Self-assembled Molecular Network Research Articles

Adsorption of Prochiral Solvent Molecules by Surface-Confined Chiral Supramolecular Assemblies: How Solvent Impacts on-Surface Chirality.

The understanding of supramolecular chirality in self-assembled molecular networks (SAMNs) on surfaces generates a lot of interest because of its relation to the production of chiral sensors, reactors, and catalysts. We herein report the adsorption of a prochiral solvent molecule in porous SAMNs formed by a chiral dehydrobenzo[12]annulene (cDBA) derivative. Through the prochirality recognition of a solvent molecule, the supramolecular chirality of the SAMN is switched: the cDBA exclusively forms a counter-clockwise pore through co-adsorption of the solvent molecule in prochiral 1,2,4-trichlorobenzene, while in 1-phenyloctane it produces the opposite chiral, clockwise pore. The prochirality recognition of the solvent molecule in the chiral SAMN pores is attributed to the adaptable conformational changes of the chiral chains of the cDBA molecule.

Tuning Preferential Molecular Adsorption and Self-Assembled Molecular Network Formation at the Liquid–Solid Interface: The Impact of Annealing and Confinement

Tuning Preferential Molecular Adsorption and Self-Assembled Molecular Network Formation at the Liquid–Solid Interface: The Impact of Annealing and Confinement

Chiral Solvent-Induced Homochiral Hierarchical Molecular Assemblies at the Liquid/Solid Interface.

We herein investigate the formation of homochiral hierarchical self-assembled molecular networks (SAMNs) via chirality induction by the coadsorption of a chiral solvent at the liquid/graphite interface by means of scanning tunneling microscopy (STM). In a mixture of achiral solvents, 1-hexanoic acid, and 1,2,4-trichlorobenzene, an achiral dehydrobenzo[12]annulene (DBA) derivative with three alkoxy and three hydroxy groups in an alternating manner forms chiral hierarchical triangular cluster structures through dynamic self-sorting. Enantiomorphous domains appear in equal probability. On the other hand, in chiral 2-methyl-1-hexanoic acid as a solvent, this molecule produces (i) homochiral small triangular clusters at a low solute concentration, (ii) a chirality-biased hierarchical structure consisting of triangular cluster structures with different cluster sizes at a medium concentration, and (iii) a dense structure with no chirality bias at a high concentration. We attribute the concentration-dependent degree of the chirality transmission to the number of coadsorbed solvent molecules in the SAMNs and to the difference in nucleus structure and size in the initial stage of the SAMN formation.

Deciphering the factors influencing electric field mediated polymerization and depolymerization at the solution–solid interface

Strong and oriented electric fields are known to influence structure as well as reactivity. The strong electric field (EF) between the tip of a scanning tunneling microscope (STM) and graphite has been used to modulate two-dimensional (2D) polymerization of aryl boronic acids where switching the polarity of the substrate bias enabled reversible transition between self-assembled molecular networks of monomers and crystalline 2D polymer (2DP) domains. Here, we untangle the different factors influencing the EF-mediated (de)polymerization of a boroxine-based 2DP on graphite. The influence of the solvent was systematically studied by varying the nature from polar protic to polar aprotic to non-polar. The effect of monomer concentration was also investigated in detail with a special focus on the time-dependence of the transition. Our experimental observations indicate that while the nucleation of 2DP domains is not initiated by the applied electric field, their depolymerization and subsequent desorption, are a consequence of the change in the polarity of the substrate bias within the area scanned by the STM tip. We conclude that the reversible transition is intimately linked to the bias-induced adsorption and desorption of the monomers, which, in turn, could drive changes in the local concentration of the monomers.

Chiral Phase Behavior of Self-Assembled Molecular Networks Formed by an Adaptable Isosceles Triangle Molecule at the Liquid/Solid Interface: Effect of Molecular Symmetry Reduction

Chiral Phase Behavior of Self-Assembled Molecular Networks Formed by an Adaptable Isosceles Triangle Molecule at the Liquid/Solid Interface: Effect of Molecular Symmetry Reduction

Highly Ordered Co-Assembly of Bisurea Functionalized Molecular Switches at the Solid-Liquid Interface.

