Isolation of a Cd-Based Coordination Polymer Containing Mixed Ligands: Time- and Temperature-Dependent Synthesis, Sulfonamide Antibiotics Detection, and Schottky Diode Fabrication.

In this study, we present a new cadmium(II)-based two-dimensional coordination polymer [Cd (L)(NA)(H2O)] (L = Iminol form of N-nicotinoyl glycinate, NA = nicotinate), 1, containing two linkers generated from N-nicotinoyl glycine. A comprehensive investigation was carried out during the synthesis of the coordination polymers by varying the reaction time interval and temperature, and it revealed the formation of three distinct phases, of which two phases were previously reported and one was a new compound (1). The structure of compound 1 was determined by single-crystal X-ray diffraction, and it shows a corrugated layer structure with hydrogen bond interactions leading to three-dimensional supramolecular arrangements. Compound 1 exhibited strong emission at 420 nm when excited at 260 nm in an aqueous medium. The emission behavior of this compound was used for the detection of various sulfonamide antibiotics, sulfadiazine, sulfamethazine, sulfachloropyridazine, sulfameter, sulfaquinoxaline, and sulfathiazole, in the presence of common water pollutants. The luminescence quenching response of compound 1 to sulfonamide antibiotics was significant, ranging from 81 to 94%, and the detection sensitivity reached parts per billion (ppb) levels (226-726 ppb). Compound 1 also used for the fabrication of Schottky diode devices with a barrier height of 0.86 eV along with an excellent ideality factor of 1.24.

Two-Dimensional Cu-Based MOF for Selective Staining of the Cellular Nucleus through Fluorescence Imaging and Selective Sorption of Dye Molecules in Aqueous Medium.

A two-dimensional copper-based metal-organic framework, [Cu(C23H14O6)(C10H8N2)2]·H2O·DMSO, 1, was synthesized using pamoic acid (C23H16O6) and 4,4'-bipyridine (C10H8N2) as an organic ligand and Cu(II) as a metal ion. Single-crystal structure X-ray diffraction studies of the as-synthesized compound showed a two- dimensional structure with free hydroxyl groups. Upon excitation at 370 nm, the aqueous dispersion of [Cu(C23H14O6)(C10H8N2)2]·H2O·DMSO, 1, showed emission centered at 525 nm resulting from the intraligand energy transfer. Fluorescence microscopic experiments using a human epithelioid cervix carcinoma HeLa cell line were carried out, clearly showing that our compound selectively stained the cellular nucleus. To utilize the porous nature of [Cu(C23H14O6)(C10H8N2)2]·H2O·DMSO, 1, its dye sorption behavior in aqueous solution was determined, and a high affinity for methylene blue (MB) dye was confirmed. Our synthesized compound sorbed 88% MB dye with an initial concentration of 32 mg L-1, and its sorption capacity for MB was found to be 29.79 mg g-1. The possible mechanism of the dye sorption behavior was discussed in terms of the size and charge of dye molecules with respect to molecular-level interactions between the framework and the dye molecules.

Chromone-Based Cd(II) Fluorescent Coordination Polymer Fabricated to Study Optoelectronic and Explosive Sensing Properties.

Here, electrical conductivity and explosive sensing properties of multifunctional chromone-Cd(II)-based coordination polymers (CPs) (1-4) have been explored. The presence of different pseudohalide linkers, thiocyanate ions, and dicyanamide ions resulted in 1D and 3D architecture in the CPs. Thin film devices developed from CPs 1-4 (complex-based Schottky devices, CSD1, CSD2, CSD3, and CSD4, respectively) showed semiconductor behavior. Their conductivity values increased under photo illumination (1.37 × 10-5, 1.85 × 10-5, 1.61 × 10-5, and 2.01 × 10-5 S m-1 under dark conditions and 5.06 × 10-5, 8.78 × 10-5, 7.26 × 10-5, and 10.21 × 10-5 S m-1 under light). The nature of the I-V plots of these thin film devices under light irradiation and dark are nonlinear rectifying, which has been observed in Schottky barrier diodes (SBDs). All four CPs (1-4) exhibited highly selective fluorescence quenching-based sensing properties toward well-known explosives, 2,4-dinitrophenol (DNP) and 2,4,6-trinitrophenol (TNP). The limit of detection (LOD) values are 55, 28, 27, and 31 µM for TNP and 78, 44, 32, and 41 µM for DNP for complexes 1-4, respectively. A structure property correlation has been established to explain optoelectronic and explosive sensing properties.

