Takuya Hosokai

Charged and metallic molecular monolayers through surface-induced aromatic stabilization

Large π-conjugated molecules, when in contact with a metal surface, usually retain a finite electronic gap and, in this sense, stay semiconducting. In some cases, however, the metallic character of the underlying substrate is seen to extend onto the first molecular layer. Here, we develop a chemical rationale for this intriguing phenomenon. In many reported instances, we find that the conjugation length of the organic semiconductors increases significantly through the bonding of specific substituents to the metal surface and through the concomitant rehybridization of the entire backbone structure. The molecules at the interface are thus converted into different chemical species with a strongly reduced electronic gap. This mechanism of surface-induced aromatic stabilization helps molecules to overcome competing phenomena that tend to keep the metal Fermi level between their frontier orbitals. Our findings aid in the design of stable precursors for metallic molecular monolayers, and thus enable new routes for the chemical engineering of metal surfaces.

Thermally-induced phase transition of pseudorotaxane crystals: changes in conformation and interaction of the molecules and optical properties of the crystals.

This paper presents a pseudorotaxane that acts as a thermally driven molecular switch in the single-crystal state. Crystals of the cationic pseudorotaxane consisting of dibenzo[24]crown-8 (DB24C8) and N-(xylylammonium)-methylferrocene as the cyclic and axle component molecules, respectively, undergo crystalline-phase transition at 128 °C with heating and 116 °C with cooling, according to differential-scanning-calorimetry measurements. X-ray crystallographic analyses revealed that the phase transition was accompanied by rotation of the 4-methylphenyl group of the axle component molecule and a simultaneous shift in the position of the PF(6)(-) counteranion. Crystalline phase transition changes the conformation and position of the DB24C8 molecule relative to the ammonium cation partially; the interaction between the cyclic component and the PF(6)(-) anion in the crystal changes to a greater extent. Moreover, there are changes in the vibration angle (θ) and birefringence (Δn) on the (001) face of the crystal transitionally; θ is rotated by +12°, and Δn is decreased from 0.070 to 0.059 upon heating across the phase transition temperature. The phase transition and accompanying change in the optical properties of the crystal occur reversibly and repeatedly upon heating and cooling processes. The switching rotation of the aromatic plane of the molecule induces a change in the optical anisotropy of the crystal, which is regarded as a demonstration of a new type of optical crystal. Partial replacement of the PF(6)(-) anion with the bulkier AsF(6)(-) anion forms crystals with similar crystallographic parameters. An increase in the AsF(6)(-) content decreases the reversible-phase-transition temperature gradually down to 99 °C (T(end)) and 68 °C (T(exo)) ([AsF(6)(-)]:[PF(6)(-)] = 0.4:0.6).

Structure and morphology of coevaporated pentacene-perfluoropentacene thin films.

The structural properties of coevaporated thin films of pentacene (PEN) and perfluoropentacene (PFP) on SiO(2) were studied using x-ray reflectivity and grazing incidence x-ray diffraction. Reciprocal space maps of the coevaporated thin films with different volume fractions reveal the coexistence of two different molecular mixed PEN-PFP phases together with the pure PEN and PFP crystallites. The crystal structure of PEN:PFP blends does not change continuously with volume fraction, instead the proportion of the appropriate phases changes, as seen from the diffraction analysis. Additional temperature dependent experiments reveal that the fraction of the two mixed PEN-PFP phases varies with growth temperature. The λ-phase (molecular plane parallel to the substrate) is metastable and induced by low growth temperature. The σ-phase (molecular plane nearly perpendicular to the substrate) is thermally stable and nucleates predominantly at high growth temperatures.

Orientational ordering of nonplanar phthalocyanines on Cu(111): strength and orientation of the electric dipole moment.

In order to investigate the orientational ordering of molecular dipoles and the associated electronic properties, we studied the adsorption of chlorogallium phthalocyanine molecules (GaClPc, Pc=C32N8H16(-2) on Cu(111) by using the x-ray standing wave technique, photoelectron spectroscopy, and quantum mechanical calculations. We find that for submonolayer coverages on Cu(111) the majority of GaClPc molecules adsorb in a Cl-down configuration by forming a covalent bond to the substrate. For bilayer coverages the x-ray standing wave data indicate a coexistence of the Cl-down and Cl-up configurations on the substrate. The structural details established for both cases and supplementary calculations of the adsorbate system allow us to analyze the observed change of the work function.

Exploring the bonding of large hydrocarbons on noble metals: Diindoperylene on Cu(111), Ag(111), and Au(111)

We present a benchmark study for the adsorption of a large

Simultaneous in situ measurements of x-ray reflectivity and optical spectroscopy during organic semiconductor thin film growth

\ensuremath{\pi}

Electronic density tailing outside π-conjugated polymer surface

-conjugated organic molecule on different noble metal surfaces, which is based on x-ray standing wave (XSW) measurements and density functional theory calculations with van der Waals (vdW) interactions. The bonding distances of diindenoperylene on Cu(111), Ag(111), and Au(111) surfaces (2.51, 3.01, and 3.10 \AA{}, respectively) determined with the normal-incidence XSW technique are compared with calculations. Excellent agreement with the experimental data, i.e., deviations less than 0.1 \AA{}, is achieved using the Perdew-Burke-Ernzerhof (PBE) functional with vdW interactions that include the collective response of substrate electrons (the

Evidence and mechanism of efficient thermally activated delayed fluorescence promoted by delocalized excited states

\mathrm{PBE}+{\mathrm{vdW}}^{\mathrm{surf}}

Epitaxial Growth of an Organic p–n Heterojunction: C60 on Single-Crystal Pentacene

method). It is noteworthy that the calculations show that the vdW contribution to the adsorption energy increases in the order

Post-growth surface smoothing of thin films of diindenoperylene

\text{Au}(111)l\text{Ag}(111)l\text{Cu}(111)