X-ray diffraction analysis, and thermogravimetric analysis (TGA). Both compounds exhibit 2-D (4,4)-sql networks but with a wavelike and a double layered arrangement, respectively. Remarkably, these two compounds not only exhibit field-induced single-ion relaxation magnetization but also exceptional catalytic activities of benzylic C-H oxidation (conv. 90.3-99%; sele. 98.1-99%).

A series of bibenzo[ b][1,4]thiazines with various functional groups has been synthesized by a free-radical condensation reaction. Bibenzo[ b][1,4]thiazines were obtained in moderate to good yield (up to 85%) through a one-step reaction of readily available 2,2'-dithiodianiline and methyl aryl ketones with AIBN as radical initiator in HOAc. Bibenzo[ b][1,4]thiazines exhibit diversiform solid-state packing.

In this study, two simple Schiff base copper complexes [Cu(H2O)2(HL)]·2H2O (Complex 1) (H3L = 2-OH-4-(OH)-C6H2CH=NCH2CO2H) and [Cu(py)2(HL)] (Complex 2) (Py = pyridine) were initially achieved and authenticated by single-crystal X-ray structure analyses (SXRD), powder X-ray diffraction analyses (PXRD), FT-IR spectroscopy, and elemental analyses. The SXRD reveals that the Cu2+ center in Complex 1 exhibited a distorted square pyramidal geometry, which is constructed based on phenolate oxygen, water molecules, carboxylate oxygen, and imine nitrogen from a deprotonated H3L ligand in an NO4 fashion. The Cu2+ atom in Complex 2 had distorted square pyramidal geometry, and was coordinated with two pyridine molecules and one Gly-Schiff base ligand, exhibiting an N3O2 binding set. Additionally, the free water molecules in Complex 1 linked independent copper complexes by intermolecular hydrogen bond to form a 2D framework. However, the one-dimensional chain supramolecular structure of Complex 2 was formed by the intermolecular O–H…O hydrogen bonds. The oxygen reduction performance of the two complexes was analyzed by cyclic voltammetry (CV) and the rotating disk electrode (RDE) method. Both complexes could catalyze the conversion of oxygen to water through a predominant four-electron pathway, and the Cu–NxOy moieties might be the functional moieties for the catalytic activity. The catalytic pathways and underlying mechanisms are also discussed in detail, from which the structure–activity relationship of the complexes was obtained.

Two Schiff base copper(II) complexes, [Cu(R-L) (CH3OH)]8 (1) and [Cu(S-L) (CH3OH)]4 (2) {[R/S-H2L = R/S-3-phenyl-2-(2-hydroxy-5-chlorobenzylideneamino)propane-1-ol]}, have been successfully achieved and fully characterized by single-crystal X-ray diffraction (SXRD), mass spectrometry (MS), Fourier transform infrared spectroscopy (FT-IR), and elemental analysis (EA). The interactions of complexes 1 and 2 with calf thymus DNA (CT-DNA) and bovine serum albumin (BSA) have been comprehensively investigated using various electronic absorption spectroscopies. The thermal denaturation, viscosity, and UV-Vis spectra data suggested non-intercalative binding between DNA and the complexes. Additionally, an in vitro cytotoxicity test on the two complexes towards four types of human cancerous cell lines (HL-60, Caco-2, A549, and HeLa) indicated that the two complexes exhibited substantial cytotoxic activity. Especially, complex 2 exhibited excellent data, with IC50 = 10.97 ± 1.22 against HL-60 cells, which indicated that the two chiral complexes play significant roles in the cytotoxicity and interactions with DNA and BSA.

