Boosting Activity and Selectivity of UiO-66 through Acidity/Alkalinity Functionalization in Dimethyl Carbonate Catalysis.

The acid-base properties of supports have an enormous impact on catalytic reactions to regulate the selectivity and activity of supported catalysts. Herein, a train of Pd-X-UiO-66 (X = NO2 , NH2 , and CH3 ) catalysts with different acidity/alkalinity functional groups and encapsulated Pd(II) species is first developed, whose activities in dimethyl carbonate (DMC) catalysis are then investigated in details. Thereinto, the Pd-NO2 -UiO-66 catalyst with acidity functionalization exhibits the best catalytic behavior: the DMC selectivity stemmed from methyl nitrite (MN) is up to 68%, the conversion of CO is 73.4%. The obtained experimental results demonstrate that the NO2 group not only affected the interaction between X-UiO-66 and Pd(II) active sites but also play an indispensable role in the adsorption and activation of MN and CO, which remarkably promote the formation of the COOCH3 * intermediate and DMC product.

Emerging catalysts for the ambient synthesis of ethylene glycol from CO2 and its derivatives.

Ethylene glycol (EG), a useful chemical raw material, has been widely applied in many aspects of modern society. The conventional preparation of ethylene glycol mainly uses the petroleum route at high temperatures and pressure. More and more approaches have been developed to synthesize EG from CO2 and its derivatives under mild conditions. In this review, the ambient synthesis of EG from thermocatalysis, photocatalysis, and electrocatalysis is highlighted. The coal-to-ethylene glycol technology, one of the typical thermal catalysis routes for EG preparation, is relatively mature. However, it still faces some problems to be solved in industrialization. The recent progress in the development of coal-to-ethylene glycol technology is introduced. The main focus is on how to realize the preparation of EG under mild conditions. The strategies include doping promoters, modification of supports, design of catalysts with special structures, etc. Furthermore, the emerging technological progress of photocatalytic and electrocatalytic ethylene glycol synthesis under ambient conditions is introduced. Compared with the thermal catalytic reaction, the reaction conditions are milder. However, there are still many problems in large-scale production. Finally, we propose future development issues and related prospects for the ambient synthesis of EG using different catalytic routes.

Ambient-pressure synthesis of ethylene glycol catalyzed by C60-buffered Cu/SiO2.

Bulk chemicals such as ethylene glycol (EG) can be industrially synthesized from either ethylene or syngas, but the latter undergoes a bottleneck reaction and requires high hydrogen pressures. We show that fullerene (exemplified by C60) can act as an electron buffer for a copper-silica catalyst (Cu/SiO2). Hydrogenation of dimethyl oxalate over a C60-Cu/SiO2 catalyst at ambient pressure and temperatures of 180° to 190°C had an EG yield of up to 98 ± 1%. In a kilogram-scale reaction, no deactivation of the catalyst was seen after 1000 hours. This mild route for the final step toward EG can be combined with the already-industrialized ambient reaction from syngas to the intermediate of dimethyl oxalate.

CO2 hydrogenation to high-value products via heterogeneous catalysis.

Recently, carbon dioxide capture and conversion, along with hydrogen from renewable resources, provide an alternative approach to synthesis of useful fuels and chemicals. People are increasingly interested in developing innovative carbon dioxide hydrogenation catalysts, and the pace of progress in this area is accelerating. Accordingly, this perspective presents current state of the art and outlook in synthesis of light olefins, dimethyl ether, liquid fuels, and alcohols through two leading hydrogenation mechanisms: methanol reaction and Fischer-Tropsch based carbon dioxide hydrogenation. The future research directions for developing new heterogeneous catalysts with transformational technologies, including 3D printing and artificial intelligence, are provided.

Impact of cross-correlated sine-Wiener noises in the gene transcriptional regulatory system.

