Tetraphenyl porphyrin substituted deoxyuridine was used as a building block to create discrete multiporphyrin arrays via site specific incorporation into DNA. The successful covalent attachment of up to 11 tetraphenyl porphyrins in a row onto DNA shows that there is virtually no limitation in the amount of substituents, and the porphyrin arrays thus obtained reach the nanometer scale (approximately 10 nm). The porphyrin substituents are located in the major groove of the dsDNA and destabilize the duplex by deltaT(m) 5-7 degrees C per porphyrin modification. Force-field structure minimization shows that the porphyrins are either in-line with the groove in isolated modifications or aligned parallel to the nucleobases in adjacent modifications. The CD signals of the porphyrins are dominated by a negative peak arising from the intrinsic properties of the building block. In the single strands, the porphyrins induce stabilization of a secondary helical structure which is confined to the porphyrin modified part. This arrangement can be reproduced by force-field minimization and reveals an elongated helical arrangement compared to the double helix of the porphyrin-DNA. This secondary structure is disrupted above approximately 55 degrees C (T(p)) which is shown by various melting experiments. Both absorption and emission spectroscopy disclose electronic interactions between the porphyrin units upon stacking along the outer rim of the DNA leading to a broadening of the absorbance and a quenching of the emission. The single-stranded and double-stranded form show different spectroscopic properties due to the different arrangement of the porphyrins. Above T(p) the electronic properties (absorption and emission) of the porphyrins change compared to room temperature measurements due to the disruption of the porphyrin stacking at high temperature. The covalent attachment of porphyrins to DNA is therefore a suitable way of creating helical stacks of porphyrins on the nanometer scale.

The self‐assembly properties of two ZnII porphyrin isomers on Cu(111) are studied at different coverage by means of scanning tunneling microscopy (STM). Both isomers are substituted in their meso‐positions by two voluminous 3,5‐di(tert‐butyl)phenyl and two rod‐like 4′‐cyanobiphenyl groups, respectively. In the trans‐isomer, the two 4′‐cyanobiphenyl groups are opposite to each other, whereas they are located at right angle in the cis‐isomer. For coverage up to one monolayer, the cis‐substituted porphyrins self‐assemble to form oligomeric macrocycles held together by antiparallel CN⋅⋅⋅CN dipolar interactions and CN⋅⋅⋅H‐C(sp2) hydrogen bonding. Cyclic trimers and tetramers occur most frequently but everything from cyclic dimers to hexamers can be observed. Upon annealing of the samples at temperatures >150 °C, dimeric macrocyclic structures are observed, in which the two porphyrins are bridged by Cu atoms, originating from the surface, under formation of two CN⋅⋅⋅Cu⋅⋅⋅NC coordination bonds. The trans‐isomer builds up linear chains on Cu(111) at low coverage, whereas for higher coverage the molecules assemble in a periodic, densely packed structure. Both cis‐ and trans‐bis(4′‐cyanobiphenyl)‐substituted ZnII porphyrins behave very differently on Cu(111) compared to similar porphyrins in literature on less reactive surfaces such as Au(111) and Ag(111). On the latter surfaces, there is no signal visible between molecular orientation and the crystal directions of the substrate, whereas on Cu(111), very strong adsorbate–substrate interactions have a dominating influence on all observed structures. This strong porphyrin–substrate interaction enables a much broader variety of structures, including also less favorable intermolecular bonding motifs and geometries.

Ordered nanostructures of meso‐(4‐cyanophenyl)‐substituted Zn(II) porphyrin molecules are formed along step edges and specific directions of KBr(001). Short and long molecular wires, ringlike structures, and oriented multiwires (see image) are observed by high‐resolution noncontact atomic force microscopy on insulating surfaces. Intermolecular distances of 0.5–0.6 nm indicate π–π stacking of the porphyrin rings, which is comparable to natural light‐harvesting structures.

Directed molecular repositioning is a key step toward the build up of molecular machines. To artificially generate and control the motion of molecules on a surface, excitations by light, chemical, or electrical energy have been demonstrated. Here, the application of local mechanical forces is implemented to achieve directed rotations of molecules. Three-dimensional force spectroscopy with sub-Ångström precision is used to characterize porphyrin derivatives with peripheral carbonitrile groups. Extremely small areas on these molecules (≈ 100 × 100 pm(2)) are revealed which can be used to control rotations. In response to the local mechanical forces, the molecular structure elastically deforms and then changes its conformation, which leads to its rotation. Depending on the selection of one of four submolecular areas, the molecule is either rotated clockwise or counterclockwise.

No abstract

SummaryThe growth of molecular assemblies at room temperature on insulating surfaces is one of the main goals in the field of molecular electronics. Recently, the directed growth of porphyrin-based molecular wires on KBr(001) was presented. The molecule–surface interaction associated with a strong dipole moment of the molecules was sufficient to bind them to the surface; while a stabilization of the molecular assemblies was reached due to the intermolecular interaction by π–π binding. Here, we show that the atomic structure of the substrate can control the direction of the wires and consequently, complex molecular assemblies can be formed. The electronic decoupling of the molecules by one or two monolayers of KBr from the Cu(111) substrate is found to be insufficient to enable comparable growth conditions to bulk ionic materials.

Tip-induced deformations of meso-(4-cyanophenyl)-substituted Zn(II) porphyrin molecular wires self-assembled on KBr(001) were studied by frequency modulation dynamic force microscopy. Since the wires are weakly bonded to the KBr substrate and to the neighboring molecules, they can easily be cut by the scanning tip. We found that the damaged molecular wires self-healed at room temperature.

The authors grew self-ordered meso-(4-cyanophenyl)-substituted Zn(II) porphyrin molecular wires on thin epitaxial NaCl(001) layers on top of the GaAs substrates under ultrahigh vacuum (UHV) conditions. Molecules assembled to one- and two-dimensional wires with a length of several 10 nm, depending on the substrate conditions. In addition, using the nanostencil tool, a shadow-masking technique in UHV, they evaporated Au and Cr electrodes having lateral dimensions in the 100 nm regime. The resulting combined molecular and metal structures were investigated in situ by means of noncontact atomic force microscopy (NC-AFM) and Kelvin probe force microscopy (KPFM). While NC-AFM enabled control of the tip-sample distance on the very complex and partly insulating surface, KPFM was used to determine and compensate changes in the local contact potential difference.