Ballbot-type motion of N-heterocyclic carbenes on gold surfaces.

Recently, N-heterocyclic carbenes (NHCs) were introduced as alternative anchors for surface modifications and so offered many attractive features, which might render them superior to thiol-based systems. However, little effort has been made to investigate the self-organization process of NHCs on surfaces, an important aspect for the formation of self-assembled monolayers (SAMs), which requires molecular mobility. Based on investigations with scanning tunnelling microscopy and first-principles calculations, we provide an understanding of the microscopic mechanism behind the high mobility observed for NHCs. These NHCs extract a gold atom from the surface, which leads to the formation of an NHC-gold adatom complex that displays a high surface mobility by a ballbot-type motion. Together with their high desorption barrier this enables the formation of ordered and strongly bound SAMs. In addition, this mechanism allows a complementary surface-assisted synthesis of dimeric and hitherto unknown trimeric NHC gold complexes on the surface.

Stereoselective formation of coordination polymers with 1,4-diaminonaphthalene on various Cu substrates.

Polymerization of 1,4-diaminonaphthalene on various Cu substrates resulting in stereoselectively well-defined metal-organic coordination polymers is reported. By using different crystallographic planes (111), (110) and (100) of a Cu substrate the structure of the resulting coordination polymer was controlled.

Decarboxylative polymerization of 2,6-naphthalenedicarboxylic acid at surfaces.

Metal-catalyzed polymerization of 2,6-naphthalenedicarboxylic acid (NDCA) to form poly-2,6-naphthalenes at various surfaces is reported. Polymerizations occur via initial formal dehydrogenation of self-assembled diacids with subsequent decarboxylation to give polymeric bisnaphthyl-Cu species at elevated temperature as intermediate structures (<160 °C). Further temperature increase eventually leads to poly-naphthalenes via reductive elimination. It is demonstrated that the Cu(111) surface works most efficiently to conduct such polymerizations as compared to the Au(111), Ag(111), Cu(100), and Cu(110) surfaces. Poly-2,6-naphthalene with a chain length of over 50 nm is obtained by using this approach. The decarboxylative coupling of aromatic diacids is a very promising tool which further enlarges the portfolio of reactions allowing for on-surface polymerizations and novel organometallic systems preparations.

Self-assembly properties of semiconducting donor-acceptor-donor bithienyl derivatives of tetrazine and thiadiazole-effect of the electron accepting central ring.

Scanning tunneling microscopy was used to study the effect of the electron-accepting unit and the alkyl substituent's position on the type and extent of 2D supramolecular organization of penta-ring donor-acceptor-donor (DAD) semiconductors, consisting of either tetrazine or thiadiazole central acceptor ring symmetrically attached to two bithienyl groups. Microscopic observations of monomolecular layers on HOPG of four alkyl derivatives of the studied adsorbates indicate significant differences in their 2D organizations. Ordered monolayers of thiadiazole derivatives are relatively loose and, independent of the position of alkyl substituents, characterized by large intermolecular separation of acceptor units in the adjacent molecules located in the face-to-face configuration. The 2D supramolecular architecture in both derivatives of thiadiazole is very sensitive to the alkyl substituent's position. Significantly different behavior is observed for derivatives of tetrazine (which is a stronger electron acceptor). Stronger intermolecular DA interactions in these adsorbates generate an intermolecular shift in the monolayer, which is a dominant factor determining the 2D structural organization. As a consequence of this molecular arrangement, tetrazine groups (A segments) face thiophene rings (D segments) of the neighboring molecules. Monolayers of tetrazine derivatives are therefore much more densely packed and characterized by similar π-stacking of molecules independently of the position of alkyl substituents. Moreover, a comparative study of 3D supramolecular organization, deduced from the X-ray diffraction patterns, is also presented clearly confirming the polymorphism of the studied adsorbates.

Surface-mediated thin terbium hydride film formation.

This work was performed to study the correlation between the surface and bulk phenomena that occur during H(2) interaction with terbium, leading to three-hydride TbH(x) (x approximately 3) formation. This reaction is accompanied by the transition of the original metal into a semiconductor. It was found that thin films are particularly useful for such studies. Measurements of work function changes DeltaPhi(H/Tb) were chosen to illustrate the surface phenomena, and the relative electrical resistance R(H/Tb)/R(0) and light transparency T(H/Tb)/T(0) correspond to the bulk properties. Additionally, BET experiments were performed to determine the influence of three-hydride formation on the area of a thin Tb film. It was observed at 298 K that a precursor state of the adsorbate arose at the beginning of the reaction, when (H/Tb < 0.1), decreasing the work function by DeltaPhi = 12 mV. A higher uptake of hydrogen caused an increased work function, followed by DeltaPhi transients. This has been interpreted as local hydride formation on the surface and its expansion into the bulk, until a concentration of H/Tb approximately 3 was reached. TbH(x) (x approximately 3) formation resulted in DeltaPhi = approximately 200 mV and an increase in the thin film area by a factor of approximately 3. These phenomena were accompanied by characteristic changes in the bulk properties. The light-reflecting thin Tb film was transformed into a transparent hydride, with an approximately 23-fold increase in R/R(0). At 78 K, only a small amount of hydrogen (H/Tb = 0.13) was consumed, leading to DeltaPhi = -23 mV. This uptake is stable up to 100 K. Increasing the temperature above this value resulted in the additional large absorption of hydrogen. This could suggest the formation of a low-temperature surface phase of the hydride.

Effect of molecular mass on supramolecular organisation of poly(4,4''-dioctyl-2,2':5',2''-terthiophene).

The effect of the chain length on the type and extent of the 2D supramolecular organization in poly(4,4''-dioctyl-2,2':5',2''-terthiophene) (PDOTT) monomolecular layers deposited on highly oriented pyrolytic graphite (HOPG) is studied by scanning tunneling microscopy (STM) and analyzed in terms of molecular modeling. The strictly monodispersed fractions of increasing molecular mass used in this study were obtained by chromatographic fractionation of the crude product of 4,4''-dioctyl-2,2':5',2''-terthiophene oxidative polymerization. STM investigations of PDOTT layers, deposited on HOPG from poly- and monodispersed fractions, show that polydispersity can be considered as a key factor seriously limiting supramolecular ordering. This is a consequence of significant differences in the type of supramolecular order observed for molecules of different chain length. It has been demonstrated that shorter molecules (consisting of 6 and 9 thiophene units) form well-defined two-dimensional islands, while the interactions between longer molecules (consisting of 12 and 15 thiophene units) become anisotropic. Consequently, for higher molecular mass fractions, the supramolecular organization is one-dimensional and consists of more or less separated rows of ordered macromolecules. In this case an increase of the chain length leads to amplification of the intermolecular interactions proceeding via interdigitation of the alkyl substituents of adjacent molecules. Polydispersed fractions show much less ordered organization because of the incompatibility of the supramolecular structures of molecules of different molecular masses. This finding is of crucial importance for the application of polythiophene derivatives in organic and molecular electronics since ordered supramolecular organization constitutes the condition sine qua non of good electrical transport properties.