We studied fluctuation-induced switching processes in the gene transcriptional regulatory system under cross-correlated sine-Wiener (CCSW) noises. It is numerically demonstrated that the increase of the multiplicative noise intensity A and cross-correlation time τ in CCSW noises can reduce the concentration of the TF-A monomer and switch to an "off" state. In addition, when the cross-correlation time τ is small, the increase of the additive noise intensity B leads to a switch of the process from "off"→"on". Simultaneously, the increase of the cross-correlation intensity λ of CCSW noises contributes to maintaining the current state. When the cross-correlation time is large, the high concentration state has two peaks and the stationary probability distribution presents a three-peak structure.

Tuning different kinds of entangled metal-organic frameworks by modifying the spacer group of aliphatic dicarboxylate ligands and the reactant ratio.

Taking advantage of the conformational flexibility of the bpp ligand and aliphatic dicarboxylic acids, six interesting entangled coordination polymers, {[Cd(fum)(bpp)(H2O)]·(H2O)}n (), {[Cd(fum)(bpp)2]·(H2O)5}n (), {[Cd2(suc)1.5(bpp)2(NO3)(H2O)2]·6H2O}n (), {[Cd(suc)(bpp)2]·(H2O)1.5}n (), {[Cd2(glu)2(bpp)3]·10H2O}n (), and {Cd(adp)(bpp)(H2O)}n () have been prepared and structurally characterized (bpp = 1,3-bi(4-pyridyl)propane, fum = fumaric, suc = succinate, glu = glutaric, adp = adipic). Compounds and are comprised of undulated 2D 4(4)-sql networks. In the structure of compound , two identical undulated layers are parallelly interpenetrated with each other to give a 2D → 2D interpenetrating framework. For , the dangling arms projected from 2D layers are intercalated into the neighboring sheets, producing a 2D → 3D polythreading framework. Compound shows a rare example of a 2D self-penetrating framework with a (3,4)-connected (4(2)·6(3)·8)(4(2)·6) topology. Compound presents an unusual 2D self-threading network with a novel 4-connected {4(2)·6(3)·8} topology. Compound displays a 3D self-penetrating system based on a 2D → 3D parallel polycatenation array. Compound exhibits an unprecedented 3D self-penetrating structure having both 1D + 1D → 1D polycatenation and 3D + 3D → 3D interpenetration characteristics. A comparison of these six compounds demonstrates that both the different spacer lengths of the aliphatic dicarboxylates and reactant ratios appear to play a significant role in the assembly of entangled frameworks. In addition, thermal stabilities and photoluminescence properties of have been examined in the solid state at room temperature.

Using alkaline-earth metal ions to tune structural variations of 1,3,5-benzenetricarboxylate coordination polymers.

Alkaline-earth metal ions were used to tune four new heterometallic frameworks, {[Cd(2.07)Mg(0.93)(BTC)(2)(H(2)O)(4)]·2H(2)O}(n) (1), {[Cd(2)Ca(BTC)(2)(H(2)O)(4)]·2H(2)O}(n) (2), {[Cd(2)Sr(BTC)(2)(H(2)O)(5)]·H(2)O}(n) (3) and [Cd(6)Ba(3)(BTC)(3)(H(2)O)(10)](n) (4) (H(3)BTC = 1,3,5-benzenetricarboxylic acid), synthesized from H(3)BTC and the corresponding metal salts. Single-crystal X-ray analysis shows that compound 1 is a three-dimensional (3D) framework based on heterometallic Cd-O-Cd-O-Mg inorganic chain subunits, compounds 2 and 3 are basically isostructural and feature a 3D framework based on Ca(II) or Sr(II) polyhedrons decorated with Cd-O-Cd inorganic chains. Compound 4 is a 3D framework templated by disordered inorganic hydrate Ba(II) ions, and also features inorganic Cd-O-Cd chains, which are connected together through corner sharing with the {Cd(1)O(6)} polyhedrons by {Ba(1)O(6)} polyhedrons, giving rise to a rare heterometallic 3D inorganic skeleton. Moreover, the solid-state fluorescence of compounds 1-4 and NLO properties of compounds 2-4 have also been investigated at room temperature.