Selective Luminescence Turn-On-Based Sensing of Phosphate in the Presence of Other Interfering Anions Using a Heterobimetallic (3d-4d) MOF with an Acidic Pocket.

A luminescent metal-organic framework with the molecular formula [YMn1.5(C7N1H3O5)3(H2O)6]·11H2O, 1 {where C7N1H3O5 = chelidamate}, was synthesized by a hydrothermal method by employing chelidamic acid as an organic ligand and Y(III) and Mn(II) as metal ions. A two-dimensional heterobimetallic structure with phenolic hydroxyl-functionalized pockets was revealed by single-crystal X-ray diffraction analysis of compound 1. PXRD, TGA, IR, BET analysis, and UV-vis spectroscopy were used for the thorough characterization of compound 1. Upon excitation at 280 nm, compound 1 shows bright blue emission, which was utilized for the selective and sensitive turn-on detection of the PO43- ion. Based on Bronsted-Lowry acid-base interactions, the photoluminescence of compound 1 was enhanced in the presence of very low concentrations of the aforementioned anion. The mechanism behind the detection of the phosphate ion has been explored in detail. It was seen that the PO43- anion entered the hydroxyl-functionalized pockets of compound 1 and stabilized the aromatic portion of compound 1 via molecular-level interactions through acid-base interactions. These molecular-level interactions are responsible for the enhancement of the photoluminescence intensity of compound 1 after the incorporation of phosphate ions by reducing the nonradiative transitions. These phenomena were also confirmed by time-correlated single photon counting (TCSPC) measurement, which shows that the excited-state lifetime increased with the increase in addition of phosphate anions. The calculated limit of detection (LOD) of 1 was 19.55 ppb for phosphate (PO43-), which was significantly lesser than the recommended level for the PO43-anion toward the human body. The luminescence enhancement coefficient, KSV, value was also much higher than those of other reported metal-organic frameworks.

Organoamine Templated Multifunctional Hybrid Metal Phosphonate Frameworks: Promising Candidates for Tailoring Electrochemical Behaviors and Size-Selective Efficient Heterogeneous Lewis Acid Catalysis.

The successful discovery of novel multifunctional metal phosphonate framework materials that incorporate newer organoamines and their utilization as a potential electroactive material for energy storage applications (supercapacitors) and as efficient heterogeneous catalysts are the most enduring challenges at present. From this perspective, herein, four new inorganic-organic hybrid zinc organodiphosphonate materials, namely, [C5H14N2]2[Zn6(hedp)4] (I), [C5H14N2]0.5[Zn3(Hhedp) (hedp)]·2H2O (II), [C6H16N2][Zn3(hedp)2] (III), and [C10H24N4][Zn6(Hhedp)2(hedp)2] (IV) (H4hedp = 1-hydroxyethane 1,1-diphosphonic acid), have been synthesized through the introduction of different organoamines and then structurally analyzed using various techniques. The compounds (I-IV) possess a three-dimensional network through alternate connectivity of zinc ions and diphosphonate ligands, as confirmed using single-crystal X-ray diffraction. The investigations of electrochemical charge storage behaviors of the present compounds indicate that compound III exhibits a high specific capacitance of 190 F g-1 (76 C g-1) at 1 A g-1, while compound II shows an excellent cycling stability of 90.11% even after 5000 cycles at 5 A g-1 in the 6 M KOH solution. Further, the present materials have also been utilized as active heterogeneous Lewis acid catalysts in the ketalization reaction. The screening of various substrate scopes during the catalytic process confirms the size-selective heterogeneous catalytic nature of the framework compounds. To our utmost knowledge, such a size-selective heterogeneous Lewis acid catalytic behavior has been observed for the first time in the amine templated inorganic-organic hybrid framework family. Moreover, the excellent size-selective catalytic efficiencies with the d10 metal system and recyclability performances make the compounds (I-IV) more efficient and promising Lewis acid heterogeneous catalysts.

