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We present the rapid synthesis of a series of metal–organic framework (MOF) thin films on indium tin oxide (ITO) glass. ITO was first electrodeposited with either copper or zinc microcrystalline fi...

We report the synthesis and antibacterial properties and mechanism of two Zn-based coordination polymers (CPs). The first, [Zn(bipy)(OH2)42+]1.5[ClO4−]3·(bipy)3(H2O), consists of a one-dimensional (1D) structure with two crystallographically independent octahedral zinc centers trans-coordinated by two 4,4′-bipy units and water groups. The second, [Zn1.5(CH3CO2)2(bipy)2+][ClO4−]·H2O, is a two-dimensional (2D) layered structure with the same polymers but bridged together into a layer by acetate and 4,4′-bipy. Both compounds exhibit sustained release of Zn2+ ions upon their gradual degradation in aqueous solution, which results in highly effective antibacterial activity towards Escherichia coli and particularly towards Staphylococcus epidermidis cells. This activity was evaluated in solution by broth dilution assays to determine minimal inhibition concentrations (MICs) as well as in the solid phase by agar diffusion tests to quantify the zones of inhibition (ZOI), and were in close agreement. Further, the biocidal mechanisms of the coordination polymers were investigated in vivo by fluorescence microscopy utilizing CellRox Green and propidium iodide as reactive oxygen species (ROS) and membrane disruption indicators, respectively. Both CPs show superior antibacterial activity compared to two standards, zinc acetate and zinc oxide, which is concluded to be due to both gradual and localized release of Zn2+ ions as well as electrostatic attraction to the bacterial cell surface afforded by their unique structures. This unique Zn release profile and interaction with bacterial surfaces affords marked antibacterial activity and suggests that manipulation of the Zn structures could lead to significant advancements in antimicrobial materials.

An amorphous nickel and boron composite (NBC) was synthesized from nickel chloride hexahydrate (NiCl2·6H2O) and sodium borohydride (NaBH4) in absolute ethanol, both in bulk and supported on mesoporous aluminosilicate nanoparticles (MASN). Comparatively, NBC-MASN demonstrated better catalytic activity for the selective reduction of the nitro group on a variety of polysubstituted nitroarenes, using hydrazine hydrate (N2H4·H2O) as the reducing agent at 25 °C. Reuse and regeneration of NBC-MASN for the reduction of p-nitrotoluene to p-toluidine were studied with NaBH4 acting as a regeneration agent. Good catalytic activity was sustained through nine reuse cycles when equimolar NaBH4 was present in situ with N2H4·H2O (99%-67% isolated aniline yield). The structure and composition of NBC and NBC-MASN were examined by electron microscopy, energy dispersive X-ray spectroscopy (EDS), powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), and inductively coupled plasma optical emission spectroscopy (ICP-OES). The results for NBC-MASN show that a thin (

We present a new method in the synthesis of metal–organic framework (MOF) thin films using zinc oxide nanowires as the substrate. This facile method involves growing zinc oxide nanowires on a substrate (glass, transparent conducting oxide glass, Si wafer), followed by immersing the nanowire substrate in an iso-reticular metal–organic framework (IRMOF) precursor solution. The resulting 25 μm thick film is highly crystalline and covers the entire substrate. Growth of the IRMOF on the nanowire substrate allows for the film to be used in potential applications in sensing, membranes, photovoltaics, catalysis, and gas storage. We have also successfully used microwaves to rapidly produce these films with comparable film quality to our original method.

Desulfurized JP-8 fuel is of great interest for use as the hydrogen feedstock of fuel cells. The refractory aromatic sulfur species present, however, are particularly challenging to remove through traditional methods. We report the first use of mesoporous silica nanoparticles (MSN) for desulfurization and the material displays a four-fold greater performance towards JP-8 fuel over previous sorbents. The bulk form of mesoporous silica shows three-fold greater level of desulfurization. Silver-impregnated nanoparticle and bulk MCM-41 were found to have saturation adsorption capacities of 32.6 mgS g−1 and 25.4 mgS g−1, respectively. MSN display a high capacity for the notoriously difficult to remove 4,6-dimethyldibenzothiophene along with a two-fold improvement in breakthrough capacity over previously published materials, of 0.98 mgS g−1 at 10 ppmwS.

