Molybdate-Templated Luminescent Silver Alkynyl Nanoclusters: Total Structure Determination and Optical Property Analysis.

Two novel MoO-templated luminescent silver alkynyl nanoclusters with 20-nuclearity ([(MoO)@Ag(C≡CBu)(PhPO)(tfa)]·(tfa) ()) and 18-nuclearity ([(MoO)@Ag(C≡CBu)(PhPO)]·(OH) ()) (tfa = trifluoroacetate) were synthesized with the green light maximum emissions at 507 and 516 nm, respectively. The nanoclusters were investigated and characterized by single-crystal X-ray crystallography, electrospray ionization mass spectrum (ESI-MS), X-ray photoelectron spectroscopy, thermogravimetry (TG), photoluminescence (PL), ultraviolet-visible (UV-vis) spectroscopy, and density functional theory calculations (DFT). The two nanoclusters differ in their structure by a supplementary [Ag(tfa)] organometallic surface motif, which significantly participates in the frontier molecular orbitals of , resulting in similar bonding patterns but different optical properties between the two clusters.

Template-Free Synthesis of Two New Luminescent One-Dimensional High-Nuclearity Silver Polyclusters.

The metallophilic properties, spherical configuration, and flexible coordination of silver ions make them prone to create various coordination modes and structural features. Therefore, with the increase of the complexities of self-assembly, the effect of various synthetic conditions in the final structure of silver compounds becomes diverse and attractive. In this study, two new silver polyclusters, 16- and 21-nuclearity, protected by multiple ligands including alkynyl, trifluoroacetate, and diphenylphosphinate, were synthesized and characterized by single-crystal X-ray diffraction, powder X-ray diffraction, and Fourier transform infrared (FTIR) spectroscopy.

Monocarboxylate-protected two-electron silver nanoclusters with high photothermal conversion performance.

The first series of monocarboxylate-protected silver nanoclusters was synthesized and fully characterized by X-ray diffraction, fourier-transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and electrospray ionization mass spectrometry (ESI-MS). Specifically, compounds [Ag(L)(9-AnCO)] (L = PhP (I), (4-ClPh)P (II), (2-furyl)P (III), and PhAs (IV)) were prepared by a solvent-thermal method under alkaline conditions. These clusters exhibit a similar unprecedented structure containing a [Ag@Ag] metal kernel, of which the 2-electron [Ag] inner core shows a flattened and puckered hexagonal bipyramid of symmetry.

Raman Study of Voltage Tolerance Up to 2.2 V of Ionic Liquid Analogue Supercapacitor Electrolytes Immune to Water Adsorption Conferred by Amphoteric Imidazole Additives.

Ionic liquid analogues (ILAs) are promising electrolytes for supercapacitors due to their low cost and considerable voltage (>2.0 V). However, the voltage is <1.

Synthesis and Study of Photothermal Properties of a Mixed-Valence Nanocluster Cu/Cu with Strong near-Infrared Optical Absorption Supported by 4--Butylcalix[4]arene Ligand.

The first mixed-valence nanocluster Cu/Cu with the highest percentage of Cu ions was synthesized by using 4--butylcalix[4]arene (Calix4), with the formula DMF⊂[(CO)@CuCu(Calix4)Cl(DMF)(HO)]•DMF (), as a photothermal nanocluster. Its structure was characterized using single-crystal X-ray diffraction, Fourier-transform infrared spectroscopy, and powder X-ray diffraction. In addition, the charge state and chemical composition of the nanocluster were determined using electrospray ionization spectrometry and X-ray photoelectron spectroscopy (XPS) spectrum.

Synthesis of Two Neutral Silver Alkynyl Nanoclusters by a Single Divalent Tetrahedral Anion Template and a Study of Their Optical Features.

The synthesis of nanoclusters from simple structural units is usually a challenging process because of the complexity and unpredictability of the self-assembly process of these types of compounds. Herein, two new neutral 19-nuclearity silver nanoclusters based on alkynyl ligands with the formulas [(CrO)@Ag(C≡CBu)(PhPO)(tfa)(CHOH)] () and [(SO)@Ag(C≡CBu)(PhPO)(tfa)(CHOH)] (), in which tfa = trifluoroacetate, were synthesized, and their structures were investigated by single-crystal and powder X-ray diffraction, electrospray ionization mass spectrometry, elemental analyses, and Fourier transform infrared spectroscopy. The surface ligands of PhPOH and trifluoroacetate were assembled through hydrogen bonding, metal-aromatic interactions, and coordination bonding around 19 silver atoms as the metal skeletons of the nanoclusters.

