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Aerobic photo-oxidation of sulfide into sulfoxide in water is of great interest in green chemistry. In this study, three highly stable Ir(III)–Zr(IV) metal–organic frameworks (Ir–Zr MOFs), namely Z...

Carbazole is an important compound in pharmaceuticals and functional materials. A new Pd(II) supramolecular cage-catalyzed protocol for the synthesis of multifunctional carbazoles from indoles is described through regioselective successive oxidative Heck reactions. This new protocol is highly efficient, with a low Pd (2.4 mol%) catalyst loading and good compatibility for both N-H free and N-protected indole substrates. Moreover, it can be used to synthesize carbazoles with various functional groups by a one-pot two-step procedure. The excellent catalytic activity can be attributed to the distinct properties of the supramolecular cage structure in uniformly distributive and well-defined Pd(II) active centers on the cage surfaces.

The assembly of mixed [1,1';3',1'']terphenyl-4,5',4''-tricarboxylic acid (H3TPTC) and [1,1'-biphenyl]-4,4'-dicarboxylic acid (H2BPDC), 2,2'-diamino-[1,1'-biphenyl]-4,4'-dicarboxylic acid (H2BPDC-NH2), or 6-oxo-6,7-dihydro-5H-dibenzo[ d, f][1,3]diazepine-3,9-dicarboxylic acid (H2BPDC-Urea) with Cu2+ ion generated the corresponding copper-paddlewheel-based metal-organic framework (MOF) [Cu5(TPTC)3(BPDC)0.5(H2O)5] (1), [Cu5(TPTC)3(BPDC-NH2)0.5(H2O)5] (1-NH2), or [Cu5(TPTC)3(BPDC-Urea)0.5(H2O)5] (1-Urea). They are isostructural with hierarchical porosity, consisting of zero-dimensional cage (19.2 A × 18.9 A) and one-dimensional pillar channel (29.7 A × 15.1 A) in a manner of face sharing. Platon analyses revealed the porous volume ratios are 80.2%, 80.0%, and 77.8% for 1, 1-NH2, and for 1-Urea, respectively. Thermogravimetric measurements suggested 53, 51, and 48 wt % guest molecules in 1, 1-NH2, and 1-Urea, respectively. 1-NH2 and 1-Urea were precisely functionalized via the introduction of amino and urea functional groups into the pillar channels. The constructed MOF 1-Urea, incorporating both exposed copper active sites and accessible urea functional groups to substrates, presents high efficiency on catalytic CO2 cycloaddition with propene oxide to produce cyclic carbonate in the yield of 98% with a TOF value of 136 h-1 at 1 atm and room temperature. This synergic effect provides a new strategy for designing high-efficient catalysts for CO2 chemical conversion under ambient conditions.

Coordination geometries of transition metals play vital roles in the self-assembly process of supramolecular coordination complexes. Herein, seven-coordinate 3d metal ions were applied as templates and catalytically active sites for subcomponent self-assembly that resulted in a new category of covalent metallacycles. Single-crystal structures showed that the sizes, configurations, and functionalization of covalent metallacycles could be tuned by the selection of rigid dihydrazide, transition metal ions, and prefunctionalized subcomponents, respectively. Moreover, metallacycles decorated with carboxylic groups could be employed as precursors to prepare aerogels through hierarchical self-assembly, which also exhibited high catalytic activity for cycloaddition of CO2 into cyclic carbonates.

A diastereoselective photooxidation of α-amino acid (AA) complexes into imino acid complexes using a chiral iridium(III) complex as a photosensitizer and stereo-controller under visible light irradiation and oxygen was developed. It was found that the oxidative rate of Δ-[Ir(pq)2(L-AA)] (pq is 2-phenylquinoline) diastereomer is significantly higher than that of the corresponding Δ-[Ir(pq)2(D-AA)] diastereomer, providing a new protocol for kinetic resolution of AAs via a nonenzymatic pathway. Moreover, the thermodynamic controlled strategy offered a complemental method for the diastereoselective hydrogenation of imine bonds using NaBH4 as a reductant under the chiral Ir(III) complex as a stereo-controller. The combination of diastereoselective photooxidation and reduction processes results in a new protocol for deracemization of α-amino acids under mild conditions. Mechanism study strongly indicates that singlet oxygen is a key participant in the reaction and the α-C–H bond cleavage of AAs is the rate-dete...