Reaction of two related rigid terpyridine ligands, 4′-(4-cyanophenyl)-4,2′:6′,4-terpyridine (L1) and its derivative, 4′-(4-carboxyphenyl)-4,2′:6′,4-terpyridine (L2), with transition metal ions (Co2+ or Cu2+/Cu+), afforded four novel coordination compounds: Co(L1)Cl2 (1), Co3(L1)3Cl6 (2), CuI9(L1)4.5(CN)9 (3), and [CuII3(L2)6(H2O)6]·4H2O (4). Crystal structure analysis reveals that 1 is comprised of single-stranded 21 helical chains, and weak interactions involving C–H···Cl weak hydrogen bonding and π–π stacking interactions exist in the structure. The structure of 2 is comprised of 32 helices, which is compared with the structure of compound 1. 3 shows a three-dimensional (3D) 4-fold interpenetration structure. 4 exhibits a one-dimensional gridlike belt structure, which further builds 3D supramolecular architecture via π–π stacking interactions. These novel coordination compounds show exceptional catalytic activity for the oxidation of benzylic C–H bonds. Notably, compound 4 shows the best catalytic prope...

By the combination of Pd-complexes and [V10O28]6-, three Pd-decavanadate compounds [Pd(NH3)4]3[V10O28]·8H2O (1), [Pd(deta)(H2O)]2(NH4)2[V10O28]·2H2O (2) (deta = diethylenetriamine) and [Pd(dpa)2](Hdpa)2(Et3NH)2[V10O28]·2H2O (3) (dpa = 2,2'-dipyridylamine) have been successfully synthesized and thoroughly characterized using single X-ray diffraction (SXRD), powder X-ray diffraction (PXRD), infrared spectroscopy (FT-IR) and elemental analyses (EA). Interestingly, in the three compounds, the molar ratios of Pd to decavanadate vary from 3 : 1 to 1 : 1 by changing N-ligands. The three Pd-decavanadates as heterogeneous catalysts are active in the aerobic oxidation of benzylic hydrocarbons under solvent-free conditions without adding any additives and co-catalysts. Moreover, compound 1 can be reused three times without losing its activity.

Four alkoxohexavanadate-based Pd-POVs [Pd(dpa)(acac)]2[V6O13(OMe)6] (1), [Pd(dpa)(acac)]2[V6O11(OMe)8] (2), [Pd(dpa)(acac)]2[V6O11(OMe)8]·H2O (3), and [Pd(DMAP)2(acac)]2[V6O11(OMe)8]·H2O (4) (POV = polyoxovanadate; dpa = 2,2'-dipyridine amine; DMAP = 4-dimethylaminopyridine; acac = acetylacetone anion) have been synthesized and fully characterized by single crystal X-ray diffraction and powder X-ray diffraction analyses, Fourier transform infrared spectroscopy, element analyses, and X-ray photoelectron spectroscopy. In 1-4, Pd complexes and hexavanadate anions are assembled through electrostatic interactions. Interestingly, the [V6O11(OMe)8](2-) cores in 2 and 3 are a pair of isomers that can be isolated by controlling crystallization temperature. Moreover, to the best of our knowledge, the {V6} core in 3 represents a new octamethoxyhexavanadates cluster. It is notable that compounds 1-4 exhibit excellent heterogeneous catalytic performance in the oxidation of benzyl-alkanes with t-butylhydroperoxide as oxidant. Among them, the catalytic activity of 1 (conv. and selec. up to 99%, respectively) outperforms others and can be reused without losing its activity.

Cluster cat: Three new imidazole-functionalized neutral hexanuclear vanadium clusters have been prepared, one of which shows exceptional catalytic activity in the selective aerobic oxidation of alcohols (see scheme). Furthermore, these new polyoxovanadium clusters can be readily recycled and reused with unchanged catalytic activity. A plausible catalytic cycle is also proposed.

A new synthetic approach is developed and nine distinct organic functionalized oxomolybdenum complexes, 1–9, are synthesized and fully characterized. Specifically by altering the functional groups on imidazoles we succeeded in making a series of crystalline structures with unique underlying topologies and/or functionalities. These imidazole derivatives can act as ligands, structural directing agents, counter cations and simultaneously, solvents where the reactions and the crystallization occur.