Ferroelectric benzimidazole additive-induced interfacial water confinement for stable 2.2 V supercapacitor electrolytes exposed to air.

Deep eutectic solvents (DESs) are known as low-cost and environmentally friendly electrolytes for supercapacitors. However, because DESs are particularly vulnerable to moisture adsorption in the air, the voltage window (<1.2 V) is significantly lower than expected.

Compact accumulation of superatomic silver nanoclusters with an octahedral Ag core ligated by trithiane.

Two superatomic solids, a bi-cluster compound, [Ag(3S)(OTf)][Ag(3S)(CCBu)](OTf) [Ag6(0)·Ag6(i)], and a homologous nanocluster, [Ag(3S)(tfa)] (Ag6), have been described here, which are both close-packed in the crystal lattice with the ligation of trithiane. Their aggregation-state-dependent absorption and fluorescence properties could be ascribed to the enhanced intercluster charge-transfer in the crystalline state.

Ultrasound Irradiation Assisted Synthesis of Luminescent Nano Amide-Functionalized Metal-Organic Frameworks; Application Toward Phenol Derivatives Sensing.

Two nano amide-functionalized metal-organic frameworks (MOFs) with molecular formula [Co(oba) (bpta)]·(DMF) TMU-50 and [Co(oba) (bpfn)]·(DMF) TMU-51 obtained under ultrasonic method without any surfactants. The only difference between the two selected amide functionalized pillar ligands, N,N'-bis(4-pyridinyl)-terephthalamide (bpta), and N,N'-bis-(4-pyridylformamide)-1,5-naphthalenediamine (bpfn), is related to the naphthyl group, which led to the different luminescence properties of the nano frameworks. In this study, the special ability of the luminescent nano MOFs were investigated to sensitize nitroaromatic compounds.

Construction of eight mixed-valence pentanuclear CuI4Cu clusters using ligands with inhomogeneous electron density distribution: synthesis, characterization and photothermal properties.

To enhance light absorption in the visible region for the utilization of sunlight, eight mixed-valence polynuclear Cu/Cu clusters have been synthesized for evaluating their photothermal conversion performance. They are fabricated considering the ligand's electron density distribution inhomogeneity using 1,2,3-triazole (3N) or tetrazole (4N) and different mono-phosphine ligands. We report here the synthesis, crystal structure, characterization, optical properties, and photothermal conversion performance of these clusters.

Stable supercapacitor electrode based on two-dimensional high nucleus silver nano-clusters as a green energy source.

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.

New 3D Porous Silver Nanopolycluster as a Highly Effective Supercapacitor Electrode: Synthesis and Study of the Optical and Electrochemical Properties.

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 at 1.

Electrochemical Applications of Ferrocene-Based Coordination Polymers.

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.

All-Carboxylate-Protected Superatomic Silver Nanocluster with an Unprecedented Rhombohedral Ag Core.

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 under alkaline conditions, yielding a single crystal of [(CH)NH][Ag(pfga)]. The [Ag(pfga)] cluster has a rhombohedral Ag core, with each of its faces protected by one dianionic perfluoroglutarate (pfga) ligand.

Comparative Study of the Supercapacitive Performance of Three Ferrocene-Based Structures: Targeted Design of a Conductive Ferrocene-Functionalized Coordination Polymer as a Supercapacitor Electrode.

As redox-active based supercapacitors are known as highly desirable next-generation supercapacitor electrodes, the targeted design of two ferrocene-functionalized (Fc(COOH) ) clusters based on coinage metals, [(PPh ) AgO CFcCO Ag(PPh ) ] ⋅7 CH OH (SC : super capacitor) and [(PPh ) CuO CFcCO Cu(PPh ) ]⋅3 CH OH (SC ), is reported. Both structures are fully characterized by various techniques. The structures are utilized as energy storage electrode materials, giving 130 F g and 210 F g specific capacitance at 1.