We have successfully synthesized a rare example of an open framework nickel oxide with succinate capping the channels. A honeycomb-like layer of 14-membered rings centered in the (11) plane are connected by vertex-sharing NiO6 octahedra and water resides in the channels. The structure is only the second example of an extended inorganic–organic hybrid material containing 3-D Ni–O–Ni connectivity and was structurally characterized by single-crystal and powder X-ray diffraction. The material displays excellent chemical stability in aqueous solution from pH ∼ 1 to 13 and thermal stability to ∼375 °C as evidenced by thermogravimetric analysis coupled mass spectroscopy. The Ni2+ ions order ferromagnetically below Tc = 5.1 K and anisotropic exchange interactions lead to a field-induced metamagnetic transition and spin-glass-like dependence on cooling conditions in magnetic field.

A photoactive manganese nitrosyl, namely [Mn(PaPy(3))(NO)](ClO(4)) ({Mn-NO}), has been loaded into the columnar pores of an MCM-41 host. Strong interaction between the polar nitrosyl and the -OH groups on the host wall leads to excellent entrapment of the NO donor within the porous host. With the aluminosilicate-based host (Al-MCM-41), the loading is further enhanced due to electrostatic interaction of the cationic species with the aluminum sites. The extent of loading has been determined via analytical techniques including N(2) adsorption/desorption isometry. Powder X-ray diffraction studies on the loaded materials afford patterns typical of an ordered mesoporous silicate consisting of a hexagonal array of unidimensional channels (with slight loss of crystallinity). Elemental mapping of the loaded particles confirms the incorporation of {Mn-NO} into the porous MCM-41 structure and attests to the homogeneity of the guest molecule distribution throughout individual particles. When suspensions of the loaded materials in saline solution are exposed to low-power (10-100 mW) visible light, rapid release of NO is observed. With continuous exposure, a steady release of 50-80 μM of NO is attained with 5 mg of material/mL buffer within 5 min, and the NO flux is maintained for a period of ~60 min. Rapid bursts of 5-10 μM NO are noted with short light pulses. Loss of either the nitrosyl or its photoproduct(s) from these materials in biological media is minimal over long periods of time. The NO release profiles suggest potential use of these powdery biocompatible materials as NO donors where the delivery of NO (a strong antibiotic) could be controlled via the exposure of light. Such prediction has been confirmed with the successful eradication of both drug-susceptible and drug-resistant Acinetobacter baumannii in a soft-tissue infection model through light-triggered NO delivery.

A three-dimensional La(III) based metal-organic framework, La2[NC5H3(CO2)2]3·3H2O, was assembled using the aromatic linker 3,5-pyridinedicarboxylate. This new compound was synthesized hydrothermally and is an unusual example of a lanthanum containing metal-organic network. The compound contains two distinct La centers, each adopting a nine-coordinate geometry. The structure is built up from zig-zag chains that link via bridging water molecules into a double chain defining edge-sharing six rings. These double chains are arranged into layers and connect through 3,5-pyridinedicarboxylate ligands to give the extended 3-D coordination framework. The material is thermally stable to ca. 360 °C and transforms to an unknown compound before finally decomposing to phase-pure La2O3 at 800 °C. The synthesis, structure, morphology and properties of the new material are described.

