Chemical Insights into the Formation of Colloidal Iridium Nanoparticles from In Situ X-ray Total Scattering: Influence of Precursors and Cations on the Reaction Pathway.

Iridium nanoparticles are important catalysts for several chemical and energy conversion reactions. Studies of iridium nanoparticles have also been a key for the development of kinetic models of nanomaterial formation. However, compared to other metals such as gold or platinum, knowledge on the nature of prenucleation species and structural insights into the resultant nanoparticles are missing, especially for nanoparticles obtained from IrxCly precursors investigated here. We use in situ X-ray total scattering (TS) experiments with pair distribution function (PDF) analysis to study a simple, surfactant-free synthesis of colloidal iridium nanoparticles. The reaction is performed in methanol at 50 °C with only a base and an iridium salt as precursor. From different precursor salts─IrCl3, IrCl4, H2IrCl6, or Na2IrCl6─colloidal nanoparticles as small as Ir∼55 are obtained as the final product. The nanoparticles do not show the bulk iridium face-centered cubic (fcc) structure but show decahedral and icosahedral structures. The formation route is highly dependent on the precursor salt used. Using IrCl3 or IrCl4, metallic iridium nanoparticles form rapidly from IrxClyn- complexes, whereas using H2IrCl6 or Na2IrCl6, the iridium nanoparticle formation follows a sudden growth after an induction period and the brief appearance of a crystalline phase. With H2IrCl6, the formation of different Irn (n = 55, 55, 85, and 116) nanoparticles depends on the nature of the cation in the base (LiOH, NaOH, KOH, or CsOH, respectively) and larger particles are obtained with larger cations. As the particles grow, the nanoparticle structure changes from partly icosahedral to decahedral. The results show that the synthesis of iridium nanoparticles from IrxCly is a valuable iridium nanoparticle model system, which can provide new compositional and structural insights into iridium nanoparticle formation and growth.

Surfactant-free syntheses and pair distribution function analysis of osmium nanoparticles.

A surfactant-free synthesis of precious metal nanoparticles (NPs) performed in alkaline low-boiling-point solvents has been recently reported. Monoalcohols are here investigated as solvents and reducing agents to obtain colloidal Os nanoparticles by using low-temperature (<100 °C) surfactant-free syntheses. The effect of the precursor (OsCl3 or H2OsCl6), precursor concentration (up to 100 mM), solvent (methanol or ethanol), presence or absence of a base (NaOH), and addition of water (0 to 100 vol %) on the resulting nanomaterials is discussed. It is found that no base is required to obtain Os nanoparticles as opposed to the case of Pt or Ir NPs. The robustness of the synthesis for a precursor concentration up to 100 mM allows for the performance of X-ray total scattering with pair distribution function (PDF) analysis, which shows that 1-2 nm hexagonal close packed (hcp) NPs are formed from chain-like [OsO x Cl y ] complexes.

Simple Setup Miniaturization with Multiple Benefits for Green Chemistry in Nanoparticle Synthesis.

The development of nanomaterials often relies on wet-chemical synthesis performed in reflux setups using round-bottom flasks. Here, an alternative approach to synthesize nanomaterials is presented that uses glass tubes designed for NMR analysis as reactors. This approach uses less solvent and energy, generates less waste, provides safer conditions, is less prone to contamination, and is compatible with high-throughput screening. The benefits of this approach are illustrated by an in breadth study with the synthesis of gold, iridium, osmium, and copper sulfide nanoparticles.

Hydrothermal synthesis and structural characterization of ammonium ion-templated lanthanide(III) carboxylate-phosphonates.

Using N-(phosphonomethyl) iminodiacetic acid (H4PMIDA), as a complexing agent, two new complexes, (NH4)La(PMIDA)(H2O)•H2O, 1 and (NH4)Yb(PMIDA), 2 have been synthesized hydrothermally. In both compounds, the metal ions are trapped by a three five-membered chelate rings by the chelating PMIDA anions giving a tricapped trigonal prismatic LaO8N and monocapped trigonal prismatic YbO6N geometries for 1 and 2, respectively. The structure of 1 consists of La(PMIDA)(H2O) chelating units, linked together by the phosphonate oxygen atoms O1 and O3 to form a chain along the c-axis. The chains are then connected together by the bridging phosphonate oxygen O2 to form a 2D layered structure with alternating 4- and 8-membered apertures. The structure of 2 consists Yb(PMIDA) chelating units, which are connected by alternating bridging carboxylate and phosphonate groups along the [010] direction forming chains with a corrugated pattern. The third phosphonate oxygen bridges the chains together along the [001] direction to build the two-dimensional layer with 4- and 6-membered apertures in the bc-plane. Under excitation of 330 nm, compound 2 shows a broad emission band at λmax = 460 nm. This emission is essentially in the blue luminescent region, which corresponds to ligand centered fluorescence.