On the basis of hard soft acid base theory, two neutral heterometallic M2Pd3 supramolecular cages, [Al2Pd3(L)6Cl6] (1) and [Fe2Pd3(L)6Cl6] (2) (where HL is 1-(4-(1H-imidazol-1-yl)phenyl)butane-1,3-dione), have been constructed by using the tripodal M(L)3 as metalloligands in combination with PdCl2 or Pd(MeCN)2Cl2. The supramolecular cage can be described as a trigonal bipyramid with two M3+ ions occupying at the two axial sites in ΔΔ or ΛΛ configurations and three Pd2+ ions sitting in the three equatorial positions with square planar geometry in trans configuration. The supramolecular cages exhibit high catalytic activity for the Suzuki–Miyaura coupling with arylbromide or arylchrolide and phenylboronic acid in biorenewable solvent glycerol under mild conditions. Moreover, the catalyst can be readily recycled and reused at least five times without loss of catalytic activity. The high catalytic performance may be attributed to the distinct properties of the cage structure with uniformly distributive and well-defined Pd active centres on the cage surfaces. The high stability in the cage structure also prevents Pd leaching out and agglomeration.

A series of porous MOFs with hendecahedron cage-liked cavity has been constructed from the [Cu2(COO)4] secondary building unit, H3L (H3L = [1,1';3',1'']Terphenyl-4,5',4''-tricarboxylic acid) and pyrazine derivatives varied with different sizes; the structural evolving of the hendecahedron cage and the application in drug delivery and controlled release were presented.

Diastereoselective synthesis of bis-cyclometalated Ir(III) stereoisomers Δ/Λ-[Ir(C∧N)2(d-pro)] and Δ/Λ-[Ir(C∧N)2(l-pro)] (where C∧N is 2-phenylpyridine (Hppy), (4,6-difluorophenyl)pyridine (Hdfppy), and 2-phenylquinoline (Hpq) and pro is proline) with dual stereogenic centers at the metal and auxiliary ligand has been developed. The diastereomers Λ-l and Λ-d, and Δ-l and Δ-d exhibit distinguishable photophysical properties in both solution and the solid state. The thermodynamically stable diastereomers Λ-[Ir(ppy)2(l-pro)], Λ-[Ir(dfppy)2(l-pro)], and Λ-[Ir(pq)2(l-pro)] emit a green emission at 524 nm (Φ = 3.5% and τ = 35 ns), a blue-green emission at 480 nm (Φ = 4.5% and τ = 59 ns), and a red emission at 588 nm (Φ = 6.5% and τ = 200 ns) in DCM solution, respectively, which are blue-shifted accompanied by a large quantum yield and long lifetime relative to the corresponding unstable diastereomers Δ-[Ir(ppy)2(l-pro)] at 537 nm (Φ = 2.3% and τ = 29 ns), Δ-[Ir(dfppy)2(l-pro)] at 489 nm (Φ = 2.8% and τ = 43 ns)...

The Cu3(BTC)2 metal–organic framework (MOF) (BTC = 1,3,5-benzenetricarboxylate), also known as HKUST-1, is one of the earliest reported stable MOFs with a very high surface area. In this study, HKUST-1 was used for the first time to absorb the pharmaceutical products of ibuprofen, anethole and guaiacol with loading amount of 0.34 g·g− 1, 0.38 g·g− 1 and 0.40 g·g− 1, respectively, which also showing good controlled drug release property. The result from this work provides a new attempt for HKUST-1 to be used as potential platform for drug delivery and release.

A novel calcium based metal-organic framework (compound 1) was assembled from the connection of nano-sized {Ca11}SBU (2.36nm) and the triple-connective triangle aromatic acid, to give the formation of 3D MOF of 1 companied with a 2D porous structure with two 1D channel (size: 10.7A×10.8A and 9.4A×8.1A, respectively). The framework of 1 can afford a drug loading content of 0.19g/g of guaiacol and exhibited slow release effect toward guaiacol in 15h in PBS solution.Image 4

The assembly of mixed [1,1';3',1'']terphenyl-4,5',4''-tricarboxylic acid (H

C36H48CoN2O28S2, monoclinic, P21/c (no. 14), a = 18.2239(13) Å, b = 7.1282(6) Å, c = 17.8550(13) Å, β = 97.883(2)°, V = 2297.5(3) Å3, Z = 2, R gt(F) = 0.0906, wR ref(F 2) = 0.1998, T = 293(2) K.

A facile solid-phase extraction (SPE) method based on bare Fe3O4 magnetic nanoparticles (Fe3O4 NPs) was developed to capture cinnamic acid (CA) from a well-known traditional Chinese medicine, Ramulus cinnamomi, for high performance liquid chromatography (HPLC) analysis. The as-prepared Fe3O4 NPs were characterized via Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), transmission electron microscopy (TEM) and vibrating sample magnetometer (VSM). Several parameters that influence CA extraction rate, such as the amount of Fe3O4 NPs, shaking time, methanol content, eluent pH, and elution time, were investigated. The experimental results show that the CA extraction was 86.9 % at optimal condition, and the mass yield of CA extraction was found to be 0.00021 %. This study demonstrates that the developed CA extraction method is simple, cheap and environmentally friendly. Therefore, the proposed method has a potential for CA separation and purification from complex biological samples.