Hexavalent Octahedral Template: A Neutral High-Nucleus Silver Alkynyl Nanocluster Emitting Infrared Light.

The first silver nanocluster with an octahedral template of TeO was synthesized as a neutral 36-nucleus nanocluster, and its structure was demonstrated using single-crystal X-ray diffraction, Fourier transform infrared spectroscopy, electrospray ionization mass spectrometry, and X-ray photoelectron spectroscopy. The peripheral ligands of the cagelike skeleton of the nanocluster are CFCOO and BuC≡C. During the synthesis, the TeO template arranged the nanocluster, and a 36-nucleus nanocluster was formed.

Ultrasonic-assisted fabrication of thin-film electrochemical detector of HO based on ferrocene-functionalized silver cluster.

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)Ag(CCBu)(CHOH)] (dppf = 1,1'-bis(diphenylphosphino)ferrocene) species consisted of four rhombic silver atom and two isolated BF counter anions.

Trivalent Tetrahedral Anion Template: A 26-Nucleus Silver Alkynyl Cluster Encapsulating Vanadate.

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.

Sonochemical effect on two new Ruthenium(II) complexes with ligand (E)-N-((6-bromopyridin-2-yl)methylene)-4-(methylthio)aniline precursors for synthesis of RuO nanoparticles.

Two novel Ru(II) complexes [(η-p-cymene)RuCl(L2)]PF (R2) and [(η-CH)RuCl(L2)]PF (R4), with ligand (E)-N-((6-bromopyridin-2-yl)methylene)-4-(methylthio)aniline (L2), were synthesized and characterized by elemental analysis, H NMR, C NMR and IR spectroscopy. Based on X-ray crystallography studies, complexes R2 and R4 have coordination environments with formulated (η-p-cymene)Ru(NCl) and (η-CH)Ru(NCl), respectively. The thermal stabilities of compounds R2 and R4 were studied by thermal gravimetric (TG) and differential scanning calorimetry (DSC).

Deposition of silver nanoparticles on polyester fiber under ultrasound irradiations.

The polyester fiber containing Ag nanoparticles was prepared through the chemical reduction under ultrasound irradiation. Influences of reduction reagents on the morphological properties of Ag nanoparticles@polyester fiber were studied. The sizes of metallic nanoparticles vary significantly with the types of reduction reagents used in the synthesis.

[Mn(III)Mn(IV)2Mo14O56](17-): A Mixed-Valence Meso-Polyoxometalate Anion Encapsulated by a 64-Nuclearity Silver Cluster.

A 64-nuclearity silver cluster encapsulating a unique POM anion [Mn(III)Mn(IV)2Mo14O56](17-) has been synthesized. The formation of the templating core performs a reassembly process for increasing nuclearities from {MnMo9} to {Mn3Mo14}. It represents a rare inorganic meso anion containing mixed-valent Mn that is built up by d-{Mn(IV)Mo7} and l-{Mn(IV)Mo7} units connecting together through a {Mn(III)} fragment.

The transformation of polyoxometalates in the formation of intercluster compound [Ag41(α-SiW(10)O37)((t)BuC≡C)27(CH3CN)3][β-SiW(12)O40].

We report a unique intercluster compound comprising a Ag41 cage encapsulating a divacant [α-SiW(10)O37](10-) anion and a complete [β-SiW(12)O40](4-) anion as a counteranion. Two electro-redox centers associated with the inner and outer POM anions show interesting electrochemical behaviours, because the stable Ag41 cage acts as an electron transfer mediator.

An organic anion template: a 24-nucleus silver cluster encapsulating a squarate dimer.

The first silver cluster encapsulating an organic anion-squarate dianion-has been synthesized. Two C4O4(2-) anions arranged in a staggered sandwich type arrangement are confined in the Ag24 cage. The incorporation of squarate anions into the silver alkynyl system leads to the red shift of absorption of the cluster in comparison to silver squarate.

Role of Anions Associated with the Formation and Properties of Silver Clusters.

Metal clusters have been very attractive due to their aesthetic structures and fascinating properties. Different from nanoparticles, each cluster of a macroscopic sample has a well-defined structure with identical composition, size, and shape. As the disadvantages of polydispersity are ruled out, informative structure-property relationships of metal clusters can be established.