Transport, phase reactions, and hysteresis of iron fluoride and oxyfluoride conversion electrode materials for lithium batteries.

Potentiostatic intermittent titration technique (PITT) was applied to FeF2, FeF3, and FeO0.67F1.33 to gain insight into the transport-related aspects of the conversion reaction by quantitative analysis of Li(+) diffusion and hysteresis. PITT derived diffusion coefficient measurements were benchmarked relative to values extracted by electrochemical impedance spectroscopy (EIS). A reverse-step PITT methodology was used to evaluate true hysteresis by eliminating nucleation induced overpotentials. This method evaluates the minimum potential hysteresis and allowed an accurate representation of the potential required to move conversion reactions forward at C/1000 rates in both lithiation and delithiation. The high resolution PITT data were also used to gain further insight into reaction mechanisms involved in the reversible conversion reactions. Physical evidence, based on pair distribution function (PDF) structural analysis, and electrochemical evidence are presented regarding a new step in the reaction during the rutile FeF2 reconversion reaction.

Homo- and heterometallic luminescent 2-D stilbene metal-organic frameworks.

Metal-organic frameworks (MOFs) can provide a matrix for the assembly of organic chromophores into well-defined geometries, allowing for tuning of the material properties and study of structure-property relationships. Here, we report on the effect of the coordinated metal ion on the luminescence properties of eight isostructural MOFs having the formula M(1)2M(2)L3(DMF)2 (M(1) = M(2) = Zn (1), Cd (2), Mn (3), Co (4); M(1) = Zn, M(2) = Cd (5), Mn (6), Co (7); M(1) = Co, M(2) = Mn (8); L = trans-4,4'-stilbene dicarboxylate), synthesized by reaction of the appropriate metal nitrate or mixtures of metal nitrates with LH2 in DMF. The crystal structures of 2, 3 and 5-8 were determined by X-ray diffraction to be composed of trinuclear metal clusters linked by stilbene dicarboxylate linkers in a paddlewheel geometry, extending to form a 2-D layered structure. In the mixed-metal cases, the larger metal ion was found to occupy the octahedral site in the cluster while the smaller ion occupies the tetrahedral positions, suggesting a selective, ligand-directed assembly process for the mixed-metal species. Variable temperature magnetic measurements for paramagnetic MOFs 3 and 6-8 were consistent with the site occupancies determined crystallographically, and indicated weak intra-cluster antiferromagnetic coupling for 3 and 8. Comparison between the crystal structures of 2, 3 and 5-8 and those reported for 1 and 4 in the literature reveal close resemblances between linker environments, with important intermolecular stilbene-stilbene geometries that are comparable in all cases. Interestingly, pale-colored 1-3 and 5-7 display very similar emission profiles upon excitation at λ(ex) = 350 nm, whereas dark-colored 4 and 8 do not exhibit detectable emission spectra. The bright, well-resolved luminescence of 1, 2 and 5 is ascribed to rigidification of the linker upon coordination to the d(10) metal ions, whereas the weaker emission observed for 3, 6 and 7 is presumably a result of quenching due to close proximity of the linker to one or more paramagnetic ions. Time-resolved measurements for 1, 2, 5 and 6 reveal biexponential emission decays, where the lifetime of the longer-lived state corresponds to observed variations in the nearest-neighbor cofacial stilbene-stilbene distances in their crystal structures. For 3, a monoexponential decay with shorter lifetime was determined, indicating significant paramagnetic quenching of its emissive state.

Supramolecular synthesis based on piperidone derivatives and pharmaceutically acceptable co-formers.

