The Electron-Rich and Nucleophilic N-Heterocyclic Imines on Metal Surfaces: Binding Modes and Interfacial Charge Transfer.

The strongly electron-donating N-heterocyclic imines (NHIs) have been employed as excellent surface anchors for the thermodynamic stabilization of electron-deficient species due to their enhanced nucleophilicity. However, the binding mode and interfacial property of these new ligands are still unclear, representing a bottleneck for advanced applications in surface functionalization and catalysis. Here, NHIs with different side groups have been rationally designed, synthesized, and analyzed on various metal surfaces (Cu, Ag). Our results reveal different binding modes depending on the molecular structure and metal surface. The molecular design enables us to achieve a flat-lying or upright configuration and even a transition between these two binding modes depending on the coverage and time. Importantly, the two binding modes exhibit different degrees of interfacial charge transfer between the molecule and the surface. This study provides essential microscopic insight into the NHI adsorption geometry and interfacial charge transfer for the optimization of heterogeneous catalysts in coordination chemistry.

An Alkyne-Bridged Covalent Organic Framework Featuring Interactive Pockets for Bromine Capture.

The high degree of corrosivity and reactivity of bromine, which is released from various sources, poses a serious threat to the environment. Moreover, its coexistence with iodine forming an equilibrium compound, iodine monobromide (IBr) necessitates the selective capture of bromine from halogen mixtures. The electrophilicity of halogens to π-electron rich structures enabled us to strategically design a covalent organic framework for halogen capture, featuring a defined pore environment with localized sorption sites. The higher capture capacity of bromine (4.6 g g-1) over iodine by ~41 % shows its potential in selective capture. Spectroscopic results uncovering the preferential interaction sites are supported by theoretical investigations. The alkyne bridge is a core functionality promoting the selectivity in capture by synergistic physisorption, rationalized by the higher orbital overlap of bromine due to its smaller atomic size as well as reversible chemical interactions. The slip stacking in the structure has further promoted this phenomenon by creating clusters of molecular interaction sites with bromine intercalated between the layers. The inclusion of unsaturated moieties, i.e. triple bonds and the complementary pore geometry offer a promising design strategy for the construction of porous materials for halogen capture.

Modus Operandi of a Pedalo-Type Molecular Switch: Insight from Dynamics and Theoretical Spectroscopy.

Molecular switches which can be triggered by light to interconvert between two or more well-defined conformation differing in their chemical or physical properties are fundamental for the development of materials with on-demand functionalities. Recently, a novel molecular switch based on a the azodicarboxamide core has been reported. It exhibits a volume-conserving conformational change upon excitation, making it a promising candidate for embedding in confined environments. In order to rationally implement and efficiently utilize the azodicarboxamide molecular switch, detailed insight into the coordinates governing the excited-state dynamics is needed. Here, we report a detailed comparative picture of the molecular motion at the atomic level in the presence and absence of explicit solvent. Our hybrid quantum mechanics/molecular mechanics (QM/MM) excited state simulations reveal that, although the energy landscape is slightly modulated by the solvation, the light-induced motion is dominated by a bending-assisted pedalo-type motion independent of the solvation. To support the predicted mechanism, we simulate time-resolved IR spectroscopy from first principles, thereby resolving fingerprints of the light-induced switching process. Our calculated time-resolved data are in good agreement with previously reported measured spectra.

Mechanical and Chemical Interactions in Atomically Defined Contacts.

