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Two functionalized metal–organic frameworks based on azobenzene and azine groups were synthesized and characterized. The ability of these materials as luminescent probes towards quinones was investigated and compared.

The OER catalytic activities of Fe-Ni3S2 nanosheets can be well manipulated by tailoring the d band center positions via interfacial engineering strategy.

Developing earth-abundant electrocatalysts for efficient oxygen evolution reaction (OER) is of paramount significance for electrochemical water splitting. Herein, an efficient in situ etching-deposition growth strategy is employed to transform pristine two-dimensional (2D) Co-metal-organic frameworks into hollow Ni/Co double hydroxide arrays (denoted as Ni/Co-DH), which not only yields a larger surface area and exposes more active sites but also decreases the activation energy to the OER. With structural and compositional benefits, the Ni/Co-DH exhibits high performance with an overpotential of 229 mV at 10 mA cm

Hydrogen production by electrochemical water splitting suffers from high kinetic barriers in the anodic oxygen evolution reaction (OER), which limits the overall efficiency. Herein, we report a structural and electronic engineering strategy by integrating self-standing Fe-doped Ni

The solvent-assisted linker exchange (SALE) method was used to produce amino-functionalized yttrium-based UiO-66 [NH

This study has developed a specific, easy, and novel approach to designing a sacrificial metal-organic framework (MOF) that can detect and measure the amount of Hg2+ in aqueous and nonaqueous solutions using the naked eye. The functionalized [Zn(oba)(RL3)0.5]n·1.5DMF (TMU-59) provides the ability of simple visual assessment or colorimetric readout without sophisticated analytical equipment. Because of the special interaction with Hg2+, degradation of the structure of this unique MOF causes the solution to change color from colorless to a pink that is easily recognizable to the naked eye. The presence of a methyl group plays a major role in naked-eye detection by a qualitative sensor. Furthermore, this qualitative sensor data for the production of a simple, instant, and portable red, green, and blue (RGB)-based quantitative sensor were used to determine the concentration of Hg2+ in different specimens. As a turn-off fluorescence sensor, this unique structure is also capable of detecting Hg2+ at very low concentrations (the limit of detection is 0.16 ppb). To the best of our knowledge, TMU-59 is the first MOF-based naked-eye sensor that can successfully and specifically display the presence of Hg2+ through a major color change.

To study the influence of pore structural properties of metal-organic frameworks (MOFs) on drug adsorption and delivery, we synthesized two MOF termed TMU-6(RL1) {[Zn(oba)(RL1)

We report the synthesis and structure of the first all-carboxylate-protected superatomic silver nanocluster. It was prepared by heating a dimethylformamide solution of perfluoroglutaric acid and AgNO3 under alkaline conditions, yielding a single crystal of [(CH3)2NH2]6[Ag8(pfga)6]. The [Ag8(pfga)6]6- cluster has a rhombohedral Ag86+ core, with each of its faces protected by one dianionic perfluoroglutarate (pfga) ligand. Electronic-structure analysis from density functional theory confirms the stability of this two-electron cluster due to the shell closing of the superatomic orbital in the (1S)2 configuration and explains the optical absorption of the cluster in the visible region as the transition from 1S to 1P orbital. The [Ag8(pfga)6]6- cluster emits bright green-yellow light in THF solution and bright orange light in the solid state. This work opens the door to using the widely available carboxylic acids to synthesize atomically precise Ag clusters of attractive properties.

As redox-active based supercapacitors are known as highly desirable next-generation supercapacitor electrodes, the targeted design of two ferrocene-functionalized (Fc(COOH)2 ) clusters based on coinage metals, [(PPh3 )2 AgO2 CFcCO2 Ag(PPh3 )2 ]2 ⋅7 CH3 OH (SC1 : super capacitor) and [(PPh3 )3 CuO2 CFcCO2 Cu(PPh3 )3 ]⋅3 CH3 OH (SC2 ), is reported. Both structures are fully characterized by various techniques. The structures are utilized as energy storage electrode materials, giving 130 F g-1 and 210 F g-1 specific capacitance at 1.5 A g-1 in Na2 SO4 electrolyte, respectively. The obtained results show that the presence of CuI instead of AgI improves the supercapacitive performance of the cluster. Further, to improve the conductivity, the PSC2 ([(PPh3 )2 CuO2 CFcCO2 ]∞ ), a polymeric structure of SC2 , was synthesized and used as an energy storage electrode. PSC2 displays high conductivity and gives 455 F g-1 capacitance at 3 A g-1 . The PSC2 as a supercapacitor electrode presents a high power density (2416 W kg-1 ), high energy density (161 Wh kg-1 ), and long cycle life over 4000 cycles (93 %). These results could lead to the amplification of high-performance supercapacitors in new areas to develop real applications and stimulate the use of the targeted design of coordination polymers without hybridization or compositions with additive materials.