Immobilization of stimulus-responsive systems on solid surfaces is beneficial for controlled signal transmission and adaptive behavior while allowing the characterization of the functional interface with high sensitivity and high spatial resolution. Positioning of the stimuli-responsive units with nanometer-scale precision across the adaptive surface remains one of the bottlenecks in the extraction of cooperative function. Nanoscale organization, cooperativity, and amplification remain key challenges in bridging the molecular and the macroscopic worlds. Here we report on the design, synthesis, and scanning tunneling microscopy (STM) characterization of overcrowded alkene photoswitches merged in self-assembled networks physisorbed at the solid-liquid interface. A detailed anchoring strategy that ensures appropriate orientation of the switches with respect to the solid surface through the use of bis-urea groups is presented. We implement a co-assembly strategy that enables the merging of the photoswitches within physisorbed monolayers of structurally similar 'spacer' molecules. The self-assembly of the individual components and the co-assemblies was examined in detail using (sub)molecular resolution STM which confirms the robust immobilization and controlled orientation of the photoswitches within the spacer monolayers. The experimental STM data is supported by detailed molecular mechanics (MM) simulations. Different designs of the switches and the spacers were investigated which allowed us to formulate guidelines that enable the precise organization of the photoswitches in crystalline physisorbed self-assembled molecular networks.

Self-assembled molecular network with waterwheel-like architecture: experimental and theoretical evaluation toward electron transport capabilities for optoelectronic devices.

In recent times, self-assembled electron transport materials for optoelectronic devices, both solar cells and organic light-emitting diodes (OLEDs), have been gaining much interest as they help in fabricating high-efficiency devices. However, designing organic small molecular materials with star-shaped self-assembled networks is a challenge. To achieve this sort of target, we chose triazine and benzene-1,3,5-tricarbonyl cores for developing such architecture, and we developed four molecular systems, vizTCpCN, TCmCN, TmCN, and TpCN. Successful isolation of single crystals followed by structural analysis of TmCN revealed interesting molecular arrangements in the solid state resulting in the formation of a waterwheel type architecture with an extended network bearing characteristic voids. Theoretical calculations was carried out to check their electron transportability. The natural transition orbital calculation helped in understanding the locally excited and charge transfer excited states. The low electron reorganization energies of these molecules indicated that these materials may have potential to be used in electron transport layers of optoelectronic devices, particularly in OLEDs. Moreover, the assembled networks have a relatively wide surface area and linked structures, which are advantageous for the conduction of carriers with poor electron recombination inside the ETL, and these may offer a straightforward channel for electron conduction to the emissive layer. Finally, the fabricated electron-only device indicated that the synthesized materials may be used as ETMs in the electron transport layer of optoelectronic devices.

Chiral induction in substrate-supported self-assembled molecular networks under nanoconfinement conditions.

Self-assembly on surfaces often produces chiral networks, even when starting from achiral building blocks. However, when achiral molecules are used to produce chiral networks, two possible enantiomorphs are created with equal probability, rendering therefore the overall surface achiral. This outcome can be changed by finding a way to promote the preferential formation of one of the two enantiomorphs. In this regard, the creation of nanoconfined space, which has been called molecular corral, having a chosen orientation with respect to the substrate symmetry has been demonstrated to be a valid way to obtain the preferential self-assembly of a network having a determined chirality. In this study we aim to further expand the understanding of the principles of such mechanism, in particular by looking at unexplored parameters that could have a role in the production of the observed bias. In this way a deeper comprehension of the mechanisms at the base of the chiral self-assembly could be obtained.

On the origin of cooperativity effects in the formation of self-assembled molecular networks at the liquid/solid interface.

In this work we investigate the behaviour of molecules at the nanoscale using scanning tunnelling microscopy in order to explore the origin of the cooperativity in the formation of self-assembled molecular networks (SAMNs) at the liquid/solid interface. By studying concentration dependence of alkoxylated dimethylbenzene, a molecular analogue to 5-alkoxylated isophthalic derivatives, but without hydrogen bonding moieties, we show that the cooperativity effect can be experimentally evaluated even for low-interacting systems and that the cooperativity in SAMN formation is its fundamental trait. We conclude that cooperativity must be a local effect and use the nearest-neighbor Ising model to reproduce the coverage vs. concentration curves. The Ising model offers a direct link between statistical thermodynamics and experimental parameters, making it a valuable tool for assessing the thermodynamics of SAMN formation.