Providing fundamental insights in atomic interactions, dedicated methods in atomic force microscopy allow measuring the threshold forces needed to move single adsorbed atoms or molecules. However, the chemical and structural properties of the probe-tip can drastically influence the results. Establishing atomically defined contacts in such experiments, the tips in the present study are functionalized with various chemically and structurally different terminations. Xenon atoms are moved along an atomically defined metal/metal-oxide boundary where all tips show a pulling mechanism and slight force variations, which are assigned to polarization effects within the tip-sample junction. Detaching Xe atoms from the boundary involves a significantly higher energy barrier where chemical reactive Cu-tips cause Xe pickup before any lateral manipulation. Passivating the tip by inert probe particles (Xe or CO) allows further approaching the surface Xe atom. Yet, the small vertical attraction and pronounced tip relaxations prevent reaching sufficient threshold forces inducing manipulation. In contrast, the high structural rigidity of oxygen-terminated Cu-tips allows manipulations even beyond the threshold where they evolve from initial pulling, via sliding to pushing mode. The detailed quantitative analysis of the processes in the atomically defined junctions emphasizes the mechanical and chemical interactions for highly controlled experiments with piconewton sensitivity.

Understanding the Molecular Origin of the Collective Movement in a Diarylethene-based Photo-Responsive Actuator.

Remotely controlling macroscopic movement is one of the key elements to realize intelligent materials for applications ranging from sensing to robotics. Over the last few years, a number of photomechanical materials based on diarylethene derivatives have been developed. However, a detailed picture of the structural evolution within these soft actuators is often missing. In this work, an atomistic investigation uncovers how the photo-induced molecular dynamics propagates to large-scale motion and results in macroscopic deformation of the crystal. By correlating the intramolecular rearrangement within the photo-responsive switching unit with the intermolecular packing, the molecular mechanism for the photomechanical phenomena is deciphered, which is fundamental for a rational development of photo-responsive actuators.

Collective structural properties of embedded molecular motors in functionalized metal-organic frameworks.

Photo-responsive molecular motors incorporated in soft porous materials enable the amplification of the motion of individual motor units by employing their collective and cooperative behavior. Metal-organic frameworks (MOFs) provide in this regard, due to their structural diversity and modular assembly, a unique matrix to construct well-defined and systematically tunable molecular environments for the embedding of molecular motors. However, despite advances in the development of such photo-responsive functional materials, a thorough understanding of the governing interactions at the atomic scale has been missing so far, limiting the possibility of predicting and fully exploring the potential of these assembled machineries. Here, we present a conformational study to unravel the collective structural behavior and elucidate the impact of motor-motor interactions on the local and global properties of the scaffold. In particular, our work highlights the impact of full conversion of the embedded molecular motors on the overall network topology of the MotorMOF and thus acts as a benchmark for future studies to further explore the correlation of responsive building units with the resulting functionality of these hierarchical systems.

A Unidirectional Surface-Anchored N-Heterocyclic Carbene Rotor.

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.

Cocrystallization Tailoring Multiple Radiative Decay Pathways for Amplified Spontaneous Emission.

Amplified spontaneous emission (ASE) is intrinsically associated with lasing applications. Inefficient photon energy transfer to ASE is a long-standing issue for organic semiconductors that consist of multiple competing radiative decay pathways, far from being rationally regulated from the perspective of molecular arrangements. Herein, we achieve controllable molecular packing motifs by halogen-bonded cocrystallization, leading to ten times increased radiative decay rate, four times larger ASE radiative decay selectivity and thus remarkable ASE threshold decrease from 223 to 22 µJ cm-2 , albeit with a low photoluminescence quantum yield. We have made an in-depth investigation on the relationship among molecular arrangements, vibration modes, radiative decay profiles and ASE properties. The results suggest that cocrystallization presents a powerful approach to tailor the radiative decay pathways, which is fundamentally important to the development of organic ASE and lasing materials.

Azo bond formation on metal surfaces.

The formation of azo compounds via redox cross-coupling of nitroarenes and arylamines, challenging in solution phase chemistry, is achieved by on-surface chemistry. Reaction products are analyzed with a cryogenic scanning tunneling microscope (STM) and X-ray photoelectron spectroscopy (XPS). By using well-designed precursors containing both an amino and a nitro functionality, azo polymers are prepared on surface via highly efficient nitro-amino cross-coupling. Experiments conducted on other substrates and surface orientations reveal that the metal surface has a significant effect on the reaction efficiency. The reaction was further found to proceed from partially oxidized/reduced precursors in dimerization reactions, shedding light on the mechanism that was studied by DFT calculations.