Aim A new Ag(I) complex (A3) was synthesized and evaluated for its anticancer activity against human cancer cell lines. Materials and methods The complex A3 was characterized by 1H, 13C, and 31P nuclear magnetic resonance (NMR), infrared (IR) spectra, elemental analysis, and X-ray crystallography. The interaction of the complex with CT-DNA was studied by electronic absorption spectra, fluorescence spectroscopy, and cyclic voltammetry; cell viability (%) was assessed by absorbance measurement of the samples. Results The interaction mode of the complex A3 with DNA is electrostatic, and this complex shows good potential in anticancer properties against HCT 116 (human colorectal cancer cells) and MDA-MB-231 (MD Anderson-metastatic breast) cell lines with 0.5 micromolar concentrations. Conclusion The Ag(I) complex could interact with DNA noncovalently and has anticancer properties.

Advancement of the synthesis and control of the self-assembly process of new high-nucleus silver clusters with desired structures is important for both the material sciences and the many applications. Herein, three new silver clusters, 20-, 22-, and 8-nucleus, based on alkynyl ligands were constructed and their structures were confirmed by single-crystal X-ray diffraction, powder X-ray diffraction, elemental analyses, and Fourier-transform infrared spectroscopy (FT-IR). For the first time, the trivalent tetrahedron anion of AsO

Three-dimensional porous coordination polymers, which are known as metal–organic frameworks (MOFs), have drawn considerable attention owing to their properties, such as highly crystalline and ordered structures, inorganic–organic-hybrid nature, tunability of chemical functionality, high porosity and surface area and moderate-to-high stability. Due to these properties, MOFs are applied extensively as probes for the detection of large varieties of organic molecules. In this line, different MOF-based instrumental and material-based methods along with different strategies have been developed to study and extend our information about the capabilities of MOFs as sensing probes for the detection of organic molecules as well as improving and developing their detection limits, selectivity and sensitivity toward specific analytes. Considering these points, we have presented and classified the content of this review based on the chemical structures of organic analytes in three categories, including (I) nitroaromatic explosives and energetic materials, (II) small organic molecules, such as solvents and volatile organic compounds, and (III) organic amines. For each group of these analytes, different material and instrumental methods using MOFs have been explained, with illustrations of remarkable examples. Finally, we compare the methods for the detection of each group of analytes and discuss which instrumentation is more effective for each group of analytes.

A one dimensional high-nucleus silver polymer (SSc: silver supercapacitor) was designed by a simple and single-step synthesis. This stable highly conductive metallic polymer without any modification steps such as pyrolysis or doping provides a desirable path for electron transfer and shows high capacitance as a non-hybrid electrode (specific capacitance of 827 F g−1 at 5 A g−1). This polymer could tolerate low to high scan rates (200 mV s−1 to 1 V s−1) and exhibit rectangular cyclic voltammetry shapes, high power density and long cycle life over 5000 cycles (90.7%). These results could promise the development of new types of high-performance supercapacitors by overcoming the low conductivity and the limited capacity challenges of known structures without the need for any modification which is unique in non-hybrid electrode materials.