Effect of charge transfer and structural rigidity on divergent luminescence response of a metal organic framework towards different metal ions: luminescence lifetime decay experiments and DFT calculations.

We have thoroughly studied the luminescence behaviour of a cadmium based MOF, [Cd(C12N2H8)(C7N1O4H3)] {C12N2H8 = 1,10-phenanthroline, C7N1O4H3 = 2,5-pyridine dicarboxylate}, 1. Both steady-state and time-resolved luminescence spectroscopic experiments were performed to understand the dissimilar responses of compound 1 towards different metal ions in aqueous medium. Upon excitation at 280 nm, compound 1 showed a luminescence spectrum centered at 365 nm, which exhibited a three-fold turn-on in the presence of a trace amount of Zn2+ in aqueous solution, whereas in the presence of Co2+, Hg2+, Ni2+, Fe2+ and Cu2+ the luminescence of compound 1 got largely quenched. Compound 1 did not show any response in the presence of other common metal ions such as K+, Mg2+, Na+, Mn2+, and Cr3+. By analysing all the experimental results, we successfully explained the versatile luminescence behaviour of compound 1. The turn-on of luminescence in the presence of Zn2+ ions was due to coordination bond formation and enhancement of the rigidity of compound 1 which resulted in the reduction of non-radiative decay processes to a large extent. The quenching of luminescence in the presence of transition metal ions was found to be static in nature, and was due to the possibility of ligand to metal charge transfer using the vacant d-orbital of the metal ions. In the case of Hg2+ which is a closed cell heavy metal ion, the quenching of luminescence was also static in nature and was due to a two-way charge transfer mechanism. We have also performed density functional theory calculations and obtained supportive results for the proposed mechanisms of luminescence turn-on and quenching. Moreover, compound 1 could be established as a selective and efficient sensor of Zn2+ in aqueous solution even in the presence of Cd2+ and other metal ions.

Detection of Pesticides in Aqueous Medium and in Fruit Extracts Using a Three-Dimensional Metal-Organic Framework: Experimental and Computational Study.

A new, three-dimensional cadmium based metal-organic framework [Cd3(PDA)1(tz)3Cl(H2O)4]·3H2O {PDA = 1,4-phenylenediacetate and tz = 1,2,4-triazolate}, 1, has been successfully synthesized using slow diffusion method at room temperature. The structure of compound 1 has been determined using single crystal X-ray diffraction. The triazolate ligands connect three different types of octahedral Cd2+ ions to form a two-dimensional structure. The chloride ion and PDA ligands connect the two-dimensional layers to form a three-dimensional structure. The phase purity of 1 was confirmed by powder X-ray diffraction, thermogravimetric analysis, and IR spectroscopy. Aqueous dispersion of compound 1 gives intense luminescence emission at 290 nm upon excitation at 225 nm. This emission was used for the luminescence based detection of pesticides, especially azinphos-methyl, chlorpyrifos, and parathion in aqueous medium. The selectivity of pesticide detection remains unaltered even in the presence of surfactant molecules. The mechanisms of luminescence quenching were successfully explained by the combination of absorption of excitation light, resonance energy transfer, and the possibility of electron transfer. Experimental findings are also well supported by the density functional theory calculations. Selectivity of pesticides detection in real samples such as apple and tomato juice has also been observed.

Highly Selective and Sensitive Luminescence Turn-On-Based Sensing of Al3+ Ions in Aqueous Medium Using a MOF with Free Functional Sites.