Multifunctional homochiral lanthanide camphorates with mixed achiral terephthalate ligands.

Seven homochiral lanthanide camphorates with mixed achiral terephthalate ligands, namely, {Ln(2)(cam)(2)(bdc)(H(2)O)(2)}·DMF [Ln = Sm (1), Eu (2), Gd (3), Tb (4), Dy (5), Ho (6), Er (7); d-H(2)cam = d-(+)-camphoric acid; H(2)bdc = 1,4-benzenedicarboxylic acid; DMF = N,N'-dimethylformamide], have been solvothermally synthesized. Single-crystal X-ray diffraction analyses reveal that compounds 1-7 are isostructural and crystallize in orthorhombic, chiral space group P2(1)2(1)2(1). These structures feature three-dimensional open frameworks based on rodlike [Ln(2)(OCO)(6)(H(2)O)(2)](n) secondary building units, with the guest DMF molecules occupying the void space of the host {Ln(2)(cam)(3)(bdc)(H(2)O)(2)} framework. The photophysical and magnetic properties of some of these complexes have been investigated. Notably, the terbium compound 4 is highly emissive with a quantum yield of 63.68%. Additionally, thermogravimetric analyses, variable-temperature IR spectroscopy, and powder X-ray diffraction of 2 as a representative were performed to determine its thermal stability, which indicates that the framework still remains intact until 300 °C.

Ag(I)-mediated in situ dehydrogenative coupling of 3-amino-1,2,4-triazole into 3,3'-azobis(1,2,4-triazole) in Cd(II) coordination polymers.

Ag(I)-mediated in situ generation of 3,3'-azobis(1,2,4-triazole) (AzTAZ) from 3-amino-1,2,4-triazole (AmTAZ) through dehydrogenative coupling has been realized during the crystallization process of two Cd(II) coordination polymers with novel topological architectures: a (3, 4, 5)-connected (4 x 6(2))(2)(4 x 6(7) x 8(2))(2)(6(5) x 10) net for [Cd(2)(AmTAZ)(2)(AzTAZ)](n) (1) and a 4-connected (6(2) x 8(4))(6(4) x 8(2))(6(5) x 8)(2) net for [Cd(AzTAZ)(2)(H(2)O)](n) (2), whereas AmTAZ retains its original form in a heterometallic complex, [Ag(2)Cd(AmTAZ)(4)](n) (3).

Temperature-controlled syntheses of substituted 1,2,4-triazolelead(II) complexes: active lone pair and N-H...X (X = Cl, Br, I) hydrogen bonds.

Three isomorphous lead(II) complexes with a new {N(3)SX}-coordinated (X = Cl, Br, I) mode have been synthesized and characterized by X-ray diffraction. The structural analyses reveal that the coordination environment around the center metal is distinctly influenced by the stereochemical 6s(2) lone pair and N-H...X hydrogen bonds. Additionally, doubly deprotonated trzS(2-) (HtrzSH = 1,2,4-triazole-3-thiol) generated in situ via deamination and dehydrazination of ahtrzS(-) (ahtrzSH = 4-amino-3-hydrazino-5-mercapto-1,2,4-triazole) was first observed in a semiconducting three-dimensional coordination network at higher reaction temperature.

Synthesis, structure, and luminescent properties of hybrid inorganic-organic framework materials formed by lead aromatic carboxylates: inorganic connectivity variation from 0D to 3D.