Extensive composition engineering research has been conducted on bandgap tunability, but the combination of two mechanisms for better photon harvesting over a wide range has rarely happened; this is of great importance for improving photocatalytic efficiency with sunlight. In order to enable concurrent heterogenic Fenton and Fenton-like reactions for dye degradation, two novel ferrocene-functionalized clusters, [(PPh3)3CuO2CFcCO2Cu(PPh3)3]·3CH3OH (D1) and [(PPh3)2AgO2CFcCO2Ag(PPh3)2]2·7CH3OH (D2) were designed, synthesized and characterized by multiple techniques. These chemically and thermally stable coinage clusters exhibit high photocatalytic activity towards the degradation of methylene blue as a model dye in the presence of H2O2 under direct sunlight irradiation. The degradation performance of complex D1 is about twice that of complex D2. The catalytic performance of D1 (15 000 mg g−1 in less than 20 min) is superior to those of other reported complexes, which can be attributed to the high level of generated hydroxyl radicals which are the most active species for dye degradation in the combination of Fenton and Fenton-like mechanisms. In addition to the degradation carried out with the aid of the Fe(III) of ferrocene, based on the Fenton mechanism, the photogenerated holes trapped by Cu(I) act as catalysts in the Fenton-like mechanism to produce an excess of hydroxyl radicals, adding to those formed via scavenging of photogenerated electrons by hydrogen peroxide. Furthermore, the performance of D1 in the presence of H2O2 as a dual photocatalyst under natural sunlight irradiation needs no pH adjustment which is a unique characteristic. This bilateral compound offers a promising strategy for the design of new photocatalysts.

In this work, we report a simple method for synthesis of the C/ZnO semiconductor nanocomposite with the high porosity (732 m2/g) from fluorinated metal–organic framework (F-MOF), namely [Zn2(hfibba)2(L1)]n. D MF (TMU-44) where (L1 = N,N'-bis-pyridin-4-ylmethylene-benzene-1,5-diamine and H2hfibba = 4,4′-(hexafluoroisopropylidene) bis(benzoic acid)) with the limited porosity. The C/ZnO nanocomposite was characterized by powder X-ray diffraction; Brunauer-Emmett-Teller (BET) surface area, FE-SEM, and EDX mapping analysis. Furthermore, the as-synthesized C/ZnO nanocomposite showed favorable electrical conductivity at room temperature.

A novel ferrocene-functionalized silver cluster (FcAgCs) has been designed and synthesized with the assistant of ultrasound treatment and fully characterized by single crystal spectroscopy, IR, UV–Vis, XRD, TGA, NMR, CV and elemental analyses. Ultrasound synthesis method facilitates and accelerates synthesis of this amazing structure and plays a vital role in the synthesis of this special cluster. Single-crystal X-ray analysis reveal that the cluster can be described as a cationic [(dppf)2Ag4(C CtBu)2(CH3OH)2]2+ (dppf = 1,1′-bis(diphenylphosphino)ferrocene) species consisted of four rhombic silver atom and two isolated BF4- counter anions. Thermal stability greater than 200 °C and solution CV results show that the title cluster is sufficiently stable and suitable for the fabricating of FcAgCs/ITO thin-films and exploring as electrochemical responding materials. Based on its properties, we use it to prepare thin-films on ITO substrate by spin coating method. Verification of synthesis, thickness, uniformity and stability of the fabricated FcAgCs/ITO thin-films were characterized and confirmed by UV, XRD, SEM and the scotch tape adhesion peel test. Moreover, we use this FcAgCs/ITO thin-film electrode as thin-film electrochemical detector which shows sensitive and quick response in the detection of H2O2.

Metal-organic frameworks or MOFs are porous compounds with special properties like controllability in terms of composition and structure coupled with high porosity. These kind of porous materials have enticed a great deal of attention in various fields including energy storage and conversion, ion exchange, separation, sensor, drug delivery, molecular recognition, and catalysis. Also, MOFs have been considered as flexible precursors for synthesis of different nano-materials and novel multifunctional nanocomposites/hybrids with preferable functional characteristics compared to their initial components. Hence, development of different strategies for size and shape controlling of MOFs is very important for obtaining ordered MOFs and their derived materials/hybrids. This review offers an overview of various template strategies for synthesis of MOFs and investigation the morphology effect in MOFs application as well as applying them as precursors and templates for directed synthesis of diverse nano-materials.

This study has developed a specific, easy, and novel approach to designing a sacrificial metal-organic framework (MOF) that can detect and measure the amount of Hg