A new metal­organic framework [Co(OBA)(DATZ)0.5(H2O)] {OBA = 4,4'-oxybis(benzoic acid) and DATZ = 3,5-diamino-1,2,4-triazole}, 1, was synthesized by hydrothermal reaction. Single-crystal X-ray data of 1 confirmed two-dimensional rhombus grid network topology with a free nitrogen site of triazole ring and two amine groups of each DATZ. Photoluminescence study of 1 in aqueous medium shows blue emission at 407 nm upon excitation at 283 nm. This emissive property was used for the sensing of Al3+ ions in aqueous medium through very high luminescence turn-on (6.3-fold) along with the blue shifting (∼24 nm) of the emission peak. However, luminescence studies in the presence of other common metal ions such as Mg2+, Zn2+, Ni2+, Co2+, Mn2+, K+, Na+, Ca2+, Cd2+, Hg2+, Cu2+, Fe2+, Fe3+, and Cr3+ in aqueous medium shows luminescence quenching in varying extent. Interestingly, the luminescence turn-on-based selectivity of Al3+ ions in aqueous medium was achieved even in the presence of the highest quenchable metal ion, Fe3+. Furthermore, very high sensitivity was observed in the case of Al3+ ions with a limit of detection of Al3+ of 57.5 ppb, which is significantly lower than the higher limit of U.S. Environmental Protection Agency recommendation of Al3+ ion for drinking water (200 ppb).

Highly Selective and Sensitive Luminescence Turn-On-Based Sensing of Al(3+) Ions in Aqueous Medium Using a MOF with Free Functional Sites.

A new metal-organic framework [Co(OBA)(DATZ)0.5(H2O)] {OBA = 4,4'-oxybis(benzoic acid) and DATZ = 3,5-diamino-1,2,4-triazole}, 1, was synthesized by hydrothermal reaction. Single-crystal X-ray data of 1 confirmed two-dimensional rhombus grid network topology with a free nitrogen site of triazole ring and two amine groups of each DATZ. Photoluminescence study of 1 in aqueous medium shows blue emission at 407 nm upon excitation at 283 nm. This emissive property was used for the sensing of Al(3+) ions in aqueous medium through very high luminescence turn-on (6.3-fold) along with the blue shifting (∼24 nm) of the emission peak. However, luminescence studies in the presence of other common metal ions such as Mg(2+), Zn(2+), Ni(2+), Co(2+), Mn(2+), K(+), Na(+), Ca(2+), Cd(2+), Hg(2+), Cu(2+), Fe(2+), Fe(3+), and Cr(3+) in aqueous medium shows luminescence quenching in varying extent. Interestingly, the luminescence turn-on-based selectivity of Al(3+) ions in aqueous medium was achieved even in the presence of the highest quenchable metal ion, Fe(3+). Furthermore, very high sensitivity was observed in the case of Al(3+) ions with a limit of detection of Al(3+) of 57.5 ppb, which is significantly lower than the higher limit of U.S. Environmental Protection Agency recommendation of Al(3+) ion for drinking water (200 ppb).

Facile Fabrication of Ni9 S8 /Ag2 S Intertwined Structures for Oxygen and Hydrogen Evolution Reactions.

Here, we report the fabrication of the unique intertwined Ni9 S8 /Ag2 S composite structure with hexagonal shape from their molecular precursors by one-pot thermal decomposition. Various spectroscopic and microscopic techniques were utilized to confirm the Ni9 S8 /Ag2 S intertwined structure. Powder X-ray Powder Diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analysis suggest that there is an enrichment of Ni9 S8 phase in Ni9 S8 /Ag2 S. The presence of Ag2 S in Ni9 S8 /Ag2 S improves the conductivity by reducing the interfacial energy and charge transfer resistance. When Ni9 S8 /Ag2 S is employed as an electrocatalyst for electrochemical oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) activity, it requires a low overpotential of 152 mV for HER and 277 mV for OER to obtain the geometrical current density of 10 mA cm-2 , which is definitely superior to that of its components Ni9 S8 and Ag2 S. This work provides a simple design route to develop an efficient and durable electrocatalyst with outstanding OER and HER performance and the present catalyst (Ni9 S8 /Ag2 S) deserves as a potential candidate in the field of energy conversion systems.

