Peculiar photoinduced properties of water-soluble,early lanthanide(III) porphyrins

Water-soluble, early lanthanide(III) mono- and bisporphyrin complexes possess very similar UV–Vis absorption as well as photophysical and photochemical properties, as a consequence of a special type of aggregation, through the peripheral substituents. In the absence of the bidentate, O-donor acetate ligand, bisporphyrin can form too, which has slightly redshifted and broadened absorption bands, compared to those of the monoporphyrin. Also the bisporphyrin displays a blueshifted and less intense fluorescence, related to the free-base porphyrin. The formation of complexes and the transformation between the mono- and bisporphyrins are very slow reactions in dark at room temperature. These reactions are accelerated by the photolysis of the system, which are considerable by-processes of the photoredox degradation. Depending on the wavelength of irradiation, two types of photoproducts can appear: during the photolysis at the Soret-band, a radical type intermediate can be observed, which disappears in dark. However, during the irradiation at the Q-bands, a new photoproduct appears, which is stable in dark and undetectable in the case of post-transition metal ions' out-of-plane porphyrin complexes.     

Multiple metal coordinating behaviour of the tetrapodal ligand 1,1,1,1-tetrakis[(salicylaldimino)methyl]methane

The tetrapodal ligand 1,1,1,1-tetrakis[(salicylaldimino)methyl]methane (H₄tsam) has been introduced for the first time for metal complexation. Two zinc(II) complexes[Zn₂(tsam)] (1) and [Zn₃(Htsam)₂]·2C₇H₈ (2) have been obtained by reacting zinc acetylacetonate with the ligand in the presence of triethylamine, while a cobalt(III) complex [Co(Htsam)]·CH₃CN·H₂O (3) is obtained when Co(ClO₄)₂·6H₂O is reacted in air. All the compounds have been characterized by their elemental analyses and ESI-MS, IR, UV-VIS and ¹H NMR spectra. The X-ray crystal structures of H₄tsam, 2 and 3 have been determined. Compounds 1 and 2 exhibit fluorescence in solution and the lifetimes of their luminescence decay have been measured. Thermal analysis (TGA, DTA) of 2 with regard to loss of encapsulated toluenes and redox behaviour of 3 have been studied.     

Metallo Salicylidenetriazol Complexes Encapsulated in Zeolite-Y: Synthesis, Physicochemical Properties and Catalytic Studies

Chromium(III), zinc(II) and nickel(II) complexes of thio-Schiff base derived from salicylaldehyde and 4-amino-2,4-dihydro-1,2,4-triazole-5-thione have been encapsulated in the nanopores of zeolite-Y by a flexible ligand method. The prepared encapsulated metal complexes have been characterized by surface analysis (XRD and N₂ adsorption/desorption), spectroscopic methods, chemical and thermal analyses. The various techniques of characterization used demonstrated that these complexes were effectively encapsulated in the zeolite supercages without structural modification or loss of crystallinity of the zeolite framework. The encapsulated complexes were screened as heterogeneous catalysts for various oxidation reactions such as phenol, cyclohexene and styrene oxidation, using H₂O₂ as an oxidant. Under the optimized conditions, these catalysts exhibited high to moderate activity. After a few cycles these catalysts were found to be stable and could be reused after recovering without detectable catalyst leaching or significant loss of activity.     

Selective oxidation of kraft lignin over zeolite‐encapsulated Co(II) [H4]salen and [H2]salen complexes

