Self-Assembly of Nanoparticles from Evaporating Sessile Droplets: Fresh Look into the Role of Particle/Substrate Interaction.

We studied the dependence of solid deposit shape obtained by free drying of sessile drops on particle concentration and Derjaguin-Landau-Verwey-Overbeek (DLVO) particle/substrate interaction. In contrast to previous contributions using pH as a control parameter of interactions, we investigated an unprecedentedly wide range of concentrations and particle/substrate DLVO forces by modifying the nature of the substrate and particles as well as their size and surface chemistry, whereas long-distance repulsive interactions between particles were maintained for most of the drying time. Our main result is that the different shapes of deposits obtained by modifying the particle concentration are the same in the different regimes of concentration regardless of particle/substrate interaction in the studied range of DLVO forces and particle concentrations. The second result is that, contrary to expectations, the dominant morphology of dry patterns at low particle concentration always shows a dotlike pattern for all the studied systems.

Morphological Control of Linear Particle Deposits from the Drying of Inkjet-Printed Rivulets.

We studied the morphology of linear particle deposits obtained by inkjet printing of a silica nanoparticle suspension in drying conditions where contact line depinning occurs. We show that this evaporation mode can be obtained by adjusting the particle concentration in different solvents. For isolated drops, deposited manually or by inkjet printing, drying induces the formation of two concentric rings in which particles self-assemble into a monolayer. For fused drops, our main result is that stable rivulets could be formed by drop overlap leading, after drying, to the formation of three parallel lines composed of a self-assembled particle monolayer. The three lines are of homogeneous thickness with two very thin outer lines (∼1 µm width) and a wider central line (∼20 µm width). We reveal how the width of the resulting lines is influenced by drop spacing in a predictable manner for a large experimental window knowing the drop size.

Self-Assembly of Gold Nanoparticles with Oppositely Charged, Long, Linear Chains of Periodic Copolymers.

We studied the assembly of nanoparticles (NPs) with oppositely charged linear and periodic copolymers (CPs), alternating ionic and polar sequences, in the dilute range of polymer concentration. For the first time, we considered CPs displaying a contour length much higher than the gold NP (AuNP) perimeter. We assumed that such CPs will enable the collection of a finite number of NPs into linear nanostructures with a gain of colloidal stability and a better structural control compared to electrostatic complexes obtained with homopolyelectrolytes. As a case study, we synthesized anionic AuNPs and CPs consisting of alternated cationic poly-l-lysine (PLL) blocks and polar sequences of poly(ethylene glycol) (PEG). We showed that complexation of AuNPs with CPs is quite similar to that observed with homo PLL. In that respect, finite size nanometric clusters, of less than 30 NPs, are formed outside the electroneutrality domain and a fast phase separation occurs at the electroneutrality. Nevertheless, the presence of PEG blocks allowed us to highlight some specific effects. First, the global charge of the positively charged clusters was found to be always lower for CP-based clusters than for homo PLL with a dependence of the charge with the number and the mass of the PEG blocks. Second, in spite of this effect which should have promoted the formation of a dense structure, the fractal dimension characterizing the structure of the clusters in bulk was found to be always below 1.8. Finally, we showed that PEG blocks influence the interparticle distance by disfavoring plasmon delocalization when the clusters are dispersed in water and collapse around the NPs when the clusters are deposited on the substrate.

N-Heterocyclic carbene-stabilized gold nanoparticles with tunable sizes.

A simple and straightforward synthesis of N-heterocyclic carbene (NHC)-protected gold nanoparticles is derived from (benz)imidazolium-AuX4 complexes and NaBH4 only. The proposed method allows size tuning, from 3 to 6 nm, by adding (benz)imidazolium bromide. Changing the reducing agent to tBuNH2BH3 shifts the size range to ca. 6-12 nm. A one pot protocol is also reported from AuCl, (benz)imidazolium bromides and NaBH4, thereby providing an even more straightforward way of producing NHC-capped gold nanoparticles. In addition, X-ray photoelectron spectroscopy (XPS) is used to unambiguously evidence, on the nanoparticles, the covalent bond formed between the NHC and the surface gold atoms.

A high-nuclearity metal-cyanide cluster [Mo6Cu14] with photomagnetic properties.

A high-nuclearity metal-cyanide cluster [Mo6Cu14] has been prepared and its photomagnetic properties investigated. The photoswitchable magnetic phenomenon observed is thermally reversible (T≈ 230 K). In the field of photomagnetism, [Mo6Cu14] represents a unique example of a nanocage and the highest nuclearity observed so far.

First evidence of light-induced spin transition in molybdenum(IV).

Photo-induced spin transition in a molybdenum-zinc complex has been evidenced and fully characterized by Squid magnetometry and several spectroscopies performed under irradiation (IR, EPR, etc.). The phenomenon has been confirmed by X-ray diffraction and DFT calculations yielding a Light-Induced Excited Spin State Trapping Effect (LIESST) on a 4d transition metal ion.

A new family of hetero-tri-metallic complexes [M(CuTb)]n (n = 1, 2, ∞; M = Co, Cr, Fe): synthesis, structure and tailored single-molecule magnet behavior.

A new family of hetero-tri-metallic complexes [M(CuTb)]n (M(III) = Co, Cr, Fe; n = 1, 2, ∞), composed of three series of three compounds (oligo- and poly-nuclear complexes based on [Cu-Tb] subunits), is presented and fully characterized. These nine compounds, viewed as different assemblies of single-molecule magnet (SMM) building blocks, connected to various hexacyanometalate centers, illustrate how the SMM behavior of the [CuTb] moiety can be modulated via the control of intermolecular interactions. Specifically, the combination of the "non-innocent" diamagnetic [Co(III)(CN)6](3-) center with a [Cu-Tb](3+) moiety enabled isolation of the magnetic entities, resulting in an improvement of the SMM behavior (ranging from Ueff = 5-7 cm(-1) to 15-17 cm(-1)).