Atomically precise silver nanoclusters (Ag-NCs) are known as a hot research area owing to their brilliant features and they have attracted an immense amount of research attention over the last year. There is a lack of sufficient understanding about the Ag-NC synthesis mechanisms that result in optimal silver nanoclusters with an appropriate size, shape, and morphology. In addition, the coexisting flexible coordination of silver ions, the argentophilic interactions, and coordination bonds result in a high level of sophistication in the self-assembly process. Furthermore, the expansion of clusters by the organic ligand to form a high dimensional structure could be very interesting and useful for novel applications in particular. In this study, a novel two-dimensional 14-nucleus silver poly-cluster was designed and synthesized by the combination of two synthetic methods. The high nucleus silver cluster units are connected together via tetradecafluoroazelaic acid (CF2) and this leads to the high stability of the polymer. This highly stable conductive poly-cluster, with bridging groups of difluoromethylene, displays a high energy density (372 F g−1 at 4.5 A g−1), excellent cycling stability, and great capacity. This nanocluster shows a high power density and long cycle life over 6000 cycles (95%) and can also tolerate a wide range of scan rates (5 mV s−1 to 1 V s−1), meaning it could act as a green energy source.

A high-nucleus silver nanopolycluster as a new type of silver-based polymer supercapacitor (SSc) by a simple and single-step synthesis process was designed and synthesized. The structural, optical, and electrochemical properties of SSc-2 were determined. This highly stable conductive 3D nanopolycluster shows great cycling stability, large capacity, and high energy density without any modification or doping process and so acts as an excellent SSc (412 F g-1 at 1.5 A g-1). In addition, there was a stable cycling performance (94% capacitance) following 7000 cycles at 3 A g-1 current density. The presence of fluorinated groups, 3D expansion of high-nucleus metallic clusters, and porosity are the advantages of SSc-2 that lead to stability, conductivity, and high capacity, respectively. These results lead to the development of a novel kind of SSc by overcoming the low conductivity and limited capacity challenges without any modification.

Anion recognition by neutral hosts that function in aqueous solution is an emerging area of interest in supramolecular chemistry. The design of neutral architectures for anion recognition still remains a challenge. Among neutral anion receptor systems, urea and its derivatives are considered as "privileged groups" in supramolecular anion recognition, since they have two proximate polarized N-H bonds exploitable for anion recognition. Despite promising advancements in urea-based structures, the strong hydrogen bond drives detrimental self-association. Therefore, immobilizing urea fragments onto the rigid structures of a metal-organic framework (MOF) would prevent this self-association and promote hydrogen-bond-accepting substrate recognition. With this aim, we have synthesized two new urea-containing metal-organic frameworks, namely [Zn(bpdc)(L2)]n·nDMF (TMU-67) and [Zn2(bdc)2(L2)2]n·2nDMF (TMU-68) (bpdc = biphenyl-4,4'-dicarboxylate; bdc = terephthalate; L2 = 1,3-bis(pyridin-4-yl)urea), and we have assessed their recognition ability toward different anions in water. The two MOFs show good water stability and anion affinity, with a particular selectivity toward dihydrogen arsenate for TMU-67 and toward fluoride for TMU-68. Crystal structure characterizations reveal 3-fold and 2-fold interpenetrated 3D networks for TMU-67 and TMU-68, respectively, where all single interpenetrated networks are hydrogen bonded to each other in both cases. Despite the absence of self-quenching, the N-H urea bonds are tightly hydrogen bonded to the oxygen atoms of the dicarboxylate ligands and cannot be directly involved in the recognition process. The good performance in anion sensing and selectivity of the two MOFs can be ascribed to the network interpenetration that, shaping the void, creates monodimensional channels, decorated by exposed oxygen atom sites selective for arsenate sensing in TMU-67 and isolated cavities, covered by phenyl groups selective for fluoride recognition in TMU-68.

We report the synthesis and structure of the first all-carboxylate-protected superatomic silver nanocluster. It was prepared by heating a dimethylformamide solution of perfluoroglutaric acid and AgNO

Ferrocene and its derivatives, especially ferrocene-based coordination polymers (Fc-CPs), offer the benefits of high thermal stability, two stable redox states, fast electron transfer, and excellent charge/discharge efficiency, thus holding great promise for electrochemical applications. Herein, we describe the synthesis and electrochemical applications of Fc-CPs and reveal how the incorporation of ferrocene units into coordination polymers containing other metals results in unprecedented properties. Moreover, we discuss the usage of Fc-CPs in supercapacitors, batteries, and sensors as well as further applications of these polymers, for example in electrocatalysts, water purification systems, adsorption/storage systems.

The first silver nanocluster with an octahedral template of TeO66– was synthesized as a neutral 36-nucleus nanocluster, and its structure was demonstrated using single-crystal X-ray diffraction, Fo...