The Co([H₄]salen) and the corresponding Co([H₂]salen) complexes were encapsulated in NaY by the impregnation (IM) and flexible ligand ship‐in‐a‐botttle (SB) method for oxidation of kraft lignin to obtain chemical compounds. The neat and encapsulated complexes were characterized by XRD, FTIR, DR UV–Vis spectroscopy and BET, which showed the observed changes in the molecular structure to be correlated to the enhanced activity of the complexes. GC‐MS confirmed that the catalytic reactions of kraft lignin in the presence of peracetic acid produced major products including 2‐methoxy phenol, 2‐hydroxy benzaldehyde, 4‐hydroxy‐3,5‐dimethoxyphenyl ethanone. The encapsulated complexes exhibited improved reactivity compared to the corresponding neat complexes. Additionally, there was a greater improvement in TOF value for complexes upon IM‐immobilization as compared to SB‐immobilization. The improved salen, that is, [H₄]salen, was beneficial to the enhancement of catalytic activity as compared to [H₂]salen, as revealed by the high TOF values due to the incorporation of a modified coordination environment of the central cobalt cation by C=N hydrogenation. Actually, Co([H₄]salen)/IM was proved to be most active. Lignin conversion and TOF were high over the neat cobalt complexes when using 100% H₂O as the solvent, and the values were high over the corresponding encapsulated analogues when using 80% H₂O + 20% CH₃OH as the solvent. It can be found that encapsulation and hydrogenation of the complexes can improve the selectivity to 2‐methoxy phenol in the oxidation of kraft lignin. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40809.     

Host (nanopores of zeolite Y)-guest (oxovanadium(IV) tetradentate schiff-base complexes) nanocomposite materials: synthesis,characterization and liquid phase hydroxylation of phenol with hydrogen peroxide

Oxovanadium(IV) tetradentate Schiff-base complexes; [VO(X₂-haacac)] (X = H, Cl, CH₃ and NO₂), X₂-haacac = substituted bis(2-hydroxyanil)acetylacetone; and encapsulated in the nanopores of zeolite NaY; [VO(X₂-haacac)]-NaY; have been synthesized and characterized. The host-guest nanocomposite materials; [VO(X₂-haacac)]-NaY; was characterized by chemical analysis and spectroscopic methods (FT-IR, UV/VIS, XRD, BET and DRS). The analytical data indicated a composition corresponding to the mononuclear complex of Schiff-base ligand. The characterization data showed the absence of extraneous complexes, retention of zeolite crystalline structure and encapsulation in the nanopores. Substitution of the aromatic hydrogen atoms of the Schiff-base ligand by electron withdrawing groups like −Cl, and −NO₂ has two major effects: (1) retention and concentration of the oxovanadium(IV) complex in the zeolite cavities is enhanced (due to the larger size of the substituents) and (2) the electronic and spectral properties of the encapsulated complex are modified. Liquid-phase selective hydroxylation of phenol with H₂O₂ to a mixture of catechol and hydroquinone in CH₃CN has been reported using oxovanadium(IV) Schiff-base complexes encapsulated in zeolite-Y as catalysts. Reaction conditions have been optimized by considering the concentration of substrate and oxidant, amount of catalyst, effect of time, volume of solvent and temperature. Under the optimized reaction conditions, [VO((NO₂)₂-haacac)]-NaY has shown the highest conversion of 42.3% after 6 h. All these catalysts are more selective toward catechol formation. Encapsulated oxovanadium(IV) complex is catalytically very efficient as compared to other neat complexes for the hydroxylation of phenol and is stable to be recycled without much deterioration.     

Adsorption and 13C N.m.r. studies of ethene,ethane and carbon monoxide on zn- and cd-exchanged A-zeolites

The adsorption of C₂H₄, C₂H₆ and CO has been studied on Zn²⁺-exchanged A-zeolites. Partial exchange with Zn²⁺ or Cd²⁺ increases the adsorption capacity for C₂H₄ and CO. Complete Zn²⁺ exchange leads to a decrease, indicating a complicated variation of cation positions with exchange level. N.m.r. measurements are consistent with adsorption of C₂H₄ as weak π-complexes on the divalent cations. Weak specific adsorption complexes are also demonstrated for CO.     