The hydro(solvo)thermal reactions of Pb(OAc)(2).3H(2)O with the aromatic carboxylic ligands 1,3,5-benzenetricarboxylic and 1,4-, 1,2-, and 1,3-benzenedicarboxylic acids (1,3,5-H(3)BTC; 1,4-, 1,2-, and 1,3-H(2)BDC) have yielded a family of inorganic-organic framework materials: [Pb(2)(1,3,5-BTC)(mu(3)-OH)(H(2)O)](n) (Iota), [NaPb(1,3,5-BTC)(H(2)O)](n) (IotaIota), [Pb(1,4-BDC)](n) (IotaIotaIota), [Pb(5)(1,2-BDC)(4)(OAc)(2)](n) (IV), and {[Pb(5)(1,3-BDC)(5)(H(2)O)(2)](2).H(2)O}(n) (V). These complexes have been characterized by means of single-crystal X-ray diffraction, X-ray powder diffraction, thermogravimetric analysis-mass spectrometry, and photoluminescence spectra. They are all three-dimensional structures except for two-dimensional IV. Topology analysis reveals that complexes I an V represent rare (4,8)-connected flu and (3,4)-connected zeolite-like nets, respectively. The five complexes exhibit diverse inorganic connectivity, including a 0D Pb(4)O(16) cluster for I, a 1D Pb-O-Pb chain for II, a 2D Pb-O-Pb network for III and IV, and an unprecedented 3D Pb-O-Pb framework for V. And the diversity in inorganic arrays leads to differences in luminescent properties of these complexes.

Breaking the mirror: pH-controlled chirality generation from a meso ligand to a racemic ligand.

To study the conversion from a meso form to a racemic form of tetrahydrofurantetracarboxylic acid (H(4)L), seven novel coordination polymers were synthesized by the hydrothermal reaction of Zn(NO(3))(2)6 H(2)O with (2S,3S,4R,5R)-H(4)L in the presence of 1,10-phenanthroline (phen), 2,2'-bipyridine (2,2'-bpy), or 4,4'-bipyridine (4,4'-bpy): [Zn(2){(2S,3S,4R,5R)-L}(phen)(2)(H(2)O)]2 H(2)O (1), [Zn(4){(2S,3R,4R,5R)-L}{(2S,3S,4S,5R)-L}(phen)(2)(H(2)O)(2)] (2), [Zn(2){(2S,3S,4R,5R)-L}(H(2)O)(2)]H(2)O (3), [Zn(4){(2S,3R,4R,5R)-L}{(2S,3S,4S,5R)-L} (2,2'-bpy)(2)(H(2)O)(2)]2 H(2)O (4), [Zn(2) {(2S,3S,4R,5R)-L}(2,2'-bpy)(H(2)O)] (5), [Zn(4){(2S,3R,4R,5R)-L}{(2S,3S,4S,5R)-L} (4,4'-bpy)(2)(H(2)O)(2)] (6), and [Zn(2) {(2S,3S,4R,5R)-L}(4,4'-bpy)(H(2)O)] 2 H(2)O (7). These complexes were obtained by control of the pH values of reaction mixtures, with an initial of pH 2.0 for 1, 2.5 for 2, 4, and 6, and 4.5 for 3, 5, and 7, respectively. The expected configuration conversion has been successfully realized during the formation of 2, 4, and 6, and the enantiomers of L, (2S,3R,4R,5R)-L and (2S,3S,4S,5R)-L, are trapped in them, whereas L ligands in the other four complexes retain the original meso form, which indicates that such a conversion is possibly pH controlled. Acid-catalyzed enol-keto tautomerism has been introduced to explain the mechanism of this conversion. Complex 1 features a simple 1D metal-L chain that is extended into a 3D supramolecular structure by pi-pi packing interactions between phen ligands and hydrogen bonds. Complex 2 has 2D racemic layers that consist of centrosymmetric bimetallic units, and a final 3D supramolecular framework is formed by the interlinking of these layers through pi-pi packing interactions of phen. Complex 3 is a 3D metal-organic framework (MOF) involving meso-L ligands, which can be regarded as (4,6)-connected nets with vertex symbol (4(5).6)(4(7).6(8)). Complexes 4 and 5 contain 2D racemic layers and (6,3)-honeycomb layers, respectively, both of which are combined into 3D supramolecular structures through pi-pi packing interactions of 2,2'-bpy. The structure of complex 6 is a 2D network formed by 4,4'-bpy bridging 1D tubes, which consist of metal atoms and enantiomers of L. These layers are connected through hydrogen bonds to give the final 3D porous supramolecular framework of 6. Complex 7 is a 3D MOF with novel (3,4,5)-connected (6(3))(4(2).6(4))(4(2).6(6).8(2)) topology. The thermal stability of these compounds was also investigated.