A review of the synthesis, structure and specifically the effect of counter-ions on the properties of ionic metal organic frameworks (ionic-MOFs) is presented, highlighting the important advances in this regard over the past decade. Most focus is on ionic porous metal–organic frameworks (MOFs) materials consisting of porous anionic or cationic frameworks and cationic or anionic guests. The structure and performance of cationic and anionic MOFs are influenced by several factors, such as organic ligands, metal ions and charge-balancing anions. These types of anionic and cationic materials have distinct advantages in comparison with neutral MOFs in the design of functional materials and their synthesis affords several distinct advantages over that for routine neutral frameworks by virtue of the isolated charged species in confined nano-spaces. The nanosized and charged pores in these ionic structures generate a strong interaction between the host and guest molecules, including enhanced adsorption towards small gases and solvent molecules. Ionic-MOFs can be easily modified via ion exchange and accommodate other charged guest molecules, making them an ideal platform for different applications, such as functional materials. The development of synthesis methods by ion exchange and the potential applications of such cationic or anionic structures have been discussed thoroughly in this review.

The binding of ruthenium(II) complexes of formulation [(η6-p-cymene)RuCl(L1)]PF6 (1) and [(η6-C6H6)RuCl(L1)]PF6 (2), L1= (E)-4-nitro-N-(quinolin-2-ylmethylene)aniline, to calf thymus–DNA (CT-DNA) were investigated via techniques include electronic absorption spectra, fluorescence and redox behavior (cyclic voltammetry) and the results of the analysis of complexes 1 and 2 are compared with the results of complexes 3 and 4, [(η6-p-cymene)RuCl(L1)]PF6 (3) and [(η6-C6H6)RuCl(L2)]PF6 (4), L2=(E)-N-((6-bromopyridin-2-yl)methylene)-4-nitroaniline. Single crystals of the complexes were separated by the slow evaporation method and they were characterized by elemental analysis, 1H NMR and 13C NMR spectroscopy and the thermal studies of them were studied by thermal gravimetric (TG) and differential scanning calorimetry (DSC). Also, it has been shown that the complexes are photosensitive molecules. RuO2 nanoparticles were prepared by calcination of the complexes and it was investigated the influence of the treating by ultrasound on the characteristics of the samples before calcination.

Aim: To study of the interactions of two new ruthenium(II) complexes (C1 and C2) with calf thymus (CT)-DNA; production of RuO2 nanoparticles using the complexes precursor. Materials & methods: Complex C1 was characterized by x-ray crystallography. The binding of the complexes with (CT)-DNA was studied using techniques that include electronic absorption spectra, fluorescence and redox behavior. The preparation of RuO2 nanoparticles was carried out by thermal decomposition. Results: The interaction mode of DNA with complexes is the type of electrostatic. It was revealed that sonication of the samples, before thermal decomposition, has been affected the morphologies and sizes of the resulting nanoparticles. Conclusion: The complexes are capable of interaction with DNA molecules and they have a good potential to prepare nanostructures.

Metal-organic frameworks (MOFs) are crystalline solids formed by inorganic clusters or metal ions (generally transition metal) linked by bi- or multifunctional organic ligands. Exploiting the advantages of the MOFs including large surface area, high metal content, and flexibility in designing the active sites, would be an innovative idea to make novel catalysts. This review gives a useful overview on the catalytic applications of MOFs regarding their structural developments toward catalyst fabrication. The catalytic applications cited in this review include the condensation of organic reaction of two or more components involved in a verity of reactions. More specifically, the review has explored the catalytic applications of MOFs in C-C and C-X (S, N, O) bond formation reactions leading to the formation of a more complicated compounds. The emphasis has been made on discussing the stability of the MOFs, their reusability and in providing a comparison of the performance of MOFs with respect to other homogeneous and heterogeneous catalysts.

