Unveiling the Potential of Redox Chemistry to Form Size-Tunable, High-Index Silicon Particles.

Silicon particles of intermediate sizes (75-200 nm) scatter visible wavelengths, making them promising candidates for optical devices. The solution synthesis of silicon particles in this size range, however, has proved challenging for chemists over the past few decades. Here, a solution-phase synthesis provides a pathway toward reaching size tunability between 45 and 230 nm via changing the reactant ratio in the reaction between a silicon Zintl phase (NaSi) with an amidinate-stabilized Si(IV) coordination complex.

Structure-Function Relationship of Iron Oxide Nanoflowers: Optimal Sizes for Magnetic Hyperthermia Depending on Alternating Magnetic Field Conditions.

Iron oxide nanoflowers (IONFs) that display singular magnetic properties can be synthesized through a polyol route first introduced almost 2 decades ago by Caruntu et al., presenting a multi-core morphology in which several grains (around 10 nm) are attached together and sintered. These outstanding properties are of great interest for magnetic field hyperthermia, which is considered as a promising therapy against cancer.

Size-tunable silicon nanoparticles synthesized in solution a redox reaction.

A current challenge in silicon chemistry is to perform liquid-phase synthesis of silicon nanoparticles, which would permit the use of colloidal synthesis techniques to control size and shape. Herein we show how silicon nanoparticles were synthesized at ambient temperature and pressure in organic solvents through a redox reaction. Specifically, a hexacoordinated silicon complex, bis(,'-diisopropylbutylamidinato)dichlorosilane, was reduced by a silicon Zintl phase, sodium silicide (NaSi).

Induced circular dichroism from helicoidal nano substrates to porphyrins: the role of chiral self-assembly.

Because the combination of chiral and magnetic properties is becoming more and more attractive for magneto-chiral phenomena, we here aim at exploring the induction of chirality to achiral magnetic molecules as a strategy for the preparation of magneto-chiral objects. To this end, we have associated free base- and metallo-porphyrins with silica nano helices, using a variety of elaboration methods, and have studied them mainly by electronic natural circular dichroism (NCD) and magnetic circular dichroism (MCD) spectroscopies. While electrostatic or covalent surface grafting uniformly yielded very low induced CD (ICD) for the four assayed porphyrins, a moderate response was observed when the porphyrins were incorporated into the interior of the double-walled helices, likely due to the association of the molecules with the chirally-organized gemini surfactant.

Magnetic Ordering in Ultrasmall Potassium Ferrite Nanoparticles Grown on Graphene Nanoflakes.

Magnetic nanoparticles are central to the development of efficient hyperthermia treatments, magnetic drug carriers, and multimodal contrast agents. While the magnetic properties of small crystalline iron oxide nanoparticles are well understood, the superparamagnetic size limit constitutes a significant barrier for further size reduction. Iron (oxy)hydroxide phases, albeit very common in the natural world, are far less studied, generally due to their poor crystallinity.

Chirality determination in crystals.

This tutorial review article discusses chirality determination in the solid state, both in single crystals and in crystal assemblies, with an emphasis on X-ray diffraction. The main principles of using X-ray diffraction to reliably determine absolute structure are summarized, and the complexity which can be encountered in chiral structures-kryptoracemates, scalemates, and inversion twinning-is illustrated with examples from our laboratories and the literature. We then address the problem of the bulk crystallization and discuss different techniques to determine chirality in a large assembly of crystal structures, with a special prominence given to an X-ray natural circular dichroism mapping technique that we recently reported.

Rapid Discrimination of Crystal Handedness by X-ray Natural Circular Dichroism (XNCD) Mapping.

An original method for determining the handedness of individual non-centrosymmetric crystals in a mixture using a tightly-focused, circularly polarized X-ray beam is presented. The X-ray natural circular dichroism (XNCD) spectra recorded at the metal K-edge on selected crystals of [Δ-M(en) ](NO ) and [Λ-M(en) ](NO ) (M=Co , Ni ) show extrema at the metal pre-edge (7712 eV for Co, 8335 eV for Ni). A mapping of a collection of some 220 crystals was performed at the respective energies by using left and right circular polarizations.