Atomistic Insight Into the Host-Guest Interaction of a Photoresponsive Metal-Organic Framework.

Photoresponsive functional materials have gained increasing attention due to their externally tunable properties. Molecular switches embedded in these materials enable the control of phenomena at the atomic level by light. Metal-organic frameworks (MOFs) provide a versatile platform to immobilize these photoresponsive units within defined molecular environments to optimize the intended functionality. For the application of these photoresponsive MOFs (pho-MOFs), it is crucial to understand the influence of the switching state on the host-guest interaction. Therefore, we present a detailed insight into the impact of molecular switching on the intermolecular interactions. By performing atomistic simulations, we revealed that due to different interactions of the guest molecules with the two isomeric states of an azobenzene-functionalized MOF, both the adsorption sites and the orientation of the molecules within the pores are modulated. By shedding light on the host-guest interaction, our study highlights the unique potential of pho-MOFs to tailor molecular interaction by light.

Cooperation of N-Heterocyclic Carbenes on a Gold Surface.

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.

Long-Range Chirality Recognition of a Polar Molecule on Au(111).

Chiral molecular self-assemblies were usually achieved using short-range intermolecular interactions, such as hydrogen-, metal-organic, and covalent bonding. However, unavoidable surface defects, such as step edges, surface reconstructions, or site dislocations may limit the applicability of short-range chirality recognition. Long-range chirality recognition on surfaces would be an appealing but challenging strategy for chiral reservation across surface defects at long distances. Now, long-range chirality recognition is presented between neighboring 3-bromo-naphthalen-2-ol (BNOL) stripes on an inert Au(111) surface across the herringbone reconstruction as investigated by STM and DFT calculations. The key to achieving such recognition is the herringbone reconstruction-induced local dipole accumulation at the edges of the BNOL stripes. The neighboring stripes are then forced to adopt the same chirality to create the opposite edged dipoles and neutralize the neighbored dipole moments.

An Electron-Rich Cyclic (Alkyl)(Amino)Carbene on Au(111), Ag(111), and Cu(111) Surfaces.

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.

Diamantane Suspended Single Copper Atoms.

Single chains of metal atoms are expected to be perfect one-dimensional nanowires in nanotechnology, due to their quantum nature including tunable electronic or spin coupling strengths. However, it is still rather difficult to fabricate such nanowires with metallic atoms under directional and separation control. Here, we succeeded in building higher-order single diamondoid-chains from the lower-order chains using a chemically well-controlled approach that employs diamondoids on metal surfaces. This approach results in higher-order diamondoid double chains by linking two neighboring single chains, and ultimately forms a central chain consisting of single Cu atoms suspended by the diamantane framework. The suspended Cu atoms are placed above the metal surface with a periodic distance of 0.67 ± 0.01 nm. Our bottom-up approach will allow detailed experimental investigations of the properties of these exciting suspended metal atoms (for example, quantized conductance, spin coupling, as well as transfer, etc.). Furthermore, we also identified different spatial configurations on the metal surfaces in on-surface reaction processes using high-resolution AFM imaging and density functional theory computations. Our findings broaden the on-surface synthesis concept from 2D planar aromatic molecules to 3D bulky aliphatic molecules.

Light on the Structural Evolution of Photoresponsive Molecular Switches in Electronically Excited States.