Synthesis, structure, and magnetic properties of a new eight-connected metal-organic framework (MOF) based on Co4 clusters.

A hydrothermal reaction of cobalt nitrate, 4,4'-oxybis(benzoic acid) (OBA), 1,2,4-triazole, and NaOH gave rise to a deep purple colored compound [Co(4)(triazolate)(2)(OBA)(3)], I, possessing Co(4) clusters. The Co(4) clusters are connected together through the tirazolate moieties forming a two-dimensional layer that closely resembles the TiS(2) layer. The layers are pillared by the OBA units forming the three-dimensional structure. To the best of our knowledge, this is the first observation of a pillared TiS(2) layer in a metal-organic framework compound. Magnetic studies in the temperature range 1.8-300 K indicate strong antiferromagetic interactions for Co(4) clusters. The structure as well as the magnetic behavior of the present compound has been compared with the previously reported related compound [Co(2)(µ(3)-OH)(µ(2)-H(2)O)(pyrazine)(OBA)(OBAH)] prepared using pyrazine as the linker between the Co(4) clusters.

Response of a Zn(II)-based metal-organic coordination polymer towards trivalent metal ions (Al3+, Fe3+ and Cr3+) probed by spectroscopic methods.

A new zinc-based two-dimensional coordination polymer, [Zn(5-AIP)(Ald-4)]·H2O (5-AIP = 5-amino isophthalate, Ald-4 = aldrithiol-4), 1, has been synthesized at room temperature by the layer diffusion technique. Single-crystal X-ray diffraction analysis of 1 showed a two-dimensional bilayer structure. An aqueous suspension of 1 upon excitation at 300 nm displayed an intense blue emission at 403 nm. The luminescence spectra were interestingly responsive and selective to Al3+, Cr3+ and Fe3+ ions even in the presence of other interfering ions. The calculated detection limits for Al3+, Cr3+ and Fe3+ were 0.35 µM ([triple bond, length as m-dash]8.43 ppb), 0.46 µM ([triple bond, length as m-dash]22.6 ppb) and 0.30 µM ([triple bond, length as m-dash]15.85 ppb), respectively. Notably, with the cumulative addition of Al3+ ions, the luminescence intensity at 403 nm decreased steadily with a gradual red shift up to 427 nm. Afterward, this red shifted peak showed a turn-on effect upon further addition of Al3+ ions. On the other hand, for Cr3+ and Fe3+ ions, there was only drastic luminescence quenching and a large red shift up to 434 nm. This indicated the formation of a complex between 1 and these metal ions, which was also supported by the UV-Visible absorption spectra of 1 that showed the appearance of a new band at 280 nm in the presence of these three metal ions. The FTIR spectra revealed that these ions interacted with the carboxylate oxygen atom of 5-AIP and the nitrogen atom of the Ald-4 ligand in the structure. The luminescence lifetime decay analysis manifested that a charge-transfer type complex was formed between 1 and Cr3+ and Fe3+ ions that resulted in huge luminescence quenching due to the efficient charge transfer involving the vacant d-orbitals, whereas for Al3+ ions having no vacant d-orbital, turn-on of luminescence occurred because of the increased rigidity of 1 upon complexation.

Metal-organic framework structures--how closely are they related to classical inorganic structures?