We describe herein a three-dimensional Cu(II) based metal−organic framework, copper hydroxide 2,6-naphthalenedisulfonate, Cu3(OH)4[C10H6(SO3)2]. The compound contains embedded positively charged 2-D copper oxide layers. This higher dimensionality of inorganic connectivity leads to far greater thermal stability (375 °C vs 245 °C) over our previously reported three-dimensional metal−organic framework containing embedded 1-D cuprate chains. Single crystal data for this material are as follows: FW = 544.92, monoclinic, space group P21/c, a = 13.549(5) A, b = 5.503(2) A, c = 9.512(4) A, β = 90.031(6)°, V = 709.2(5) A3, Dc = 2.552 g·cm−3, and Z = 4. The structure, crystallinity, morphology, and properties of the material are discussed. The magnetic susceptibility exhibits a broad maximum centered at 80 K, indicative of low-dimensional antiferromagnetic interactions. Control of inorganic dimensionality embedded within an MOF is an often overlooked yet key feature in determining the stability and important proper...

A three-dimensional Bi(III) based metal–organic framework was synthesized under hydrothermal conditions using the multidentate organic linker 3,5-pyridinedicarboxylate. Bismuth oxide 3,5-pyridinedicarboxylate, Bi2O2[NC5H3(CO2)2], contains embedded 1-D cationic bismuth oxide chains that propagate along the crystallographic c-axis. The oxygens of the Bi2O2 core are three-coordinate and bond strongly to the Bi atoms. Thermogravimetric analysis shows that the material possesses high thermal stability up ca. 400 °C before decomposing to phase-pure Bi2O3 at 800 °C. The structure, crystallinity, morphology and properties of the material are discussed.

We have discovered a rare example of a cationically charged inorganic material. The layered structure is an example outside the extensively studied isostructural set of anionic clays/layered double hydroxides and our previously reported lead fluoride nitrate. For the present compound, the antimony oxide hydroxide layers are positively charged and are templated by anionic alkylenedisulfonate. The organic molecules are only bonded electrostatically to the layers with sulfonate oxygen to antimony distances beyond the covalent range. The material catalyzes a ketal formation reaction as a Lewis acid without the need for drying the solvent before the reaction or a nonaqueous medium such as toluene. The catalyst is heterogeneous and is completely recovered after the catalysis for reapplication.

We report the synthesis and characterization of a seven coordinate europium complex, [EuCl3(C10H8N2O2) AE 2CH3OH]. The growing interest in developing efficient light conversion molecular devices (LCMDs) necessitates the need for new fluorescent materials. Ideal physicochemical properties of the materials include ligand absorption, efficient metal to ligand transfer, and strong luminescence with a relatively long decay time. The design of such material requires distinct absorbing (ligand) and emitting (metal ion) components. While Eu 3+ cation has a non-degenerate emitting level, 2,2 0 -bipyridine N,N dioxide is a heterocyclic ligand known to exhibit strong lumines

We describe a cationic erbium-based material [Er12(OH)29(H2O)5][O3SCH2CH2SO3]3.5·5H2O. As synthesized, the material is water stable and capable of complete organic anion exchange for a variety of α,ω-alkanedicarboxylates. We chose these anions as initial examples of exchange and as an analog for pharmaceutical waste, some of which have a carboxylate functionality at neutral pH range. Free-floating and partially anchored organosulfonate anions reside between the cationic corrugated layers and allow for exchange. The structure also displays a reversible hydration event above 100 °C. Both the as-synthesized and the exchanged materials are characterized by a variety of analytical techniques.