Two novel Ru(II) complexes [(η6-p-cymene)RuCl(L2)]PF6 (R2) and [(η6-C6H6)RuCl(L2)]PF6 (R4), with ligand (E)-N-((6-bromopyridin-2-yl)methylene)-4-(methylthio)aniline (L2), were synthesized and characterized by elemental analysis, 1H NMR, 13C NMR and IR spectroscopy. Based on X-ray crystallography studies, complexes R2 and R4 have coordination environments with formulated (η6-p-cymene)Ru(N2Cl) and (η6-C6H6)Ru(N2Cl), respectively. The thermal stabilities of compounds R2 and R4 were studied by thermal gravimetric (TG) and differential scanning calorimetry (DSC). Thermal decomposition of these complexes was at 280°C and 260°C under air atmosphere respectively. The interaction of these complexes with calf thymus DNA (CT-DNA) was explored through electronic absorption spectra, fluorescence and redox behavior studies. The results showed that the complexes bind to CT-DNA with electrostatic interactions. Nanoparticles of RuO2 were prepared by calcination of R2 and R4. Also the role of the ultrasound waves on the characteristics of the RuO2 nanoparticles was studied. The nanoparticles were characterized by IR spectroscopy and X-ray diffraction (XRD). Also size and morphology of nanoparticles were studied by scanning electron microscopy (SEM).

Two novel Ru(II) complexes [(η6-p-cymene)RuCl(L1)]PF6 (R1) and [(η6-C6H6)RuCl(L1)]PF6 (R3) with ligand (E)-4-(methylthio)-N-((quinolin-2-yl)methylene)benzenamine (L1), were synthesized and investigated using elemental analysis, IR, 1H NMR, 13C NMR spectroscopy and X-ray crystallography. Complexes R1 and R3 have coordination environments with formulated (η6-p-cymene)Ru(N2Cl) and (η6-C6H6)Ru(N2Cl) respectively. The thermal stabilities of compounds R1 and R3 were studied by thermal gravimetric (TG) and differential scanning calorimetry (DSC). The binding of the complexes R1 and R3 to calf thymus DNA (CT DNA) was investigated by using electronic absorption spectra, fluorescence and redox behavior studies. Such experimental data showed that there are interactions between complexes and CT-DNA and the nature of this binding is electrostatic interaction type. Calcination of ultrasonic treated R1 and R3 results in the formation of nanoparticles of RuO2. The nanoparticles were characterized by IR spectroscopy and X-ray diffraction (XRD). Also size and morphology of nanoparticles were investigated by scanning electron microscopy (SEM).

The compounds [(η6-p-cymene)RuCl2(4-nitroaniline)] and [(η6-p-cymene)RuCl2(2-halogen-4-nitroaniline)] were synthesized and characterized by various means. The [(η6-p-cymene)RuCl2(4-nitroaniline)] and [(η6-p-cymene)RuCl2(2-fluoro-4-nitroaniline)] compounds were determined by X-ray diffraction, appearing in a distorted piano-stool type of arrangement with similar bond lengths and angles around the ruthenium. The compounds exhibited moderate to strong in vitro cytotoxicity against A549 and MCF-7 human cancer cells. Substitution of heavy halogen atom on the ortho position of para-nitroaniline weakened the cytotoxicity against both of MCF-7 and A549, except the cases of fluorine substitution for hydrogen atom regarding A549 and bromine substitution for chlorine atom regarding MCF-7, which showed minor deviation.

Aim A new Ag(I) complex (A3) was synthesized and evaluated for its anticancer activity against human cancer cell lines. Materials and Methods The complex A3 was characterized by 1H, 13C, and 31P nuclear magnetic resonance (NMR), infrared (IR) spectra, elemental analysis, and X-ray crystallography. The interaction of the complex with CT-DNA was studied by electronic absorption spectra, fluorescence spectroscopy, and cyclic voltammetry; cell viability (%) was assessed by absorbance measurement of the samples. Results The interaction mode of the complex A3 with DNA is electrostatic, and this complex shows good potential in anticancer properties against HCT 116 (human colorectal cancer cells) and MDA-MB-231 (MD Anderson-metastatic breast) cell lines with 0.5 micromolar concentrations. Conclusion The Ag(I) complex could interact with DNA noncovalently and has anticancer properties.

In order to study the charge effect on the formation of an anion-templated silver cluster, a trivalent tetrahedral anion was incorporated into the silver assembly. A 26-nuclear silver cluster was prepared, and its structure was confirmed by single-crystal X-ray diffraction. Also, the resulting structure was characterized by powder X-ray diffraction data. Its light absorption and photoluminescent properties were studied by solid-state UV diffuse-reflectance and fluorescence spectroscopy. Compared with the other reported silver clusters with tetrahedral anion templates, the more negative VO43- anion led to the formation of a bigger silver cluster. Also, the supramolecular motif O-H(CH3OH)···O(trifluoroacetate) was confirmed on the cluster surface for the first time.