Tracking the Transformation Process of a Pair of Zn(II) Coordination Clusters: Crystallography and Mass Spectrometry

Two zinc clusters Zn₄(H₃L)₄(NO₃)₄?5H₂O ( Zn₄ , H₄L=(1,2‐bis(1H‐benzo[d]imidazol‐2‐yl)ethane‐1,2‐diol) and [Zn₅(H₂L′)₆](NO₃)₄]?8H₂O?2CH₃OH ( Zn₅ , H₃L′=(1,2‐bis(benzo[d] imidazol‐2‐yl)‐ethenol) have been obtained by the reaction of Zn(NO₃)₂?6H₂O with H₄L at 80 °C or 140 °C under solvothermal condition. Powder X‐ray Diffraction (PXRD) of precipitate and Electrospray Ionization Mass Spectrometry (ESI‐MS) of reaction solution revealed the existence of transformation behavior from Zn₄ to Zn₅ by increasing the temperature from 80 °C to 140 °C, or directly heating Zn₄ at 140 °C via solvothermal reaction. Here we proposed a possible mechanism involves split process of Zn₄ and reassembly to form Zn_{5 .} ESI‐MS for single crystals revealed [Zn₄(H₃L)₄?3H]⁺ splits to [Zn(H₃L)]⁺ via [Zn₂(H₃L)₂?H]⁺. Time dependent ESI‐MS of reaction solution revealed the [Zn(H₂L′)]⁺→[Zn₂(H₂L′)₂?H]⁺→[Zn₅(H₂L′)₆?H]³⁺ stepwise assembly. It also has been captured the in situ reaction mainly occurs in the step of [Zn(H₃L)]⁺ to [Zn(H₂L′)]⁺.     

Cucurbit[n]uril Host-Guest Complexes of Acids,Photoacids, and Super Photoacids

The supramolecular chemistry of host-guest complexes of cucurbit[n]urils (CB[n]) with acidic guests in the ground (HG⁺) and excited states (HG⁺*) are reviewed. The effects of CB[n] complexation on the guests’ pK_a and/or pK_a* values are related to relative binding constants and host-guest structures of the acid form of the guest and its conjugate base. Included are carbon acids, guests of biological and medicinal interest, dyes and related polyaromatic guests, and other organic and organometallic guests. The applications of the pK_a shifts to the solubility, stability, and bioavailabilty of drug molecules, the stability and enhanced spectral properties of dyes, and in pH-induced self-sorting, micelle formation, host-guest shuttling, and controlled guest release, are discussed.     

Asymmetric Solvation of the Zinc Dimer Cation Revealed by Infrared Multiple Photon Dissociation Spectroscopy of Zn2+(H2O)n (n = 1–20)

Investigating metal-ion solvation—in particular, the fundamental binding interactions—enhances the understanding of many processes, including hydrogen production via catalysis at metal centers and metal corrosion. Infrared spectra of the hydrated zinc dimer (Zn₂⁺(H₂O)_n; n = 1–20) were measured in the O–H stretching region, using infrared multiple photon dissociation (IRMPD) spectroscopy. These spectra were then compared with those calculated by using density functional theory. For all cluster sizes, calculated structures adopting asymmetric solvation to one Zn atom in the dimer were found to lie lower in energy than structures adopting symmetric solvation to both Zn atoms. Combining experiment and theory, the spectra show that water molecules preferentially bind to one Zn atom, adopting water binding motifs similar to the Zn⁺(H₂O)_n complexes studied previously. A lower coordination number of 2 was observed for Zn₂⁺(H₂O)₃, evident from the highly red-shifted band in the hydrogen bonding region. Photodissociation leading to loss of a neutral Zn atom was observed only for n = 3, attributed to a particularly low calculated Zn binding energy for this cluster size.     

Kinetic Modeling and Toxicity Assessment of Diethyl Phthalate Treated by H2O2/UV-C Process

In the present study, the treatability of aqueous DEP solution employing H₂O₂/UV-C oxidation and the changes in acute and/or chronic toxicity of untreated and H₂O₂/UV-C treated DEP solutions was investigated. For DEP removal and its ultimate oxidation (mineralization), an optimum initial H₂O₂ concentration of 40 mM was required. The HO^? bimolecular reaction rate constant of DEP was found as 2.33 ± 0.27×10⁸ M^?1 s^?1. Activated sludge inhibition experiments inferred that H₂O₂/UV-C treated DEP solutions were composed of a mixture of oxidation intermediates which exhibited higher degree of inhibition to heterotrophic biomass with respect to DEP. According to the results obtained in this work, the complete mineralization of DEP by H₂O₂/UV-C process would be a better option.     