The first example of a unidimensional zirconium hydroxide fluoride was synthesized under mild solvothermal treatment and characterized by X-ray diffraction and thermal techniques. Monoprotonated ethylenediamine cations reside between the anionic chains. Crystal data for this material are as follows: [C2N2H9][Zr(OH)2F3], M=243.35, orthorhombic, space group Pca21, a = 6.8 0 1 6 ( 1 3 ) , b = 6.1 3 9 3 ( 1 2 ) , c = 1 4.8 6 7 ( 3 ) A , V = 6 2 0.8 ( 2 ) A 3 , T = 2 9 4 ( 2 ) K , Z = 4 , D c = 2.6 0 4 g cm - 3 , μ(Mo-Kα)=1.777 mm−1, λ = 0.7 1 0 7 3 A . The material transforms to an unknown layered material at ∼175 °C, a common occurrence for 1D structures where the chains are arranged in hydrogen-bonded layers and separated by interlayer organoammoniums. Collapse to the known condensed mineral phase Zr(FO)2.7 occurs at ca. 275 °C before finally transforming to the baddeleyite form of ZrO2 at ca. 460 °C.

We report the hydrothermal synthesis and characterization of a layered cobalt phenylphosphonate. Unlike most metal phosphonates reported to date, the structure was solved by single crystal X-ray diffraction (SC-XRD). Co(ii) centres are hexa-coordinated by oxygen and the octahedra corner-share into a layer. The layers are capped by phenylphosphonate groups, where the phenyl groups define a hydrophobic bilayer region. The material was also characterized by powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA) and SQUID (superconducting quantum interference device) magnetometry. The material undergoes an antiferromagnetic transition at a relatively low Néel temperature of 4.0 K, while the Curie-Weiss temperature of -76.5 K reflects the low-dimensionality of the magnetic structure. The effective magnetic moment of 5.01 micro(B) per Co(2+) verifies a high-spin configuration and an octahedral coordination of the metal centres. This layered material was correctly predicted in the literature from powder data, adds to the structural diversity of the cobalt phosphonates, and may be useful as an intercalation or exfoliation compound.

The hydrothermal inorganic reaction of cobalt chloride, tin oxalate and phosphoric acid yields a three-dimensional metal phosphate structure containing cobaltate layers. Hydrated tin phosphate chains connect the layers, defining unidimensional channels that contain occluded water molecules. Thermal and magnetic behaviour are also discussed. A cusp around 3.5 K and a negative Curie temperature of −35.9 K indicate antiferromagnetic exchange interactions between the Co(II) centers in the solid. The magnetic behavior follows the Curie–Weiss law in the 25–300 K range, with an effective magnetic moment of 3.18 μB.

A new compound, sodium tin trifluoride (NaSnF 3 , which we denote BING-12 for SUNY at Binghamton, Structure No. 12), was synthesized solvothermally from a pyridine–water solvent system. The new compound crystallized in the monoclinic space group C 2/ c (No. 15), with a =11.7429(12) A, b =17.0104(18) A, c =6.8528(7) A, β =100.6969(2)°, V =1345.1(2) A 3 and Z =16. The layered structure consists of outer pyramidal SnF 3 units, where the fluorides surround a central layer of six- and seven-coordinate sodium atoms. The layers are stabilized by charged Na + galleries that reside in the center of the layers. Tin trifluorophosphate (Sn 3 F 3 PO 4 , Compound 2 ) was isolated from a related synthetic system, and crystallized in the rhombohedral space group R 3 (No. 146), with a =11.8647(11) A, c =4.6291(6) A, V =564.34(10) A 3 and Z =3. The framework is made up of helical –Sn–F– chains, which are connected by phosphate groups. The materials were characterized by powder X-ray diffraction (PXRD), variable temperature PXRD (VT-PXRD), thermogravimetric analysis (TGA) and scanning electron microscopy (SEM).