Three Ru(II) half-sandwich complexes containing (N,N)-bound Schiff-base ligands, [(η6-C6H6) RuCl(L1)]PF6 (1) L1 = (E)-1-(6-methylpyridin-2-yl)-N-(p-tolyl)methanimine, [(η6-p-cymene)RuCl(L1)]PF6 (2) and [(η6-p-cymene)RuCl(L2)]PF6 (3) L2 = (E)-1-(6-bromopyridin-2-yl)-N-(p-tolyl)methanimine, were synthesized, characterized and their supramolecular structures were analyzed. The crystal packing of these compounds was studied using geometrical analysis and Hirshfeld surface analysis. The fluorescence behavior of these compounds was also studied. TD-DFT calculations were carried out to better understand the fluorescence properties of complexes 1–3. These compounds could be promising for the design of organometallic dye systems.

Two typical highly porous metal-organic framework (MOF) materials based on lead(II), [Pb(4-bpdh)(NO3)2(H2O)]n (TMU-1) and [Pb(4-bpdh)(NO3)2]n (TMU-2) have been used for the removal of harmful dyes (anionic dye methyl orange (MO) and cationic dye methylene blue (MB)) from contaminated water via adsorption. The adsorption capacities of TMU-1 and TMU-2 are much higher than those of an activated carbon. Our results show that the difference between MO and MB adsorption in TMU-1 and TMU-2 could be relate to pore size and coordinated H2O interactions. Dye elimination has also been studied by the use of adsorption/desorption process. The delivery of dyes from compounds in methanol at room temperature was determined by UV/vis spectroscopy.

Many piesce of research have been performed to detect nitroaromatic-compounds (NACs) by metal-organic frameworks (MOFs). Despite extensive studies, there are still significant challenges like selective detection of specific NAC group in presence of other NACs. Here, we have integrated two functionalization strategies through decoration of pore-walls of the MOFs with trifluoromethyl groups and extension in π-conjugated system. Based on this idea, trifluoromethyl TMU-44 (with the formula [Zn2(hfipbb)2(L1)]n. D MF, H2hfipbb = 4,4′-(hexafluoroisopropylidene) bis(benzoic acid), L1 = N,N′-bis-pyridin-4-ylmethylene-benzene-1,4-diamine) and TMU-45 (with formula [Zn2(hfipbb)2(L2)]n. D MF, L2 = N,N′-bis-pyridin-4-ylmethylene-naphthalene-1,5-diamine) frameworks have been synthesized. The aromatic skeleton of TMU-44 is based on phenyl rings while TMU-45 aromatic skeleton is extended by replacement of phenyl with naphthyl core. Measurements reveal that these MOFs are highly sensitive to phenolic NACs especially 2,4,6-trinitrophenol (TNP) with high quenching efficiency of 90% for TMU-44 (KSV = 10,652 M−1, LOD = 6.9 ppm) and 99% for TMU-45 (KSV = 34,741 M−1, LOD = 2.07 ppm). The proposed detection mechanism can be associated with hydrogen bonding between OH group of phenolic NACs and trifluoromethyl groups of TMU-MOFs as well as π(rich)∙∙∙π(deficient) interaction between π-conjugated backbone of TMU-frameworks and π-deficient ring of NACs.

Designing porous and functionalized adsorbents and achieving high efficiency in heavy metals removal from wastewater is in the spotlight of environmental science. On the other hand, upon removal, adsorbents are still highly hazardous requiring that great care be taken in its packaging, transporting and storing. A fundamental route in the synthesis of functional extended structures is the ability to combine different chemical entities in a controlled way in order to achieve high performance. Herein, we report the systematic design of dual-functionalized metal organic framework (TMU-81) by incorporating sulfonyl and amide groups for the removal of Cd(II), Cu(II) and Cr(II) ions from simulated aqueous solutions. TMU-81 showed significant enhancement in heavy metals uptake suggesting that the strong host - guest interactions between cations and the donor sites play a major role in adsorption process. The maximum adsorption capacity for Cd2+ was 526 mg/g which is among the highest values reported for similar MOFs and other porous materials. The good performance in uptake and selectivity of TMU-81 can be attributed to the network structure that shaping the void, create mono-dimensional channels, decorated by exposed oxygen atom sites selective for Cadmium ion. Environmental "compatibility" of a treated MOFs was studied in order to evaluate its possible recycling as a new template for different applications by using pyrolysis method. Engineering of the pore surface provides a potential for MOF with a hybrid interface to act as a versatile tool for the design of multifunctional nanoparticles to meet specific application requirements.