New metal catalysts for soybean oil transesterification

We report here the synthesis, characterization, and use of tin (3-hydroxy-2-methyl-4-pyrone)₂(H₂O)₂, lead (3-hydroxy-2-methyl-4-pyrone)₂ (H₂O)₂, mercury (3-hydroxy-2-methyl-4-pyrone)₂-(H₂O)₂, and zinc (3-hydroxy-2-methyl-4-pyrone)₂(H₂O)₂ as catalysts in the transesterification reaction of soybean oil with methanol. All complexes are active in this reaction, with the following decreasing activities: Sn²⁺≫Zn²⁺>Pb²⁺≈Hg²⁺. The catalytic activities of these complexes were also compared with classical alkali and acid transesterification catalysis (with NaOH and H₂SO₄).     

Syntheses,crystal structures of two coordination polymers constructed from imidazole-based dicarboxylate ligands containing alkyl group

Two new coordination polymers, |DMF|[Zn₂(C₇N₂O₄H₆)₂(C₁₀N₂H₈)] (1) and |(H₂O)₃|[Co(C₈N₂O₄H₉)₂(H₂O)₂] (2) have been synthesized based on 2-ethyl-1H-imidazole-4,5-dicarboxylic acid (H₃EtImDC) and 2-propyl-1H-imidazole-4,5-dicarboxylic acid (H₃PrImDC) as organic ligands, respectively. Single-crystal X-ray diffraction analysis reveals that compound 1 is a two dimensional layered structure constructed from two types of six-membered metallocycle, and the layers are stacked in an –ABCABC– sequence. For 2, the mononuclear [Co(C₈N₂O₄H₉)₂(H₂O)₂] molecules are connected with each other through hydrogen bonds forming a three dimensional supermolecular structure. Further characterizations including elemental analyses, IR spectra, and thermogravimetric analyses have been studied.     

Triazidotrinitro Benzene: 1,3,5‐(N3)3‐2,4,6‐(NO2)3C6

Triazidotrinitro benzene, 1,3,5‐(N₃)₃‐2,4,6‐(NO₂)₃C₆ ( 1 ) was synthesized by nitration of triazidodinitro benzene, 1,3,5‐(N₃)₃‐2,4‐(NO₂)₂C₆H with either a mixture of fuming nitric and concentrated sulfuric acid (HNO₃/H₂SO₄) or with N₂O₅. Crystals were obtained by the slow evaporation of an acetone/acetic acid mixture at room temperature over a period of 2 weeks and characterized by single crystal X‐ray diffraction: monoclinic, P 2₁/c (no. 14), a=0.54256(4), b=1.8552(1), c=1.2129(1) nm, β=94.91(1)°, V=1.2163(2) nm³, Z=4, ϱ=1.836 g⋅cm⁻³, R_all =0.069. Triazidotrinitro benzene has a remarkably high density (1.84 g⋅cm⁻³). The standard heat of formation of compound 1 was computed at B3LYP/6‐31G(d, p) level of theory to be ΔH°_f=765.8 kJ⋅mol⁻¹ which translates to 2278.0 kJ⋅kg⁻¹. The expected detonation properties of compound 1 were calculated using the semi‐empirical equations suggested by Kamlet and Jacobs: detonation pressure, P=18.4 GPa and detonation velocity, D=8100 m⋅s⁻¹.     

