Aurophilic Molecules on Surfaces. Part II. (NapNC)AuCl on Au(111).

Although aurophilicity is a well-known phenomenon in structural gold chemistry and is found in many crystals of Au(I) complexes, its potential for self-assembly in thin films is not yet explored. This paper is Part II of a study, in which we investigated the ultrathin film formation of chlorido(2-naphthyl isonitrile) gold(I) on gold surfaces. Here, we present the data for the growth of (NapNC)AuCl on isotropic Au(111) surfaces. Already during physical vapor deposition, the condensation of ultrathin films is monitored by photoelectron emission microscopy (PEEM) and incremental and spectrally resolved changes in the optical reflectance (DDRS). Additional structural data obtained by scanning tunneling microscopy (STM) and low-energy electron diffraction (LEED) reveal that the "crossed swords" packing motif known from the bulk is also present in thin films.

Aurophilic Molecules on Surfaces. Part I. (NapNC)AuCl on Au(110).

Aurophilicity is a well-known phenomenon in structural gold chemistry and is found in many crystals of Au(I) complexes. However, these attractive dispersion forces between and within complexes containing Au(I) moieties have not been well studied in ultrathin films. In this paper, we elucidate the interaction of chlorido(2-naphthyl isonitrile)gold(I) on and with Au(110) surfaces. Already during physical vapor deposition, the condensation of ultrathin films is monitored by photoelectron emission microscopy (PEEM) and by incremental and spectrally resolved changes in the optical reflectance (DDRS). Additional structural data obtained by STM and LEED reveal that the "crossed swords" packing motif known from the bulk is also present in thin films. The molecular arrangement changes several times during thin-film deposition.

Attenuation of Photoelectron Emission by a Single Organic Layer.

We report an in situ study of the thin-film growth of cobalt-phthalocyanine on Ag(100) surfaces using photoelectron emission microscopy (PEEM) and the Anderson method. Based on the Fowler-DuBridge theory, we were able to correlate the evolution of the mean electron yield acquired with PEEM for coverages up to two molecular layers of cobalt-phthalocyanine to the global work function changes measured with the Anderson method. For coverages above two monolayers, the transients measured with the Anderson method and those obtained with PEEM show different trends. We exploit this discrepancy to determine the inelastic mean free path of the low-energy electrons while passing through the third layer of CoPc.

Standard deviation of microscopy images used as indicator for growth stages.

Photoelectron emission microscopy (PEEM) and low energy electron microscopy (LEEM) can easily distinguish between organic molecules adsorbed in crystallites or in the wetting layers as well as the bare metal substrate due to their different electronic properties. Already before (and during) the condensation of such solid phases (2D islands or 3D crystallites), there is a dilute 2D gas phase. Such a 2D gas phase consists of molecules, which are highly mobile and diffuse across the surface. The individual molecules are too small to be resolved in PEEM/LEEM images. Here, we discuss, how image features below and above the resolution limit of a PEEM/LEEM affect the mean electron yield and its (normalized) standard deviation. We support our findings with two experimental examples: the deposition of cobalt phthalocyanine (CoPc) on Ag(100) and of perfluoro-pentacene on Ag(110). Our results demonstrate, how a spatial and temporal analysis of image series can be used to obtain information about molecular phases, which cannot be directly resolved in microscopy images.

Aggregation of Au(i)-complexes on amorphous substrates governed by aurophilicity.

In single crystals of 2-naphthylisonitrile-gold(i)-halide (halide = Cl, Br, I) complexes, AuAu distances are found to be significantly shorter than twice the van der Waals radius, indicating attractive interactions between gold atoms in adjacent molecules. In the particular case of the studied 2-naphthylisonitrile-gold(i) complexes, homodimers are the common structural motifs, in which the linearly coordinated gold exhibits a crossed swords arrangement with the Au atoms of two molecules being at the intersection point. The crossed swords motif is preserved upon physical vapour deposition of both the chlorine and bromine derivatives on amorphous substrates like glass and glassy carbon. The determined activation energies of desorption for the chlorine (0.9 eV) and the bromine (1.2 eV) derivative are comparable to that of unsubstituted naphthalene. Using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and ion scattering (RBS), we confirmed the chemical integrity of the molecules in thin films and revealed the orientation of the crossed swords dimers with respect to the substrate surface.

Quinacridone on Ag(111): Hydrogen Bonding versus Chirality.

Quinacridone (QA) has recently gained attention as an organic semiconductor with unexpectedly high performance in organic devices. The strong intermolecular connection via hydrogen bonds is expected to promote good structural order. When deposited on a substrate, another relevant factor comes into play, namely the 2D-chirality of the quinacridone molecules adsorbed on a surface. Scanning tunneling microscopy (STM) images of monolayer quinacridone on Ag(111) deposited at room temperature reveal the formation of quasi-one-dimensional rows of parallel quinacridone molecules. These rows are segmented into short stacks of a few molecules in which adjacent, flat-lying molecules of a single handedness are linked via hydrogen bonds. After annealing to a temperature of T = 550-570 K, which is close to the sublimation temperature of bulk quinacridone, the structure changes into a stacking of heterochiral quinacridone dimers with a markedly different intermolecular arrangement. Electron diffraction (LEED) and photoelectron emission microscopy (PEEM) data corroborate the STM findings. These results illustrate how the effects of hydrogen bonding and chirality can compete and give rise to very different (meta)stable structures of quinacridone on surfaces.