A novel binuclear Cu(II) complex based on ferrocene dicarboxylate was synthesized through ultrasonic and solvothermal processes and its structure confirmed by spectroscopy (IR), ultraviolet-visible spectrum (UV–Vis) and powder X-ray diffraction analysis (PXRD). Structural characterization of the complex was performed through single-crystal X-ray diffraction and thermal stability of it was perused via thermogravimetric analysis (TGA). The title Cu(II) complex was used as an effective sensor for H2O2. The electrochemical method is one of the most effective methods for material sensing. In many electrochemical techniques to increase the efficiency of activity, the electrochemically active agent is supported on a substrate. Instead of using substrate, the chemical active agent can be applied as a part of the complex structure. In this work, ferrocene dicarboxylate as an active agent in the Cu(II) complex has been used for sensing of H2O2. Due to the effect of particle size on electrochemical activity, the nano-sized complex was synthesized by ultrasonic technique (as an environmentally friendly method) and also, CuO nanoparticles were also obtained by thermal decomposition of ultrasonic treated complex at 500 °C. The size and morphology of the nanoparticles were explored by scanning electron microscopy (SEM). As well as, they were characterized through X-ray diffraction (XRD) and elemental mapping.

A novel ferrocene-functionalized silver cluster (FcAgCs) has been designed and synthesized with the assistant of ultrasound treatment and fully characterized by single crystal spectroscopy, IR, UV-Vis, XRD, TGA, NMR, CV and elemental analyses. Ultrasound synthesis method facilitates and accelerates synthesis of this amazing structure and plays a vital role in the synthesis of this special cluster. Single-crystal X-ray analysis reveal that the cluster can be described as a cationic [(dppf)

Water pollution by heavy metal ions especially Hg(II) and Pb(II) is one of the most important concerns because of their harmful effects on human health and environment sustainability. Here, we developed Fe3O4@TMU-32 metal-organic framework (MOF)-based nanocomposite by applying pore functionalization and surface-charge modulation strategies. Based on synergic effects of these strategies, Fe3O4@TMU-32 nanocomposite shows very high capacity toward Hg(II) and Pb(II) metal ions. TMU-32 (with formula [Zn(OBA)(DPU)]·2DMF·H2O where H2OBA and DPU are (4,4′-oxybis(benzoic acid)) and 1,3-di(pyridin-4-yl)urea)) is decorated with urea functional groups containing carbonyl and amine groups that can interact with metal ions. As results, TMU-32 show very high capacity toward Hg(II) and Pb(II) ions. To improve the TMU-32 capacity toward Hg(II) and Pb(II) cations, we tried to modulate the surface-charge of TMU-32 as a host-framework. Surface-charge modulation strategy had been conducted through encapsulation of Fe3O4 nanoparticles by TMU-32 in an in-situ synthesis procedure and synthesis of Fe3O4@TMU-32 nanocomposite. Fe3O4@TMU-32 nanocomposite shows improved removal capacity (45 % and 54 % toward Pb(II) and Hg(II)) rather pristine TMU-32 framework because of urea decorated framework and charge modulated surface. Fe3O4@TMU-32 nanocomposite adsorb 1600 mg.g-1 of Pb(II) and 905 mg.g-1 of Hg(II) which extremely rare in the literature. Such improvement can be related to the electrostatic interaction between cationic nature of Pb(II) and Hg(II) and negative charge of the Fe3O4@TMU-32 adsorbent.

To study of the interactions of two new ruthenium(II) complexes (C1 and C2) with calf thymus (CT)-DNA; production of RuOComplex C1 was characterized by x-ray crystallography. The binding of the complexes with (CT)-DNA was studied using techniques that include electronic absorption spectra, fluorescence and redox behavior. The preparation of RuOThe interaction mode of DNA with complexes is the type of electrostatic. It was revealed that sonication of the samples, before thermal decomposition, has been affected the morphologies and sizes of the resulting nanoparticles.The complexes are capable of interaction with DNA molecules and they have a good potential to prepare nanostructures.