Specific Engineered G Protein Coupling to Histamine Receptors Revealed from Cellular Assay Experiments and Accelerated Molecular Dynamics Simulations

G protein-coupled receptors (GPCRs) are targets of extracellular stimuli and hence occupy a key position in drug discovery. By specific and not yet fully elucidated coupling profiles with α subunits of distinct G protein families, they regulate cellular responses. The histamine H₂ and H₄ receptors (H₂R and H₄R) are prominent members of Gs- and Gi-coupled GPCRs. Nevertheless, promiscuous G protein and selective Gi signaling have been reported for the H₂R and H₄R, respectively, the molecular mechanism of which remained unclear. Using a combination of cellular experimental assays and Gaussian accelerated molecular dynamics (GaMD) simulations, we investigated the coupling profiles of the H₂R and H₄R to engineered mini-G proteins (mG). We obtained coupling profiles of the mGs, mGsi, or mGsq proteins to the H₂R and H₄R from the mini-G protein recruitment assays using HEK293T cells. Compared to H₂R–mGs expressing cells, histamine responses were weaker (pEC₅₀, E_max) for H₂R–mGsi and –mGsq. By contrast, the H₄R selectively bound to mGsi. Similarly, in all-atom GaMD simulations, we observed a preferential binding of H₂R to mGs and H₄R to mGsi revealed by the structural flexibility and free energy landscapes of the complexes. Although the mG α5 helices were consistently located within the HR binding cavity, alternative binding orientations were detected in the complexes. Due to the specific residue interactions, all mG α5 helices of the H₂R complexes adopted the Gs-like orientation toward the receptor transmembrane (TM) 6 domain, whereas in H₄R complexes, only mGsi was in the Gi-like orientation toward TM2, which was in agreement with Gs- and Gi-coupled GPCRs structures resolved by X-ray/cryo-EM. These cellular and molecular insights support (patho)physiological profiles of the histamine receptors, especially the hitherto little studied H₂R function in the brain, as well as of the pharmacological potential of H₄R selective drugs.     

Coordination assemblies of CdII/ZnII/CoII with the 3-(pyridin-4-yl) benzoate tecton: Structural diversity and properties

Three novel coordination polymers{[CdL₂(HL)(H₂O)]·(H₂O)}_n (1), [Zn₂(OH)L₃]_n (2) and [CoL₂(H₂O)]_n (3) have been hydrothermally synthesized from M(NO₃)₂·nH₂O (M^II = Cd^II, Zn^II and Co^II) and an unsymmetrical tecton 3-(pyridin-4-yl) benzoic acid (HL). All complexes show interesting structural patterns, namely, unprecedented 1D double-stranded supramolecular clasp for 1, novel (3,5,6)-connected helical tubular double layer for 2, 2-fold interpenetrating cds network for 3. The fluorescent and thermal properties of complexes 1, 2 and/or 3 have also been investigated.     

From 1D chain to 2D layer and 3D network: Solvent-free syntheses of new metal oxalates

Four metal oxalates, Hdpa⋅Cr(ox)₂ (1), (Hdpa)₂⋅ Zn₂(ox)₃ ⋅ 2H₂O (2), Zn(H₂O)(ox) (3), and (Hgua)(H₃O) ⋅ Cd(C₂O₄)₂ (4), have been synthesized under solvent-free conditions, where dpa = diisopropylamine, ox = oxalate, and gua = guanidine. These compounds have extended structures varying from 1D chain (for 1), to 2D layer (for 2 and 3), and 3D framework network (for 4). The temperature dependence of the magnetic susceptibility of compound 1 indicates the existence of antiferromagnetic interactions between the chromium ions. Upon excitation at 230 nm, compound 3 exhibits an extensive luminescence with a peak centered at 501 nm.     

Synthesis, characterization, DNA interaction and antibacterial activities of two tetranuclear cobalt(II) and nickel(II) complexes with salicylaldehyde 2-phenylquinoline-4-carboylhydrazone

Salicylaldehyde 2-phenylquinoline-4-carboylhydrazone (H₂L), and its novel tetranuclear cobalt(II), nickel(II) complexes have been synthesized and characterized. The crystal structure of (NiL)₂·[NiL(H₂O)(DMF)]₂·H₂O·DMF obtained from DMF solutions of compound 2 was determined by X-ray diffraction analysis. The DNA-binding investigation suggests that the two complexes bind to DNA via groove binding mode. The in vitro antibacterial activity of complexes against Escherichia coli, Staphylococcus aureus, Bacillus subtilis was screened and compared to the activity of the free ligand, the antibacterial activity of complex 1 is active than complex 2 which is in consistent with their DNA-binding behaviors.     