Metal-organic frameworks (MOFs) have emerged as an important family of compounds for which new properties are increasingly being found. The potential for such compounds appears to be immense, especially in catalysis, sorption and separation processes. In order to appreciate the properties and to design newer frameworks it is necessary to understand the structures from a fundamental perspective. The use of node, net and vertex symbols has helped in simplifying some of the complex MOF structures. Many MOF structures are beginning to be described as derived from inorganic structures. In this tutorial review, we have provided the basics of the node, the net and the vertex symbols and have explained some of the MOF structures. In addition, we have also attempted to provide some leads towards designing newer structures/topologies.

Luminescent metal-organic framework-based phosphor for the detection of toxic oxoanions in an aqueous medium.

A terbium-doped yttrium-based metal-organic framework, [Tb0.2Y0.8(FDA)(Ox)0.5(H2O)2]·H2O, 1 {where H2FDA = furan-2,5-dicarboxylic acid and Ox = oxalate}, was successfully synthesized using the hydrothermal technique as a phosphor material along with a large Stokes shift and low self-quenching of luminescence for the rapid visible detection of toxic anions in an aqueous medium. To confirm the structure and phase purity of compound 1, single crystals of the isomorphous pure yttrium-based compound [Y(FDA)(Ox)0.5(H2O)2]·H2O, 1a, were synthesized under similar experimental conditions. The single crystal X-ray data of compound 1a confirmed the three-dimensional metal-organic framework formed by the connectivity of the Y3+ ion with furan-2,5-dicarboxylate and the oxalate moiety. The phase purity of compounds 1 and 1a was confirmed by powder X-ray diffraction. Compound 1 was systematically characterized via TGA, SEM and EDX elemental mapping analysis. The aqueous dispersion of compound 1 showed highly intense visible green emission upon excitation at 265 nm. The emissions of compound 1 were utilized for the luminescence-based visible detection of toxic anions in the aqueous medium through luminescence quenching. The observed limit of detection (LOD) was 1.1 nM, 2.2 nM and 6.5 nM for chromate (CrO42-), permanganate (MnO4-) and phosphates (PO43-, H2PO4- and HPO42-), respectively, and the observed KSV values were superior to those of all other metal-organic frameworks previously reported. More importantly, the LODs are significantly lower than the level recommended for these anions towards human life.

Quasi-2D XY magnetic properties and slow relaxation in a body centered metal organic network of [Co4] clusters.

Octahedral Co(2+) centers have been connected by mu(3)-OH and mu(2)-OH(2) units forming [Co(4)] clusters which are linked by pyrazine forming a two-dimensional network. The two-dimensional layers are bridged by oxybisbenzoate (OBA) ligands giving rise to a three-dimensional structure. The [Co(4)] clusters bond with the pyrazine and the OBA results in a body-centered arrangement of the clusters, which has been observed for the first time. Magnetic studies reveal a noncollinear frustrated spin structure of the bitriangular cluster, resulting in a net magnetic moment of 1.4 microB per cluster. For T > 32 K, the correlation length of the cluster moments shows a stretched-exponential temperature dependence typical of a Berezinskii-Kosterlitz-Thouless model, which points to a quasi-2D XY behavior. At lower temperature and down to 14 K, the compound behaves as a soft ferromagnet and a slow relaxation is observed, with an energy barrier of ca. 500 K. Then, on further cooling, a hysteretic behavior takes place with a coercive field that reaches 5 T at 4 K. The slow relaxation is assigned to the creation/annihilation of vortex-antivortex pairs, which are the elementary excitations of a 2D XY spin system.

Reversible water intercalation accompanied by coordination and color changes in a layered metal-organic framework.