Stimuli-responsive materials are attracting extensive interest as they offer the opportunity to transform external inputs such as light into a functionality by control at the molecular level. As a result, a large number of molecular building units have been developed that enable switching between two or more states. Since the trajectory describing the transition between the various states defines the efficiency of the usually immobilized unit and the resulting functionality, it does not suffice to merely consider the initial and final states of the switching process. A key challenge is in fact to decipher at the atomic scale the actual motion that takes place after photoexcitation. Understanding and being able to manipulate this trajectory is crucial for an efficient implementation of photoactive molecular switches into functional materials, as well as to rationally develop novel tailor-made materials. In this Concept article, we highlight the potential to characterize in detail photoinitiated switching mechanisms by combining quantum chemical calculations with advanced laser spectroscopic techniques that probe the vibrational manifold of electronically excited states and its evolution.

Site-Specific Adsorption of Aromatic Molecules on a Metal/Metal Oxide Phase Boundary.

Nanostructured surfaces are ideal templates to control the self-assembly of molecular structures toward well-defined functional materials. To understand the initial adsorption process, we have investigated the arrangement and configuration of aromatic hydrocarbon molecules on nanostructured substrates composed of an alternating arrangement of Cu(110) and oxygen-reconstructed stripes. Scanning tunneling microscopy reveals a preferential adsorption of molecules at oxide phase boundaries. Noncontact atomic force microscopy experiments provide a detailed insight into the preferred adsorption site. By combining submolecular resolution imaging with density functional theory calculations, the interaction of the molecule with the phase boundary was elucidated excluding a classical hydrogen bonding. Instead, a complex balance of different interactions is revealed. Our results provide an atomistic picture for the driving forces of the adsorption process. This comprehensive understanding enables developing strategies for the bottom-up growth of functional molecular systems using nanotemplates.

Understanding the Mechanocatalytic Conversion of Biomass: A Low-Energy One-Step Reaction Mechanism by Applying Mechanical Force.

On the way to establishing biomass as a renewable and environmentally friendly source to cover the ever-increasing global demand on energy and chemicals, one great challenge is the efficient depolymerization of cellulose. Enhanced conversion rates have been discovered in ball-milling experiments, thus opening a mechanocatalytic approach. However, an understanding of the impact of mechanical forces on the acid-catalyzed cleavage of glycosidic bonds at the molecular level is still missing. Herein, we contribute such fundamental insight based on atomistic modeling. Mechanically stressing the macromolecular backbone radically changes the depolymerization pathway from a complex high-barrier reaction upon thermal activation to a low-energy single-step mechanocatalytic process. In addition to revealing a regioselective increase in basicity under a mechanical force, our results provide molecular-level explanations of the experimental findings and might therefore guide rational ways to improve such mechanocatalytic processes.

Elucidating the Binding Modes of N-Heterocyclic Carbenes on a Gold Surface.

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.

Glass formation of a DMSO-water mixture probed with a photosynthetic pigment.

Despite their extensive industrial usage, glass-forming liquids are not fully understood, and methods to investigate their dynamical heterogeneity are sought after. Here we show how the appearance of a second component in the visible absorption spectrum of a photosynthetic pigment upon cooling can be used to probe the glass transition of a dimethylsulfoxide-water mixture. The changes in the relative ratio of the two components with respect to temperature follow a sigmoid curve, and we show that the second component arises due to protonation of the pigment at low temperatures. Furthermore, from visible transient absorption spectra we show that, unlike the first component, the dynamics of the second component slows down significantly at lower temperatures, suggesting that there are two distinct environments with fast and slow fluctuations. Our results therefore enable a new method to characterize the dynamical heterogeneity of glass-forming liquids.

Photoinduced Pedalo-Type Motion in an Azodicarboxamide-Based Molecular Switch.

Well-defined structural changes of molecular units that can be triggered by light are crucial for the development of photoactive functional materials. Herein, we report on a novel switch that has azodicarboxamide as its photo-triggerable element. Time-resolved UV-pump/IR probe spectroscopy in combination with quantum-chemical calculations shows that the azodicarboxamide functionality, in contrast to other azo-based chromophores, does not undergo trans-cis photoisomerization. Instead, a photoinduced pedalo-type motion occurs, which because of its volume-conserving properties enables the design of functional molecular systems with controllable motion in a confined space.