The target complexes, bis{(E,E)-3,5-bis[4-(diethylamino)benzylidene]-4-oxopiperidinium} butanedioate, 2C27H36N3O(+)·C4H4O4(2-), (II), and bis{(E,E)-3,5-bis[4-(diethylamino)benzylidene]-4-oxopiperidinium} decanedioate, 2C27H36N3O(+)·C10H16O4(2-), (III), were obtained by solvent-mediated crystallization of the active pharmaceutical ingredient (API) (E,E)-3,5-bis[4-(diethylamino)benzylidene]-4-piperidone and pharmaceutically acceptable dicarboxylic (succinic and sebacic) acids from ethanol solution. They have been characterized by melting point, IR spectroscopy and single-crystal X-ray diffraction. For the sake of comparison, the structure of the starting API, (E,E)-3,5-bis[4-(diethylamino)benzylidene]-4-piperidone methanol monosolvate, C27H35N3O·CH4O, (I), has also been studied. Compounds (II) and (III) represent salts containing H-shaped centrosymmetric hydrogen-bonded synthons, which are built from two parallel piperidinium cations and a bridging dicarboxylate dianion. In both (II) and (III), the dicarboxylate dianion resides on an inversion centre. The two cations and dianion within the H-shaped synthon are linked by two strong intermolecular N(+)-H···(-)OOC hydrogen bonds. The crystal structure of (II) includes two crystallographically independent formula units, A and B. The cation geometries of units A and B are different. The main N-C6H4-C=C-C(=O)-C=C-C6H4-N backbone of cation A has a C-shaped conformation, while that of cation B adopts an S-shaped conformation. The same main backbone of the cation in (III) is practically planar. In the crystal structures of both (II) and (III), intermolecular N(+)-H···O=C hydrogen bonds between different H-shaped synthons further consolidate the crystal packing, forming columns in the [100] and [101] directions, respectively. Salts (II) and (III) possess increased aqueous solubility compared with the original API and thus enhance the bioavailability of the API.

Linear chain aluminium(III) carboxymethylphosphonate with encapsulated ammonium ions.

An aluminium carboxymethylphosphonate of composition (NH(4))(2)Al(H(1/2)O(3)PCH(2)CO(2))(2) has been prepared hydrothermally. The aluminium cation is chelated by six membered rings formed from bonding by both the carboxylate and phosphonate oxygens. These chelate rings in turn form larger eight membered rings by connecting to similar chelate groups to form chains running along the a-axis.

Anticancer properties of an important drug lead podophyllotoxin can be efficiently mimicked by diverse heterocyclic scaffolds accessible via one-step synthesis.

Structural simplification of an antimitotic natural product podophyllotoxin with mimetic heterocyclic scaffolds constructed using multicomponent reactions led to the identification of compounds exhibiting low nanomolar antiproliferative and apoptosis-inducing properties. The most potent compounds were found in the dihydropyridopyrazole, dihydropyridonaphthalene, dihydropyridoindole, and dihydropyridopyrimidine scaffold series. Biochemical mechanistic studies performed with dihydropyridopyrazole compounds showed that these heterocycles inhibit in vitro tubulin polymerization and disrupt the formation of mitotic spindles in dividing cells at low nanomolar concentrations, in a manner similar to podophyllotoxin itself. Separation of a racemic dihydropyridonaphthalene into individual enantiomers demonstrated that only the optical antipode matching the absolute configuration of podophyllotoxin possessed potent anticancer activity. Computer modeling, performed using the podophyllotoxin binding site on ß-tubulin, provided a theoretical understanding of these successful experimental findings.

Electronic properties of the 2,6-diiododithieno[3,2-b:2',3'-d]thiophene molecule and crystal: a joint experimental and theoretical study.

The electronic properties of the 2,6-diiododithieno[3,2-b:2',3'-d] thiophene molecule and crystal are investigated by means of UV-vis spectroscopy, cyclic voltammetry, X-ray crystallography, and density functional theory. The experimental and calculated properties of the compound are compared to those exhibited by the parent molecule, dithieno[3,2-b:2',3'-d]thiophene. Quantum-chemical studies of the 2,6-diiododithieno[3,2-b:2',3'-d]thiophene crystal suggest uniaxial hole-transport character with an effective mass of about 2m(0), comparable to that in the pentacene single crystal.

From small structural modifications to adjustment of structurally dependent properties: 1-methyl-3,5-bis[(E)-2-thienylidene]-4-piperidone and 3,5-bis[(E)-5-bromo-2-thienylidene]-1-methyl-4-piperidone.