Controlled generation of acentric and homochiral coordination compounds from a versatile asymmetric ligand 4-(1H-1,2,4-triazol-3-yl)-4H-1,2,4-triazole.

Luminescent acentric and homochiral coordination compounds, which possess new topological networks, multiple helical structures and NLO properties, have been generated through the control of a versatile asymmetric ligand as well as inorganic anions, and this suggests a new protocol for preparing acentric and chiral materials.

Topology analysis and nonlinear-optical-active properties of luminescent metal-organic framework materials based on zinc/lead isophthalates.

Two 3D Zn(II) and Pb(II) isophthalates, [Zn(ip)]n (1) and [Pb4(mu4-O)(ip)3(H2O)]n (2) (H2ip = isophthalic acid), have been prepared under hydro(solvo)thermal conditions and characterized by single-crystal X-ray diffraction. The two complexes crystallize in different space groups (P4(3)2(1)2 for 1 and P2(1)/c for 2) and have different bridging modes of the ip ligand. The 3D framework of 1 is constructed by the interconnection of ZnO4 polyhedra via ip ligands, which represents a chiral net with PtS-type topology. In contrast, complex 2 is formed by the combination of Pb4O-cluster secondary building units and has a novel (3.4.5)(3(2).4(5).5(6).6(7).7(2)) topology, which is the first ever example of a (3,7)-connected net. Complex 1 displays a second harmonic generation efficiency of about 1.5 times that of KH2PO4. Optical properties and thermal stabilities of the two complexes have been studied. Additionally, the calculations of band structure and density of states of 1 have also been performed with the density functional theory method.

Organically templated metal-organic framework with 2-fold interpenetrated {3(3).5(9).6(3)}-lcy net.

A new organic cation templated Zn(II) complex (Et3NH)[Zn4(ip)3(bta)3] (, ip = isophthalate, Hbta = benzotriazole) which consists of plate-like Zn4(bta)3 units bridged by ip ligands is reported; it is the first example of a 6-connected uninodal {3(3).5(9).6(3)}-lcy net which has never been observed previously in MOFs but has been theoretically anticipated.

Synthesis, structure, and physical properties of a new anions-controlled Cd(II)-guanazole (3,5-diamino-1,2,4-triazole) hybrid family.

Nine members of a new anions-controlled Cd(II)-guanazole (3,5-diamino-1,2,4-triazole=Hdatrz) hybrid family, that is, [Cd3(datrz)6(H2O)2] (1), [Cd3(datrz)4F2] (2), [Cd5(datrz)4Cl4(OH)2] (3), [Cd5(datrz)4Br4(OH)2] (4), [Cd3(datrz)2(SO3)2].(H2O) (5), [Cd3(datrz)2(O2CMe)4] (6), [Cd(datrz)(O2CEt)] (7), [Cd(Hdatrz)(O2CtBu)2] (8), and [Cd(Hdatrz)2(H2Edta)] (9) have been synthesized by exploiting hydrothermal reactions of guanazole with suitable cadmium salts under appropriate reaction conditions. With effective control of inorganic or organic anions, the coordination diversity of the guanazole ligand in 1-9 manifests an unprecedented enrichment with five bridging modes varying from bidentate to quadridentate, two of which are first reported. Compound 1 is the first reported three-dimensional chiral complex constructed from the guanazole ligand which adopts a novel N1, N2, amino N-bridging mode. Halogen anions F-, Cl-, and Br- controlled compounds 2-4 are all three-dimensional, with their guanazole ligands possessing another novel quadridentate bridging mode. Sulfite anions controlled compound 5 displays a three-dimensional network with peculiar cage-like hexnuclear cadmium clusters. As for organic anions, low dimensional structures have been found for alkylcarboxylate anions MeCO2-, EtCO2-, and tBuCO2- controlled compounds 6, 7, and 8 (two-dimensional) and for H2Edta2- controlled compound 9 (zero-dimensional), and their guanazole ligands manifest low coordination numbers as well. These hybrid materials also present interesting structure-induced physical properties. The chiral compound 1 exhibits the second-order nonlinear optical properties at room temperature. Compounds 2-9 except 6 all exhibit photoluminescence of blue fluorescent emissions in the solid state at ambient temperature, which may be assigned to the intraligand pi-pi* transitions. Some structure related red or blue emission shifts have been investigated. Thermal studies show that most compounds of this study possess a high thermal stability.