A solvothermal pyridine−HF−tin oxalate system has given rise to two new layered and one new chain crystal structures: BING-4, -7, and -8. BING-4 [SUNY at Binghamton, Structure No. 4, Sn(C2O4)(C5H5N), triclinic, P-1, a = 5.4202(6) A, b = 8.3824(9) A, c = 9.3506(10) A, α = 87.982(2)°, β = 87.916(2)°, γ = 85.650(2)°, Z = 2] consists of charge-neutral chains of alternating tin and oxalate groups, with pyridine molecules completing the fifth coordination of the tin centers and capping the chains. Both BING-7 ([Sn(C2O4)F-][NH4+], monoclinic, P21/c, a = 8.2736(4) A, b = 9.6386(5) A, c = 7.7473(4) A, β = 111.229(1)°, Z = 4) and BING-8 ([Sn(PO4H)F-][NH4+], orthorhombic, Pnma, a = 6.6789(4) A, b = 5.3402(4) A, c = 15.2795(10) A, Z = 4) are anionic, fluorinated, tin oxalate and tin phosphate layers, respectively, with interlamellar charge-balancing ammonium cations. Characterization methods included single-crystal X-ray diffraction (SC-XRD), powder X-ray diffraction (PXRD), in-situ variable temperature (VT) PXRD, t...

This paper demonstrates the use of poly(dimethylsiloxane) (PDMS), polyurethane (PU), epoxy, and poly(methyl methacrylate) (PMMA) as mandrils to fabricate metallic heat exchangers having 300-700 /spl mu/m internal channels. The mandrils were prepared using two soft lithographic techniques-replica molding and microembossing. To fabricate the heat exchangers, the polymeric mandrils were coated with a thin layer of metal by thermal evaporation or sputtering; this layer acted as the cathode for electrodeposition of a shell of nickel or copper that was 100 /spl mu/m thick. The polymers were removed by burning them out at 400/spl deg/C in air, or by dissolving them with a tetrahydrofuran solution of tetrabutylammonium fluoride. Studies of heat dissipation showed that the nickel heat exchangers with features that range in size from 150-750 /spl mu/m have thermal resistances ranging from 0.07 to 0.12/spl deg//sup -2/C W/sup -1/ cm at flow rates of water of /spl sim/20 L h/sup -1/ and pressures of 8.6-83/spl times/10/sup 3/ N m/sup -2/.

The title compound, [HgI2(C10H8N2O2)], is a further example of a mercury halide complex of the chelating BipyO2 ligand (BipyO2 is 2,2′-bipyridine N,N′-dioxide). As observed for similar compounds, the coordination polyhedron of the Hg atom is a severely distorted tetrahedron, in which Hg is coordinated by two I atoms and two O atoms of the ligand.

A new ReI complex has been synthesized by reflux methods, viz. μ-ethyl­ene-1,2-di-4-pyridyl-κ2N:N′-bis­[fac-tri­carbonyl(4,4′-tert-butyl-2,2′-bi­pyridine)­rhenium(I)] hexa­fluoro­phos­phate di­chloro­methane disolvate, [Re(μ-C12H12N2)(C18H24N2)2(CO)6](PF6)2·2CH2Cl2. The compound is a centrosymmetric dinuclear complex. The self-assembled structure contains octahedral Re centers, connected by a 1,2-bis(4-pyridyl)­ethyl­ene linking group.

Two metal-organic frameworks containing barium were synthesized hydrothermally and investigated for their catalytic properties. Ba(2)F(2)[O(3)SC(2)H(4)SO(3)] has barium fluoride layers linked by organic 1,2-ethanedisulfonate molecules. Ba[O(3)SC(2)H(4)SO(3)] has discrete barium centers arranged in layers and connected covalently by ethanedisulfonate bridges. Thermogravimetric analysis showed that Ba(2)F(2)[O(3)SC(2)H(4)SO(3)] is stable to ca. 325 °C and Ba[O(3)SC(2)H(4)SO(3)] to ca. 375 °C. These materials expand the metal-organic frameworks available for group II metals bound to organodisulfonate linkers and are potentially useful for a range of heterogeneous acid catalysis reactions.

The title compound, KSn(C2O4)F, is a two-dimensional material related to our previously reported three-dimensional framework, Na4Sn4(C2O4)3F6. Both are alkali-metal tin–oxalate materials, but here the compound is layered and has potassium in place of sodium. The material was synthesized solvothermally at 423 K and crystallized in the monoclinic space group P21/c. The structure consists of potassium fluoride layers in the bc plane, which are sandwiched on both sides by tin–oxalate chains that extend along the c axis.