A porous MOF constructed from a [Cu2(COO)4] secondary building unit, H3L (H3L = [1,1';3',1'']terphenyl-4,5',4''-tricarboxylic acid), and pyrazine ligands features a unique hendecahedron cage-like cavity with good stability and a high BET surface area of 3235 m(2) g(-1), showing good controlled drug release property of ibuprofen over those of anethole and guaiacol.

Hydrothermal reaction of Co(ClO4)2·6H2O with 2-ethoxy-6-(iminomethyl)phenol (Heimp) or 3-ethoxysalicylaldoxime (H2eosa) leads to the formation of two completely different CoII complexes [Co7(eimp)6(OMe)6]·2ClO4 (1) and [Co13(eosao)8(Heosao)6(ClO4)4]·H2O (2). Compound 1 is a disc-like heptanuclear CoII cluster with all the eimp− ligands displaying the η1: η2: η1: μ2 binding mode. Compound 2 is a butterfly-like nano-tridecanuclear CoII cluster and the oximation of iminomethyl group results in its complicated binding modes. Four of the six Heosao− ligands adopt the η1: η2: η1: μ2 mode and the other two take the η1: η2: η1: η1: μ3 fashion, while eight eosao2− ligands are in the η2: η1: η2: μ4, η1: η3: η1: η2: μ5 manner. Microwave heating during the synthetic process will dramatically improve the reaction rate and yield of 1, which however, is not valid for the formation of 2. Electrospray ionization mass spectrometry (ESI-MS) solution analysis was performed, which reveals a ligand substitution reaction of the core bridge for 1. For 2, the result of ESI-MS indicates that the Co13 cluster still exists in solution, and maintains a conformation similar to that observed in the crystal structure. Magnetic studies show that 1 exhibits a dominated ferromagnetic coupling between the CoII ions below 30 K, while 2 is a typical antiferromagnetic system.

Two hexanuclear CoII clusters, NHEt3[Co6(phendc)6 ⊃ X]·MeOH·3H2O (X = Cl− (1) or F− (2)), were obtained accidently by the in situ formation of the coordinating ligand H2phendc (1,10-phenanthroline-...

Solvothermal reaction assisted with microwave leads to the formation of two unique heterometallic cubic clusters [Ni{sub 3}M'(L){sub 3}(OH)(CH{sub 3}CN){sub 3}]{sub 2}.CH{sub 3}CN (M'=K for 1 and M'=Na for 2, where L is an anion of 2-[(2-hydroxy-3-methoxy-benzylidene)-amino]-ethanesulfonate) with higher efficiency, yields and purity than those without it. The 6-metallacrown-3 [Ni{sub 3}(OH)(L){sub 3}]{sup -} groups exhibit interesting ion trapping and self-assembly of size-different Na{sup +} and K{sup +} through form recognition and coordination activity in 1 and 2. The magnetic studies for 1 and 2 suggest that the {l_brace}Ni{sub 3}M'O{sub 4}{r_brace} (M'=K and Na) cores both display dominant ferromagnetic interactions from the nature of the binding modes of mu{sub 3}-O (oxidophenyl) and mu{sub 3}-OH. - Graphical abstract: Solvothermal reaction assisted with microwave leads to two heterometallic cubic clusters with 6-metallacrown-3 structure [Ni{sub 3}O{sub 3}(OH)]{sup -} acting as a host for a K{sup +} or Na{sup +} ion. The {l_brace}Ni{sub 3}M'O{sub 4}{r_brace} (M'=K, Na) cores display dominant ferromagnetic interactions.

[Pb2(boa)(Hbbp)2] has been synthesized by treating 4-carboxylphenoxyacetic (H2boa) and 2,6-bis(benzimidazolyl)pyridine (H2bbp) with metal salts under hydrothermal conditions. Adjacent metal centers forms dinuclear metal complex through carboxylato groups as building blocks. The arrangement of the half deprotonated H2bbp ligand and carboxylate groups exhibits a coordination gap around the Pb(II) ion, occupied possibly by a stereoactive lone pair of electrons on Pb(II), with the coordination environment around the lead atoms is hemidirected. This system is a particularly clear example that coordination sphere of a unique dinuclear Pb(II) compound was controlled by lone pair activity, weak Pb···O interactions, π–π stacking and the hydrogen bonds. The above weak interactions influence differently strong red-shifted effect about the solution and solid-state photoluminescence of the compound, compared to the free ligand.