Space Charge-Limited Current Transport Mechanism in Crossbar Junction Embedding Molecular Spin Crossovers.

Spin crossover complexes are among the most studied classes of molecular switches and have attracted considerable attention for their potential technological use as active units in multifunctional devices. A fundamental step toward their practical implementation is the integration in macroscopic devices adopting hybrid vertical architectures. First, the physical properties of technological interest shown by these materials in the bulk phase have to be retained once they are deposited on a solid surface.

Resolution, structures, and vibrational circular dichroism of helicoidal trinickel and tricobalt paddlewheel complexes.

It has been recently shown that enantiomers of the helicoidal paddlewheel complex [Co (dpa) (CH CN) ] (dpa = the anion of 2,2'-dipyridylamine) can be resolved using the chiral [As (tartrate) ] anion (AsT) and that these complexes demonstrate a strong chiroptical response in the ultraviolet-visible and X-ray energy regions. Here we report that the nickel congener, [Ni (dpa) (CH CN) ] , can likewise be resolved using AsT. Depending on the stereochemistry of the enantiopure AsT anion, one or the other of the trinickel enantiomers crystallize from CH CN and diethyl ether in space group P42 2 as the (NBu ) [Ni (dpa) (CH CN) ](AsT) ·[solvent] salt.

Synchrotron-based Mössbauer spectroscopy characterization of sublimated spin crossover molecules.

The spin crossover (SCO) efficiency of [Fe(bpz)(phen)] (where bpz = bis(pyrazol-1-yl)borohydride and phen = 9,10-phenantroline) molecules deposited on gold substrates was investigated by means of synchrotron Mössbauer spectroscopy. The spin transition was driven thermally, or light induced via the LIESST (light induced excited spin-state trapping) effect. Both sets of measurements show that, once deposited on a gold substrate, the efficiency of the SCO mechanism is modified with respect to molecules in the bulk phase.

Study of the Photoswitching of a Fe(II) Chiral Complex through Linear and Nonlinear Ultrafast Spectroscopy.

Photoswitching the physical properties of molecular systems opens large possibilities for driving materials far from equilibrium toward new states. Moreover, ultrashort pulses of light make it possible to induce and to record photoswitching on a very short time scale, opening the way to fascinating new functionalities. Among molecular materials, Fe(II) complexes exhibit an ultrafast spin-state transition during which the spin state of the complex switches from a low spin state (LS, = 0) to a high spin state (HS, = 2).

Enantiopure Chiral Coordination Polymers Based on Polynuclear Paddlewheel Helices and Arsenyl Tartrate.

Herein, we report the preparation of chiral, one-dimensional coordination polymers based on trinuclear paddlewheel helices [M₃(dpa)₄] (M = Co(II) and Ni(II); dpa = the anion of 2,2'-dipyridylamine). Enantiomeric resolution of a racemic mixture of [M₃(dpa)₄] complexes was achieved by chiral recognition of the respective enantiomer by [Δ-As₂(tartrate)₂] or [Λ-As₂(tartrate)₂] in ,-dimethylformamide (DMF), affording crystalline coordination polymers formed from [(Δ-Co₃(dpa)₄)(Λ-As₂(tartrate)₂)]·3DMF (Δ-), [(Λ-Co₃(dpa)₄)(Δ-As₂(tartrate)₂)]·3DMF (Λ-), [(Δ-Ni₃(dpa)₄)(Λ-As₂(tartrate)₂)]·(4 - )DMF∙Et₂O (Δ-) or [(Λ-Ni₃(dpa)₄)(Δ-As₂(tartrate)₂)]·(4 - )DMF∙Et₂O (Λ-) repeating units. UV-visible circular dichroism spectra of the complexes in DMF solutions demonstrate the efficient isolation of optically active species.

Effect of solvent on silicon nanoparticle formation and size: a mechanistic study.