BING-1 [tetrasodium tetratin tris­(oxalate) hexafluoride] was synthesized solvothermally at 423 K and crystallized in the triclinic system, with the P\overline 1 space group. The asymmetric unit consists of two types of tin(II) centres, connected by oxalate groups. The Sn atoms are also bonded to fluoride ions, which bond the tin oxalate layers together via interlayer Na atoms, to define a three-dimensional framework.

We have successfully synthesized three cadmium-based metal–organic frameworks by utilizing two separate organic linkers to direct the structure. The first material is a three-dimensional neutral framework based on 2D cadmium ethanedisulfonate layers pillared by a 4,4′-bipyridine linker. The other two materials are 3D cationic frameworks and are the first with propanedisulfonate and butanedisulfonate as extraframework charge balancing anions. Both structures occupy a high symmetry hexagonal crystal system where Cd-bipy chains are arranged into three crystallographically distinct layers that stack spirally along [001]. The framework is stabilized by alkanesulfonate anions that are electrostatically and hydrogen bonded to the framework. Each material was characterized by single-crystal and powder X-ray diffraction. The thermal and luminescent properties were also investigated by thermogravimetric analysis and photoluminescence spectroscopy, respectively. All three materials exhibit high thermal stability to above 300 °C and efficient blue emissive photoluminescence centered at 425 nm to 450 nm upon 350 nm excitation.

We report two new extended inorganic materials based on gadolinium. The first, [Gd(CO(3))(2)H(2)O][NH(4)], consists of negatively charged 2-D sheets of gadolinium carbonate with one coordinated water molecule and an ammonium cation between the layers. The coordinated water and one carbonate extend into the interlayer space, connecting the layers via an extensive hydrogen bonding network which includes the ammonium ions. The second, a closely related yet more condensed framework structure, [Gd(2)(CO(3))(3)NH(3)H(2)O], is formed at a higher hydrothermal temperature and was characterized by single crystal X-ray diffraction data collected at a synchrotron. This second structure contains layers that are isostructural to the first, bridged together by carbonate, and coordinated by water and ammonia. The properties of these materials were studied by thermogravimetric analysis-mass spectrometry, photoluminescence, electron paramagnetic resonance, and Raman and infrared spectroscopy. The 2-D [Gd(CO(3))(2)H(2)O][NH(4)] is stable to about 175 degrees C, though water and ammonium loss continues through the entire thermogravimetric analysis trace. The 3-D material remains intact until about 325 degrees C. Both structures exhibit broad luminescence bands in the near-ultraviolet region centered at 354 nm. Electron paramagnetic resonance and magnetic susceptibility show spin-spin coupling between adjacent gadolinium atoms in both structures and confirm that they are paramagnetic. These materials show interesting photoluminescent and paramagnetic properties that could possibly be exploited for chemical sensing or magnetic materials applications.

Ceramic coatings can be effectively used as a surface protective layer for silicon-based devices due to their inertness and good mechanical properties. One challenge is to avoid the weaknesses that ceramic coatings inherently possess, i.e., low strain tolerance, brittleness, high temperature required to process the film, and difficulty to produce a uniform, dense layer. Therefore, in an attempt to process strain-tolerant ceramic coatings at low temperatures, we develop an aqueous solution precursor processing route. Nanometer scale organic coatings, fabricated by self-assembly processes on the silicon, are used as a ‘template’ to aid the subsequent deposition of hard ceramic coatings (ZrO2 ). The ceramic coatings are deposited by spin coating. The organic self-assembled monolayer (SAM) coating provides temporary strain tolerance for the overlying hard coating upon mechanical and thermomechanical stresses before being decomposed at high temperatures. Molecular level understanding of the coating microstructure and micromechanics involved in the coating processes is systematically approached via experimental tools such as AFM and nanoindenter, as well as numerical simulation.Copyright © 2003 by ASME