The molecules of the title compounds, C(16)H(15)NOS(2), (I), and C(16)H(13)Br(2)NOS(2), (II), are E,E-isomers and consist of an extensive conjugated system, which determines their molecular geometries. Compound (I) crystallizes in the monoclinic space group P2(1)/c. It has one thiophene ring disordered over two positions, with a minor component contribution of 0.100 (3). Compound (II) crystallizes in the noncentrosymmetric orthorhombic space group Pca2(1) with two independent molecules in the unit cell. These molecules are related by a noncrystallographic pseudo-inversion center and possess very similar geometries. The crystal packings of (I) and (II) have a topologically common structural motif, viz. stacks along the b axis, in which the molecules are bound by weak C-H...O hydrogen bonds. The noncentrosymmetric packing of (II) is governed by attractive intermolecular Br...Br and Br...N interactions, which are also responsible for the very high density of (II) (1.861 Mg m(-3)).

Dipolar Second-Order Nonlinear Optical Chromophores Containing Ferrocene, Octamethylferrocene, and Ruthenocene Donors and Strong π-Acceptors: Crystal Structures and Comparison of π-Donor Strengths.

Crystal structures have been determined for six dipolar polyene chromophores with metallocenyl - ferrocenyl (Fc), octamethylferrocenyl (Fc″), or ruthenocenyl (Rc) - donors and strong heterocyclic acceptors based on 1,3-diethyl-2-thiobarbituric acid or 3-dicyanomethylidene-2,3-dihydrobenzothiophene-1,1-dioxide. In each case, crystals were found to belong to centrosymmetric space groups. For one example, polymer-induced heteronucleation revealed the existence of two additional polymorphs, which were inactive in second-harmonic generation, suggesting that they were also centrosymmetric. The bond-length alternations between the formally double and single bonds of the polyene bridges are reduced compared to simple polyenes, indicating significant contribution from charge-separated resonance structures, although the metallocenes are not significantly distorted towards the [(η(6)-fulvene)(η(5)-cyclopentadienyl)metal(II)](+) extreme. DFT geometries are in excellent agreement with those determined crystallographically; while the π-donor strengths of the three metallocenyl groups are insufficiently different to result in detectable differences in the crystallographic bond-length alternations, the DFT geometries, as well as DFT-calculations of partial charges for atoms, suggest that π-donor strength decreases in the order Fc″ ≫ Fc > Rc. NMR, IR and electrochemical evidence also suggests that octamethylferrocenyl is the stronger π-donor, exhibiting similar π-donor strength to a p-(dialkylamino)phenyl group, while ferrocenyl and ruthenocenyl show very similar π-donor strengths to one another in chromophores of this type.

A novel helical double-layered cobalt(II)-organic framework with tetranuclear [Co4(mu3-OH)2] clusters linked by an unsymmetrical pyridylbenzoate ligand.

A novel cobalt(II)-organic framework, [Co2(OH)(3,4-PBC)3]n (I), has been acquired by the reaction of CoO with an unsymmetrical pyridylbenzoate ligand, 3-pyrid-4-ylbenzoic acid (3,4-PBC). Single-crystal X-ray diffraction studies reveal that it is comprised of [CoII4(mu3-OH)2] clusters linked by the unsymmetrical ligand 3,4-PBC, forming a novel helical double-layered metal-organic architecture. A significant overall antiferromagnetic behavior has been observed for this compound.

Isolation and crystal structures of two singlet bis(triarylamine) dications with nonquinoidal geometries.

We report the first structural data for bis(diarylamine) "bipolarons": we have isolated and crystallographically characterized salts of the dications obtained by two-electron oxidation of E-4,4'-bis[di(p-anisyl)amino]stilbene and E,E-2,5-bis{4-[di(p-anisyl)amino]styryl}-3,4-di(n-butoxy)thiophene, [1](2+) and [2](2+) respectively. ESR, NMR, and magnetometry suggest both species have singlet ground states. X-ray structures, together with (1)H NMR coupling constants for [2](2+), indicate geometries in which the bond lengths are shifted toward a quinoidal pattern relative to that in the neutral species, but not to a fully quinoidal extent. In particular, the bond-length alternations across the vinylene bridging groups approach zero. DFT calculations with closed-shell singlet configurations reproduce the observed structures well. Our results indicate that singlet species for which one might expect quinoidal geometries (with differences of ca. 0.1 A between formally single and double bonds) on the basis of a limiting valence-bond representation of the structure can, in fact, show structures with significantly different patterns of bond lengths.

A mixed-valence bis(diarylamino)stilbene: crystal structure and comparison of electronic coupling with biphenyl and tolane analogues.

The E-4,4'-bis[di(p-anisyl)amino]stilbene cation is a class-III mixed-valence species with electronic coupling comparable to that in its biphenyl-bridged analogue, whereas its tolane-bridged analogue belongs to class II.