Tuning the binding mode of N-heterocyclic carbenes on metal surfaces is crucial for the development of new functional materials. To understand the impact of alkyl side groups on the formation of NHC species at the Au(111) surface, we combined scanning tunneling microscopy, X-ray photoelectron spectroscopy, and density functional theory calculations. We reveal two significantly different binding modes depending on the alkyl chain length. In the case of a short alkyl substituent, an up-standing configuration with one Au adatom is preferred, whereas the longer alkyl groups result exclusively in NHC-Au-NHC complexes lying flat on the surface. Our study highlights how well-defined structural modifications of NHCs allow for controlling the local binding motif on surfaces, which is important to design designated catalytic sites at interfaces.
The synthesis of new Pt(II) complexes bearing tailored cyclometalated C^N*N^C luminophores is reported along with their photophysical properties. The emission of the monomeric species can be blue shifted upon formal isosteric replacement of two C-H units by N atoms at the two cyclometalating rings. Their remarkable stability upon sublimation was demonstrated by means of scanning tunneling microscopy, which also revealed a defined self-assembly behavior leading to supramolecular arrays, showing a 3-fold symmetry in 2D-confined monolayers. The supramolecular organization is driven by van der Waals interactions of the side chains and does not depend on the nature of the luminophores, as also observed in the crystalline phases showing no significant Pt-Pt interactions in 3D. Conversely, the luminescence properties in glassy matrices at 77 K and in amorphous solids are indicative of intermolecular interactions with sizable intermetallic coupling, which was demonstrated by reproducing the emission spectra of dimeric species by means of (TD)DFT calculations. The tendency toward aggregation was also traceable by cyclic voltammetry, whereas thermogravimetric analyses confirmed their stability. Solution-processed and vacuum-deposited OLED devices showed a concentration-dependent electroluminescence that red shifts with increasing doping ratios. Due to the stability of the complexes, solution-processed and vacuum-deposited devices showed identical electroluminescence spectra. Besides favoring aggregation, introduction of two N atoms has a detrimental effect on the device performance, due to the prolonged excited-state lifetimes favoring triplet-triplet annihilation.
Molecular machines are a key component in the vision of molecular nanotechnology, and have the potential to transport molecular species and cargo on surfaces. The motion of such machines should be triggered remotely, ultimately allowing a large number of molecules to be propelled by a single source, with light being an attractive stimulus. Here, we report upon the photo-induced translation of molecular machines across a surface by characterizing single molecules before and after illumination. Illumination of molecules containing a motor unit results in an enhancement in the diffusion of the molecules. The effect vanishes if an incompatible photon energy is used or if the motor unit is removed from the molecule, revealing that the enhanced motion is due to the presence of the wavelength-sensitive motor in each molecule.Molecular machines with internal motors are fascinating objects that transform energy into useful motion at the nanoscale. [1][2][3][4][5][6] In nature many processes depend on molecular motors that perform specific mechanical tasks in living cells, 7 a prototypical process is the directional motion of myosin. 8 Several synthetic molecular motors have been synthesized, 2,9,10 including a molecular motor developed by Feringa and co-workers that rotates at a frequency in the MHz regime. [11][12][13][14] For ultimate control of molecular machines it is essential that the motor exhibits only one sense of rotation, resulting in unidirectional translation of the molecular machine on a surface, thus only forward and no backward motion, in contrast to random motion in all directions. 2 For synthetic molecular machines to contribute to the vision of nanotechnology by transporting molecular species and cargo on surfaces, the motion of
The structural properties and binding motif of a strongly σ‐electron‐donating N‐heterocyclic carbene have been investigated on different transition‐metal surfaces. The examined cyclic (alkyl)(amino)carbene (CAAC) was found to be mobile on surfaces, and molecular islands with short‐range order could be found at high coverage. A combination of scanning tunneling microscopy (STM), X‐ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations highlights how CAACs bind to the surface, which is of tremendous importance to gain an understanding of heterogeneous catalysts bearing CAACs as ligands.
Molecular rotors on solid surfaces are fundamental components of molecular machines. No matter whether the rotation is activated by heat, electric field or light, it is determined by the intrinsic rotational potential landscape. Therefore, tuning the potential landscape is of great importance for future applications of controlled molecular rotors. Here, using scanning tunneling microscopy (STM), we demonstrate that both tip-molecule distance and sample bias can modify the rotational potential of molecular rotors. We achieve the potential energy difference variations of ∼0.3 meV/pm and ∼18 meV/V between two configurations of a molecular rotor, a tetra- tert-butyl nickel phthalocyanine molecule on Au(111) substrate. Further analysis indicates that the mechanism of modifying the rotational potential is a combination of the van der Waals interaction and the interaction between the molecular dipole and an electric field. This work provides insight into the methods used to modify the effective rotational potential energy of molecular rotors.
A molecular rotor based on N-heterocyclic carbenes (NHCs) has been rationally designed following theoretical predictions, experimentally realized, and characterized. Utilizing the structural tunability of NHCs, a computational screening protocol was first applied to identify NHCs with asymmetric rotational potentials on a surface as a prerequisite for unidirectional molecular rotors. Suitable candidates were then synthesized and studied using scanning tunneling microscopy/spectroscopy (STM/STS), analytical theoretical models, and molecular dynamics simulations. For our best NHC rotor featuring a mesityl N substituent on one side and a chiral naphthylethyl substituent on the other, unidirectional rotation is driven by inelastic tunneling of electrons from the NHC to the STM tip. While electrons preferentially tunnel through the mesityl N substituent, the chiral naphthylethyl substituent controls the directionality. Such NHC-based surface rotors open up new possibilities for the design and construction of functionalized molecular systems with high catalytic applicability and superior stability compared with other classes of molecular rotors.
Atomically precise tailoring of interface structures is crucial for developing functional materials. We demonstrate an N‐heterocyclic carbene (NHC) based molecular tool, which modifies the structure of a gold surface with atomic accuracy by the formation of gold nanorods. After adsorption on the gold surface, individual surface atoms are pulled out by the NHCs, generating single‐atom surface defects and mobile NHC‐Au species. Atomistic calculations reveal that these molecular “ballbots” can act as assembling tools to dislocate individual surface atoms. The predicted functionality of these carbene‐based complexes is confirmed by scanning tunneling microscopy measurements. Cooperative operation of these NHC‐Au species induces a step‐wise formation of gold nanorods. Consequently, the surface is re‐structured by a zipper‐type mechanism. Our work presents a foundation to utilize molecular‐based nanotools to design surface structures.
Molecular architectures (Kagome networks, coordinated/covalent dimers and branched coordination chains) via self-assembly, Ullmann reaction and pyridine coordination of 4-[(4-bromophenyl)ethynyl]pyridine are found to be sensitive to the underlying metallic surfaces. The molecular species were characterised on the surface by low-temperature scanning tunnelling microscopy (LT-STM) at sub-molecular level.
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