Silicon has emerged as the most desirable material for optical dielectric metamaterials, however chemists struggle to obtain the required silicon nanoparticle dimensions. Here the average diameter of silicon nanoparticles is varied between 3 and 15 nm by changing the reaction solvent. Electrochemistry and NMR elucidate the role of solvent on the synthetic mechanism.

Pressure-Induced Spin-Crossover Features at Variable Temperature Revealed by In Situ Synchrotron Powder X-ray Diffraction.

An accurate high-pressure X-ray diffraction investigation, at various temperatures, on a powder of a spin-crossover (SCO) complex has allowed the rare deconvolution of the structural features of the high-spin and low-spin phases. As a result, the pressure dependence of the structural parameters of the high-spin and low-spin phases can be discussed independently in the pressure domain where both phases co-exist within the powder. Consequently, crucial unprecedented information is given, such as the variation of bulk moduli with temperature, similar here in amplitude for both spin phases, the temperature-dependence of the pressure-induced SCO abruptness, the temperature dependence of the pressure at which SCO occurs, and arguments for a possible piezo-hysteresis.

Design and Study of Structural Linear and Nonlinear Optical Properties of Chiral [Fe(phen)] Complexes.

The dependence of nonlinear optical properties upon the spin state in molecular switches is still an unexplored area. Chiral [Fe( phen)] complexes are excellent candidates for those studies because they are expected to show nonlinear optical properties of interest and at the same time show photoconversion to a short-lived metastable high-Spin state by ultrafast optical pumping. Herein, we present the synthesis, crystallographic, and spectroscopic comparison of chiral [Fe( phen)] complexes obtained with chiral anions, a new lipophilic derivative of the D-symmetric (As(tartrate)), and D-symmetric tris(catechol)phosphate(V) (TRISCAT), tris(catechol)arsenate(V) (TRISCAS), and 3,4,5,6-tetrachlorocatechol phosphate(V) (TRISPHAT).

Enantiomeric resolution and X-ray optical activity of a tricobalt extended metal atom chain.

A simple procedure based on anion exchange was employed for the enantiomeric resolution of the extended metal atom chain (EMAC) [Co(dpa)(MeCN)]. Use of the chiral salt (NBu)[As(tartrate)], (Λ- or Δ-), resulted in the selective crystallization of the EMAC enantiomers as [Δ-Co(dpa)(MeCN)](NBu)[Λ-As(tartarte)], (Δ-) and [Λ-Co(dpa)(MeCN)](NBu)[Δ-As(tartrate)] (Λ-), respectively, in the 422 space group, whereas a racemic mixture of yielded [Co(dpa)(MeCN)][As(tartrate)]·2MeCN (-), which crystallized in the 2/ space group. The local electronic and magnetic structure of the EMAC enantiomers was studied, exploiting a variety of dichroisms in single crystals.

Locking and Unlocking the Molecular Spin Crossover Transition.

The Fe(II) spin crossover complex [Fe{H B(pz) } (bipy)] (pz = pyrazol-1-yl, bipy = 2,2'-bipyridine) can be locked in a largely low-spin-state configuration over a temperature range that includes temperatures well above the thermal spin crossover temperature of 160 K. This locking of the spin state is achieved for nanometer thin films of this complex in two distinct ways: through substrate interactions with dielectric substrates such as SiO and Al O , or in powder samples by mixing with the strongly dipolar zwitterionic p-benzoquinonemonoimine C H (-⋯ NH ) (-⋯ O) . Remarkably, it is found in both cases that incident X-ray fluences then restore the [Fe{H B(pz) } (bipy)] moiety to an electronic state characteristic of the high spin state at temperatures of 200 K to above room temperature; that is, well above the spin crossover transition temperature for the pristine powder, and well above the temperatures characteristic of light- or X-ray-induced excited-spin-state trapping.

A fascinating multifaceted redox-active chelating ligand: introducing the ,'-dimethyl-3,3'-biquinoxalinium "methylbiquinoxen" platform.