A pair of novel helical Zn(II) enantiomers constructed from l- and d-threonine Schiff bases: Synthesis,crystal structures and properties

Two novel homochiral helical Zn(II) coordination polymers, {[Zn₂(nap-l-thr)₂(H₂O)₂]·H₂O}_n (1) and {[Zn₂(nap-d-thr)₂(H₂O)₂]·H₂O}_n (2) (H₂nap-l-thr = N-(2-hydroxy-1-naphthylmethylidene)-l-threonine, H₂nap-d-thr = N-(2-hydroxy-1-naphthylmethylidene)-d-threonine) have been successfully synthesized and characterized by elemental analysis, IR, UV–visible and single-crystal X-ray diffraction. It is interesting to note that both complexes are a pair of enantiomers: 1 exhibits 1D right-handed helical chain of [Zn-COO⁻]_∞ and 2 is 1D left-handed helical chain of [Zn-COO⁻]_∞. There are various hydrogen bonds between the adjacent helical chains which result in a 2D homochiral supramolecular layer structure. Notably, under similar synthetic procedure by using the NO₃⁻, CH₃COO⁻, Cl⁻ salts of Zn^2 + ion as a starting reagent, and identical compounds were obtained. In addition, the chiral nature of complexes 1 and 2 are confirmed by the results of circular dichroism (CD) spectra measurements. Thermal stability and luminescence properties were also investigated.     

Sulfate Chemistry for High-Voltage Insertion Materials: Synthetic,Structural and Electrochemical Insights

Rechargeable batteries based on Li and Na ions have been growing leaps and bounds since their inception in the 1970s. They enjoy significant attention from both the fundamental science point of view and practical applications ranging from portable electronics to hybrid vehicles and grid storage. The steady demand for building better batteries calls for discovery, optimisation and implementation of novel positive insertion (cathode) materials. In this quest, chemists have tried to unravel many future cathode materials by taking into consideration their eco-friendly synthesis, material/process economy, high energy density, safety, easy handling and sustainability. Interestingly, sulfate-based cathodes offer a good combination of sustainable syntheses and high energy density owing to their high-voltage operation, stemming from electronegative SO₄²⁻ units. This review delivers a sneak peak at the recent advances in the discovery and development of sulfate-containing cathode materials by focusing on their synthesis, crystal structure and electrochemical performance. Several family of cathodes are independently discussed. They are 1) fluorosulfates [AMSO₄F], 2) bihydrated fluorosulfates [AMSO₄F ⋅ 2H₂O], 3) hydroxysulfate [AMSO₄OH], 4) bisulfates [A₂M(SO₄)₂], 5) hydrated bisulfates [A₂M(SO₄)₂ ⋅ nH₂O], 6) oxysulfates [Fe₂(SO₄)₂O] and 7) polysulfates [A₂M₂(SO₄)₃]. A comparative study of these sulfate-based cathodes has been provided to offer an outlook on the future development of high-voltage polyanionic cathode materials for next-generation batteries.     

Novel oligonuclear ZnII4, ZnII8 and ZnII2NiII2 complexes with bis(benzoylacetone)-1,3-diiminopropan-2-ol

Reactions of bis(benzoylacetone)-1,3-diiminopropan-2-ol (abbreviated as H₃L) with zinc salts in the presence of triethylamine afforded the compounds [Zn₄(HL)₄]·4CH₃CN (1·4CH₃CN) and [Zn₈L₄(OH)₄]·2CH₃CN (2·2CH₃CN). Further reaction of 1 with Ni(CH₃COO)₂·4H₂O gave the heteronuclear species [Zn₂Ni₂(L)₂(CH₃O)₂(CH₃OH)₂] (3). The crystal structures of 1·4CH₃CN, 2·2CH₃CN and 3 were determined by the X-ray diffraction method.