Frédéric Niess

Light-triggered self-construction of supramolecular organic nanowires as metallic interconnects

The construction of soft and processable organic material able to display metallic conduction properties-a large density of freely moving charges-is a major challenge for electronics. Films of doped conjugated polymers are widely used as semiconductor devices, but metallic-type transport in the bulk of such materials remains extremely rare. On the other hand, single-walled carbon nanotubes can exhibit remarkably low contact resistances with related large currents, but are intrinsically very difficult to isolate and process. Here, we describe the self-assembly of supramolecular organic nanowires between two metallic electrodes, from a solution of triarylamine derivative, under the simultaneous action of light and electric field triggers. They exhibit a combination of large conductivity values (>5 × 10(3) S m(-1)) and a low interface resistance (<2 × 10(-4) Ω m). Moreover, the resistance of nanowires in series with metal interfaces systematically decreases when the temperature is lowered to 1.5 K, revealing an intrinsic metallic behaviour.

Interconversion between a vertically oriented transition metal-complexed figure-of-eight and a horizontally disposed one.

A large ring containing two pairs of transition metal-complexing fragments with alternating bi- and tridentate chelates has been shown to behave as a bimodal figure-of-eight. When coordinated to a preferentially octahedrally coordinated Fe(II) or Cu(II) center, the height of the molecule along the coordinating axis of the tridentate ligands (vertical on the drawing) is only ∼11 Å, whereas the height of the molecule along the same vertical axis is several times as large for the complex of the tetrahedrally coordinated copper(I) center. This new type of molecular machine-prototype could be used as constitutive element in muscle-like dynamic systems.

Light-triggered self-assembly of triarylamine-based nanospheres

Tailored triarylamine units modified with terpyridine ligands were coordinated to Zn(2+) ions and characterized as discrete dimeric entities. Interestingly, when these complexes were subsequently irradiated with simple visible light in chloroform, they readily self-assembled into monodisperse spheres with a mean diameter of 160 nm.

Heteroleptic Copper(I) Pseudorotaxanes Incorporating Macrocyclic Phenanthroline Ligands of Different Sizes

A series of copper(I) pseudorotaxanes has been prepared from bis[2-(diphenylphosphino)phenyl] ether (POP) and macrocyclic phenanthroline ligands with different ring sizes (m30, m37, and m42). Variable-temperature studies carried out on the resulting [Cu(mXX)(POP)]+ (mXX = m30, m37, and m42) derivatives have revealed a dynamic conformational equilibrium due to the folding of the macrocyclic ligand. The absorption and luminescence properties of the pseudorotaxanes have been investigated in CH2Cl2. They exhibit metal-to-ligand charge-transfer emission with photoluminescence quantum yields (PLQYs) in the range 20-30%. The smallest system [Cu(m30)(POP)]+ shows minimal differences in spectral shape and position compared to its analogues, suggesting a slightly distorted coordination environment. PLQY is substantially enhanced in poly(methyl methacrylate) films (∼40-45%). The study of emission spectra and excited-state lifetimes in powder samples as a function of temperature (78-338 K) reveals thermally activated delayed fluorescence, with sizable differences in the singlet-triplet energy gap compared to the reference compound [Cu(dmp)(POP)]+ (dmp = 2,9-dimethyl-1,10-phenanthroline) and within the pseudorotaxane series. The system with the largest ring ([Cu(m42)(POP)]+) has been tested as emissive material in OLEDs and affords bright green devices with higher luminance and greater stability compared to [Cu(dmp)(POP)]+, which lacks the macrocyclic ring. This highlights the importance of structural factors in the stability of electroluminescent devices based on Cu(I) materials.