New coordination motifs of melamine directed by N-H---X (X = Cl or Br) hydrogen bonds.

Unusual mu(2)- and mu(3)-coordination modes of melamine are found in two organic-inorganic hybrid copper halides, [Cu(2)Br(2)(MA)](n) (1) and [Cu(3)Cl(3)(MA)](n) (2) (MA = melamine), in which the MA ligand affords two N-heterocycle N atoms to link (Cu(2)Br(2))infinity stairs and serves as a novel mu(3) bridge to give a 3D framework, respectively.

catena-Poly[[diaquazinc(II)]-micro-4,4'-sulfonyldibenzoato-kappa2O:O'].

The title compound, [Zn(C(14)H(8)O(6)S)(H(2)O)(2)](n), is the first reported metal complex of the 4,4'-sulfonyldibenzoate anion. The structure comprises zigzag chains of alternating [Zn(H(2)O)(2)](2+) and sulfonyldibenzoate units, the central Zn and S atoms of which lie on crystallographic twofold axes. The Zn(II) centre occupies a strongly distorted tetrahedral environment [O-Zn-O = 83.30 (7)-136.19 (8) degrees], coordinated by the two water O atoms [Zn-O = 1.986 (2) A] and one O atom from each of two carboxylate groups [Zn-O = 1.9942 (19) A], with much longer contacts to the other O atoms of these carboxylates [Zn-O = 2.528 (2) A]. Hydrogen bonds between carboxylate O atoms and coordinated water molecules in adjacent chains lead to the formation of a three-dimensional network structure.

Poly[mu2-trans-1,2-di-4-pyridylethylene-kappa2N:N'-mu2-sulfato-kappa2O:O'-zinc(II)].

The title compound, [Zn(SO(4))(C(12)H(10)N(2))](n), features a layered structure based on [Zn(SO(4))](n) spirals linked by 1,2-di-4-pyridylethylene (bpe) ligands, with the tetrahedral Zn and S atoms lying on twofold axes. The bpe ligands are centrosymmetric. The layers are linked by weak C-H...O interactions.

Two cobalt(II) 5-aminoisophthalate complexes and their stable supramolecular microporous frameworks.

Two stable supramolecular microporous cobalt(II) polymers, namely [Co(HAIP)2]n.3nH2O (1) and [Co(AIP)(H2O)]n (2), AIP = 5-aminoisophthalate, were hydrothermally synthesized and characterized by single-crystal X-ray diffraction, IR spectra, thermogravimetric analyses, and variable-temperature magnetic susceptibility measurements. The two complexes are constructed from the same Co2(CO2)2 SBU, which is extended into a 1D chain in 1 and a 2D layer in 2. As a result, 1 and 2 are 2D and 3D coordination polymers, respectively. The 3D supramolecular network of complex 1 is held up by strong hydrogen bonds formed between carboxylate groups and shows very high stability when the free H2O molecules are removed, indicating an extraordinarily stable H-bonding system. Upon water ligands being liberated, complex 2 becomes a stable microporous solid with coordination-unsaturated Co centers. The behavior of the susceptibility curve of 1 suggests the occurrence of an interesting intrachain antiferromagnetic coupling between the Co(II) ions and the presence of a significant orbital contribution, whereas the features of 2 indicate an antiferromagnetic coupling with T(N) = 3.5 K and a long-range antiferromagnetic order with a field-induced magnetic transition.