An important aspect of chemical reactions involves understanding the intermediate steps from reactants to products. The iterative use of mass spectrometry and X-Ray crystallography is demonstrated to be a powerful combination in this respect. We have applied them in identifying molecular clusters in solution followed by their solid-state structural characterizations. We used a key ligand, 2-[(2-hydroxy-3-methoxy-benzylidene)-amino]-ethanesulfonate (L), which serves as chelating/bridging units to stabilize the precursor [Li₄Ni₆(OH)₂(L)₆(CH₃CN)₆](ClO₄)₂·4CH₃CN. The results of subsequent reactions witness a cascade of processes involving fragmentation, inner bridging ligand substitution (OH⁻ to OCH₃⁻), changing modes of binding (chelate to monodentate) of the key ligand, ion-trapping and exchange (Li⁺, Na⁺ and Ca²⁺) and their site preferences, coordinating and non-coordinating solvents (CH₃CN to CH₃OH, H₂O and EtOH) replacement. The flexibility of the Ni₃OL₃ species in solution permits the formation of six derivatives. The complimentary techniques open a broader prospect for cluster design and applications.

A comparative evaluation of the solvothermal method of synthesis of magnetic Ni(7) discs with four different ligands using the same concentrations of reagents and temperature found microwave heating is more effective than the traditional oven one. Where the former only needs minutes, the latter needs days with an equivalence of 10 min microwave to 1 day of traditional. The size of crystals has a narrow distribution and increases with time for the microwave but is a rather wide distribution for the traditional one. Furthermore the shape of the crystals is more regular for the microwave. The four Ni(7)(II) discs of formulas [Ni(7)L(6)(μ(3)-OMe)(6)](ClO(4))(2) (1-3) and {[Ni(7)(L(4))(6)(μ(3)-OMe)(6)][Ni(L(4))(2)]}(ClO(4))(2) (4) were synthesized as green hexagonal rods from Ni(ClO(4))(2)·6H(2)O in mixed MeOH/MeCN solution and salicylalde Schiff base ligands (L(1) = 2-methoxy-6-(iminomethyl)phenol, L(2) = 2-ethoxy-6-(iminomethyl)phenol, L(3) = 2-methoxy-6-((methylimino)methyl)phenol, L(4) = 2-ethoxy-6-((methylimino)methyl)phenol). X-ray structural analyses show six symmetrically positioned Ni(2) around a central Ni(1) bridged by the μ(3)-methoxide and surrounded by the ligand L which also isolates the discs from one another. The perchlorate sits in the interstices, and the planar [Ni(L(4))(2)] of 4 also inserts itself between the discs. The structures of 1-3 can be regarded as ordered discotic liquid crystals. Electrospray ionization mass spectrometry of solutions showed an exchange of methoxide for hydroxide and a different distribution of [Ni(7)] phase with mixed (MeO/OH) core bridges, confirming a probable "step by step" substitution of MeO(-) by OH(-). Magnetic studies indicate ferromagnetic interaction between Ni(1) and Ni(2) and possible antiferromagnetic between Ni(2) and Ni(2), resulting in a noncollinear system which only reaches half of the moment in 50 kOe at 2 K.

The dinuclear title compound, [Pb(2)(C(6)H(8)O(4))(NO(3))(2)(C(19)H(13)N(5))(2)], lies with the mid-point of the butyl chain of the bridging adipate unit on a center of inversion. The Pb(II) ion is covalently bonded to the nitrate anion and is bonded to a carboxyl-ate group of the adipate unit by another covalent bond. The N-heterocycle functions in a chelating tridentate mode. The metal atom exists in a Ψ-octa-hedral coordination environment. When weaker Pb⋯O inter-actions are also considered, the geometry is a Ψ-tricapped trigonal prism in which the lone-pair electrons occupy one face of the trigonal prism. Adjacent mol-ecules are linked into a layer structure by N-H⋯O hydrogen bonds.

The dinuclear title compound, [Pb2(C6H8O4)(NO3)2(C19H13N5)2], lies with the mid-point of the butyl chain of the bridging adipate unit on a center of inversion. The PbII ion is covalently bonded to the nitrate anion and is bonded to a carboxyl­ate group of the adipate unit by another covalent bond. The N-heterocycle functions in a chelating tridentate mode. The metal atom exists in a Ψ-octa­hedral coordination environment. When weaker Pb⋯O inter­actions are also considered, the geometry is a Ψ-tricapped trigonal prism in which the lone-pair electrons occupy one face of the trigonal prism. Adjacent mol­ecules are linked into a layer structure by N—H⋯O hydrogen bonds.