We report the synthetic conditions, physical properties and potential applications of late group 14 metal (Sn) 0D, 1D, 2D and 3D extended materials. The structures are primarily neutral chain and anionic layered compounds. The latter are charge-balanced by ammonium cations, as in and BING-7 [Sn(C2O4)F-] [NH4+] and BING-8 [Sn(PO4H)F-] [NH4+]. The neutral layered compound and chain compounds BING-1 [Na4Sn4(C2O4)F6], BING-2 [KSn(C2O4)F] and BING-4 [Sn(C2O4)(C5H5N)] have also been synthesized solvothermally. Thermogravimetric analysis (TGA) under nitrogen and in-situ variable temperature X-ray diffraction show that the materials decompose in the 200°C to 300°C range to more stable phases. Nuclear magnetic resonance (NMR) was used to monitor the ion-exchange properties of some of the materials. The intercalation properties of these materials are still being investigated.

Poly[tin(II)-mu-phenylphosphonato], [Sn(C(6)H(5)O(3)P)](n), was synthesized solvothermally at 423 K and crystallized in the monoclinic system, space group Cc. The inorganic layers consist of alternating pyramidal Sn and tetrahedral P centers, joined by doubly bridging O atoms. The corner-sharing SnO(3) and PO(3)C(6)H(5) polyhedra define a corrugated layer of six-membered rings. The layers are connected along the unique b axis by interdigitated phenyl rings of the phenylphosphonate groups.

A photoactive manganese carbonyl complex namely, fac-[Mn(pqa)(CO)3]ClO4 (abbreviated as {Mn–CO}, pqa = (2-pyridylmethyl)(2-quinolylmethyl)amine) has been incorporated in the pores of 60 nm mesoporous Al-MCM-41 nanoparticles. Strong electrostatic interactions with the negatively charged walls of the aluminosilicate host entrap the cationic carbonyl complex in the resulting material {Mn–CO}@Al-MCM-41 which has been characterized by various physical techniques and chemical analysis. The sample morphology and microstructure of the material have been established by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Results of powder X-ray diffraction (PXRD) data and the SEM-EDX elemental maps of Si, O, Al and Mn confirm that the carbonyl complex is within the pores of the nanoparticles. The 2% manganese content of {Mn–CO}@Al-MCM-41, determined by acid digestion followed by inductively coupled plasma-optical emission spectroscopy (ICP-OES), indicates efficient loading of the carbonyl complex in the nanoparticles. In biological buffer solutions, less than 2% leaching of {Mn–CO} from the nanoparticles was noted within a period of 24 h. When exposed to a broadband visible light source (λ > 350 nm), {Mn–CO}@Al-MCM-41 rapidly releases CO, as confirmed by the reduced myoglobin assay. The utility of light-induced CO delivery by {Mn–CO}@Al-MCM-41 has been established by its capacity to relax rat aorta muscle rings in tissue bath experiments.

In the crystal structure of the title compound, [HgCl2(C10H8N2O2)], the Hg atom has severely distorted tetrahedral coordination by two Cl atoms and by two O atoms of the chelating ligand. Additional weak Hg⋯Cl bonds link the mol­ecules into a chain.

We report a rapid and inexpensive method to fabricate double-layer porous TiO2 electrodes for quasisolid dye-sensitized solar cells. Polymethylmethacrylate mixed with titanium alkoxide in methyl ethyl ketone was used as template precursor. Thermal removal of the polymer at 500°C leads to mesoporous double-layer TiO2 thin films of nanocrystalline anatase. The cells show a high open-circuit voltage of ∼1.18V and overall photoelectric conversion efficiency of 2.05% under an illumination of one sun (AM1.5 global, 100mW∕cm2).