A new two-dimensional 3d-4f mixed-metal mixed dicarboxylate (homocyclic and heterocyclic) of the formula [Gd(2)(H(2)O)(2)Ni(H(2)O)(2)(1,2-bdc)(2)(2,5-pydc)(2)].8H(2)O (1; 1,2-H(2)bdc = 1,2-benzenedicarboxylic acid and 2,5-H(2)pydc = 2,5-pyridinedicarboxylic acid) has been prepared by employing the hydrothermal method. The structure has infinite one-dimensional -Gd-O-Gd- chains formed by the edge-shared GdO(9) polyhedral units, resulting exclusively from the connectivity between the Gd(3+) ions and the 1,2-bdc units. The chains are connected by the [Ni(H(2)O)(2)(2,5-pydc)(2)](2-) metalloligand, forming the two-dimensional layer arrangements. The stacking of the layers creates hydrophilic and hydrophobic spaces in the interlamellar region. A one-dimensional water ladder structure, formed by the extraframework water molecules, occupies the hydrophilic region while the benzene ring of 1,2-bdc occupies the hydrophobic region. To the best of our knowledge, the present compound represents the first example of a 3d-4f mixed-metal carboxylate in which two different aromatic dicarboxylate anions act as the linkers. The stabilization energies of the water clusters have been evaluated using density functional theory calculations. The water molecules in 1 are fully reversible accompanied by a change in color (greenish blue to brown) and coordination around Ni(2+) ions (octahedral to distorted tetrahedral).

A three-dimensional metal-organic framework with a distorted Kagome related layer showing canted antiferromagnetic behaviour.

Three-dimensional [Mn(3){C(6)H(3)(COO)(3)}(2)] comprising two-dimensional -Mn-O-Mn- distorted Kagome layers, formed by two geometrically different hexa-coordinated Mn(2+) ions, show less frustration and spin canted long range ordering possibly due to antisymmetric exchange.

Role of temperature and time in the formation of infinite -M-O-M- linkages and isolated clusters in MOFs: a few illustrative examples.

The role of temperature and time of reaction in the formation of metal-organic frameworks (MOFs) has been studied in two systems of compounds, manganese oxybis(benzoate) and manganese trimellitates, and the results compared and contrasted with other similar studies in the literature. The investigation reveals the formation of six different phases in oxybis(benzoate) and three phases in trimellitate systems. The low-temperature phases in both systems of compounds possess Mn 4 cluster units linked by the carboxylate ligands, while the high-temperature phase, irrespective of the duration of the reaction, has a three-dimensional structure with -Mn-O-Mn- linkages with brucite-related layers pillared by oxybis(benzoate) and Kagome-related layers pillared by trimellitate ligands. In all of the preparation, the reactions appear to have thermodynamic control as a function of the temperature. The isolation of low-dimensional structures in manganese oxybis(benzoate) at moderate time and temperature indicates possible kinetic control. The formation of reactive low-dimensional phases has been rationalized by considering the local charge distribution around the Mn site and also invoking a possible dissolution-recrystalization mechanism.

Ultra-high sensitivity of luminescent ZnCr2O4 nanoparticles toward nitroaromatic explosives sensing.

Here, we report the luminescence based sensing of trace amounts of nitroaromatic explosive organic compounds. The luminescence emission of nanosized spinel oxide ZnCr2O4 with high chemical and thermal stabilities has been used as a potential probe to detect such organic explosives. Low temperature solution combustion synthesized ZnCr2O4 oxide with an average particle size of ∼9 nm exhibits strong luminescence emission at 410 nm upon excitation at 260 nm in an aqueous suspension. The presence of nitroaromatics in ZnCr2O4 suspension dramatically suppresses the luminescence emission providing an opportunity to detect it quantitatively. The detection limit for 2,4,6-trinitrophenol (TNP) is as low as 23 ppb. A number of organic compounds have been investigated for a comprehensive understanding. The astonishing sensitivity of ZnCr2O4 nanoparticles towards nitro explosives is appealing for sensing application. A plausible explanation of such luminescence quenching has been ascribed to a two-fold mechanism. The underling mechanism is further substantiated by a similar study on ZnO nanoparticles.

The role of temperature on the structure and dimensionality of MOFs: an illustrative study of the formation of manganese oxy-bis(benzoate) structures.

Three new manganese oxy-bis(benzoate) compounds, synthesized by increasing the reaction temperature, with increasing dimensionality and decreasing Mn-Mn distances, indicate a possible pathway through an entropy driven dehydration route.