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This paper reports the efficient synthesis, absorption and emission spectra, and the electrochemical properties of a series of 2,6‐disubstituted naphthalene‐1,4,5,8‐tetracarboxdiimide (NDI) tripodal molecules with thioacetate anchors for their surface investigations. Our studies showed that, in particular, the pyrrolidinyl group with its strong electron‐donating properties enhanced the fluorescence of such core‐substituted NDI chromophores and caused a significant bathochromic shift in the absorption spectrum with a correspondingly narrowed bandgap of 1.94 eV. Cyclic voltammetry showed the redox properties of NDIs to be influenced by core substituents. The strong electron‐donating character of pyrrolidine substituents results in rather high HOMO and LUMO levels of ‐5.31 and ‐3.37 eV when compared with the parental unsubstituted NDI. UHV‐STM measurements of a sub‐monolayer of the rigid tripodal NDI chromophores spray deposited on Au(111) show that these molecules mainly tend to adsorb flat in a pairwise fashion on the surface and form unordered films. However, the STML experiments also revealed a few molecular clusters, which might consist of upright oriented molecules protruding from the molecular island and show electroluminescence photon spectra with high electroluminescence yields of up to 6×10−3. These results demonstrate the promising potential of the NDI tripodal chromophores for the fabrication of molecular devices profiting from optical features of the molecular layer. [ABSTRACT FROM AUTHOR]

We present a self-assembled template that consists of tetraphenylmethane derivatives and adopts a periodic lateral arrangement on a Au(111) surface with acetyl groups sticking out of the molecular film. By using the tip of a scanning tunneling microscope, these acetyl groups can be removed in a spatially controlled way without significantly affecting the remaining molecular assembly. The chemically modified molecules can be readily distinguished from the original ones such that information can be engraved in the molecular film. Both the modified nature of an individual molecule and the order of the molecular film are shown to persist at room temperature. The mesh size of this molecular graph paper can be tuned by varying the length of the molecular spacer so that writing and reading information on the nanoscale with variable letter sizes becomes possible. [ABSTRACT FROM AUTHOR]

The efficient synthesis of tripodal platforms based on tetraphenylmethane with three acetyl-protected thiol groups in either meta or para positions relative to the central sp3 carbon for deposition on Au (111) surfaces is reported. These platforms are intended to provide a vertical arrangement of the substituent in position 4 of the perpendicular phenyl ring and an electronic coupling to the gold substrate. The self-assembly features of both derivatives are analyzed on Au (111) surfaces by low-temperature ultra-high-vacuum STM, high-resolution X-ray photoelectron spectroscopy, near-edge X-ray absorption fine structure spectroscopy, and reductive voltammetric desorption studies. These experiments indicated that the meta derivative forms a well-ordered monolayer, with most of the anchoring groups bound to the surface, whereas the para derivative forms a multilayer film with physically adsorbed adlayers on the chemisorbed para monolayer. Single-molecule conductance values for both tripodal platforms are obtained through an STM break junction experiment. [ABSTRACT FROM AUTHOR]

Magneto-electric coupling offers a new pathway to information storage in magnetic memory devices. This phenomenon has been observed in various materials ranging from insulators to semiconductors. In bulk metallic systems, magneto-electric coupling has been disregarded as the electric field cannot enter bulk metals. In this work, we show that a substantial magneto-electric coupling exists in metallic Fe nano-islands grown on Cu(111). Using the electric field in the tunnel junction of a scanning tunneling microscope, the magnetic order parameter and the crystal structure of Fe was changed on the nanometer scale. This allows high density nonvolatile information storage by means of magneto-electric coupling in a simple metallic system. [ABSTRACT FROM AUTHOR]

The growth of spin-crossover Fe(1,10-phenanthroline)2(NCS)2 molecules on Cu(100) surfaces in the coverage range from 0.1 to 1.8 molecular layers was studied using a scanning tunneling microscope (STM) operated in ultrahigh vacuum at low temperature (~4 K). STM imaging allowed us to extract the molecular adsorption geometry. While the first-layer molecules point their NCS groups toward the surface and their phenanthroline groups upwards, the adsorption geometry is reversed for the molecules in the second layer. For submonolayer coverages, a coexistence of molecules in the high- and low-spin states was found that is not correlated with the coverage. This coexistence is reduced for second-layer molecules, leading to a dominant spin state at low temperatures. Differential conductance spectra acquired at negative bias voltage on first- and second-layer molecules suggest that second-layer molecules are in the high-spin state and are partially electronically decoupled from the substrate. Furthermore, increasing the tip-to-sample voltage reduces the distance between the two lobes of the molecule. The current dependence of this effect suggests that a smooth spin crossover from a high- to a low-spin state occurs with increasing sample voltage. This analog spin-state switching is well described within a simple transition-state model involving modifications to the energy barriers between low- and high-spin states due to a tip-induced electric field through the Stark effect. [ABSTRACT FROM AUTHOR]