To intimately combine a chelating ligand function with the numerous properties of a viologen-like redox-active centre would offer a rare possibility to design controllable multi-redox states, whose properties arise from strongly correlated phenomena between the organic ligand as well as with any metalloid coordinated centres. Such a concept previously proved to be feasible, however is not widely applicable owing to challenges in terms of synthesis, isolation, and aerial sensitivity of both the ligand and its metal complexes. Here we report the first stable example of such a redox-active molecule, ,'-dimethyl-3,3'-biquinoxalinium˙ "methylbiquinoxen, MBqn˙", which shows a rich redox chemistry and chelates a metal ion in the case of the metal complex [CdCl(MBqn)].

Zwitterionic Cobalt Complexes with Bis(diphenylphosphino)(N-thioether)amine Assembling Ligands: Structural, EPR, Magnetic, and Computational Studies.

The coordination of two heterofunctional P,P,S ligands of the N-functionalized DPPA-type bearing an alkylthioether or arylthioether N-substituent, (Ph2P)2N(CH2)3SMe (1) and (Ph2P)2N(p-C6H4)SMe (2), respectively, toward cobalt dichloride was investigated to examine the influence of the linker between the PNP nitrogen and the S atoms. The complexes [CoCl2(1)]2 (3) and [CoCl2(2)]2 (4) have been isolated, and 3 was shown by X-ray diffraction to be a unique dinuclear, zwitterion containing one CoCl moiety bis-chelated by two ligands 1 and one CoCl3 fragment coordinated by the S atom of a thioether function. The FT-IR, UV-vis, and EPR spectroscopic features of 3 were analyzed as the superposition of those of constitutive fragments identified by a retrosynthetic-type analysis.

Synthesis, Structures, and Single-Molecule Magnet Behaviour of High-Nuclearity Nickel(II) Dicubane-Type Complexes with Pyridyl-Alcohol Ligands.

The condensation reaction between two chemically different tetranuclear cubane-like clusters [Ni(μ -Cl)(Cl)(HL)] (1; HL=2-methyl-1-(pyridin-2-yl)propan-2-ol) and [Ni(μ -OH)(Cl)(HL)] (2) provides new access to higher nuclearity complexes, as shown with the synthesis of the octanuclear complex [Ni (μ -Cl) (μ -OH) (μ-Cl) Cl (HL) ] (3). In one instance, we also isolated the heptanuclear complex [Ni (μ -Cl) (μ -OH) Cl (H O) (HL) ]Cl (4). Magnetic properties measured by superconducting quantum interference device (SQUID) susceptometry evidenced S=8 and S=5 ground states for complexes 3 and 4, respectively.

Unsymmetrical Chelation of N-Thioether-Functionalized Bis(diphenylphosphino)amine-Type Ligands and Substituent Effects on the Nuclearity of Iron(II) Complexes: Structures, Magnetism, and Bonding.

Starting from the short-bite ligands N-thioether-functionalized bis(diphenylphosphino)amine-type (Ph2P)2N(CH2)3SMe (1) and (Ph2P)2N(p-C6H4)SMe (2), the Fe(II) complexes [FeCl2(1)]n (3), [FeCl2(2)]2 (4), [Fe(OAc)(1)2]PF6 (5), and [Fe(OAc)(2)2]PF6 (6) were synthesized and characterized by Fourier transform IR, mass spectrometry, elemental analysis, and also by X-ray diffraction for 3, 4, and 6. Complex 3 is a coordination polymer in which 1 acts as a P,P-pseudochelate and a (P,P),S-bridge, whereas 4 has a chlorido-bridged dinuclear structure in which 2 acts only as a P,P-pseudochelate. Since these complexes were obtained under strictly similar synthetic and crystallization conditions, these unexpected differences were ascribed to the different spacer between the nitrogen atom and the −SMe group.

The spin state of a molecular adsorbate driven by the ferroelectric substrate polarization.

The spin state of [Fe(H2B(pz)2)2(bipy)] thin films is mediated by changes in the electric field at the interface of organic ferroelectric polyvinylidene fluoride with trifluoroethylene (PVDF-TrFE). Signatures of the molecular crossover transition are evident in changes in the unoccupied states and the related shift from diamagnetic to paramagnetic characteristics. This may point the way to the molecular magneto-electric effect on devices.