Investigation of the temperature effect on the formation of a two-dimensional self-assembled network at the liquid/solid interface.

In this work, we investigate the temperature effect on the formation of self-assembled molecular networks (SAMNs) at the liquid/solid interface, focusing on an alkylated achiral glycine derivative at the 1-phenyloctane/HOPG interface. Using STM with an in situ heating stage, we comprehensively examine the concentration-temperature phase space for 2D network formation. This study allows us to determine the enthalpic and entropic contributions to the Gibbs free energy (ΔG) of monolayer formation, revealing that the process is enthalpically driven. Moreover, we further develop our previously established Ising code by incorporating temperature dependence, which provides valuable insights into the interplay of enthalpic and entropic factors. Our findings, supported by both experimental and theoretical analyses, demonstrate a strong agreement in thermodynamic parameters, validating our model as a proof of concept for studying temperature effects in SAMN formation. This research underscores the importance of understanding enthalpic and entropic contributions for the successful utilization of 2D molecular self-assembly.

Direct C-H Arylation of Dithiophene-Tetrathiafulvalene: Tuneable Electronic Properties and 2D Self-Assembled Molecular Networks at the Solid/Liquid Interface.

Invited for the cover of this issue is the group of Manuel Souto and co-workers at the University of Aveiro and CICECO-Aveiro Institute of Materials. The image depicts the direct C-H arylation of dithiophene-tetrathiafulvalene (DT-TTF) and the self-assembly of DT-TTF-tetrabenzoic acid studied by using scanning tunnelling microscopy. Read the full text of the article at 10.1002/chem.202300572.

Direct C-H Arylation of Dithiophene-Tetrathiafulvalene: Tuneable Electronic Properties and 2D Self-Assembled Molecular Networks at the Solid/Liquid Interface.

Tetrathiafulvalene is among the best known building blocks in molecular electronics due to its outstanding electron-donating and redox properties. Among its derivatives, dithiophene-tetrathiafulvalene (DT-TTF) has attracted considerable interest in organic electronics, owing to its high field-effect mobility. Herein, we report the direct C-H arylation of DT-TTF to synthesise mono- and tetraarylated derivatives functionalised with electron-withdrawing and electron-donating groups in order to evaluate their influence on the electronic properties by cyclic voltammetry, UV-vis spectroscopy and theoretical calculations. Self-assembly of the DT-TTF-tetrabenzoic acid derivative was studied by using scanning tunnelling microscopy (STM) which revealed the formation of ordered, densely packed 2D hydrogen-bonded networks at the graphite/liquid interface. The tetrabenzoic acid derivative can attain a planar geometry on the graphite surface due to van der Waals interactions with the surface and H-bonding with neighbouring molecules. This study demonstrates a simple method for the synthesis of arylated DT-TTF derivatives towards the design and construction of novel π-extended electroactive frameworks.

Molecular Alignment and Chiral Bias under Dynamic Nanoconfinement Conditions: The Impact of Molecular Symmetry

When molecules assemble in self-assembled molecular networks on highly oriented pyrolytic graphite, typically six orientational domains are formed, which can be grouped into two sets of three, each set characteristic of a packing chirality. Under dynamic nanoconfinement conditions, where the scanning tunneling microscopy (STM)-based lithography process gradually increases the area available for molecule adsorption and self-assembly, the orientational domain equivalence is often disrupted. Additionally, this phenomenon can sometimes be accompanied by the selective formation of one of the two enantiomorphic packings. Until now, the preferential orientation of domains, sometimes accompanied by the favored formation of enantiomorphic packing patterns, has been investigated for anisotropic molecules with a single alkyl chain. We reasoned that a system where different alkyl chains may adsorb along various directions on the substrate, while also adopting different orientations concerning the line-wise movement of the STM tip, can potentially hinder molecular alignment in the nanocorrals and eventually limit the extent of enantiomorph-selective adsorption. To address this hypothesis, in this study, we investigate the self-assembly of an achiral molecule with four alkyl chains, in pairs directed along two different directions, under dynamic nanoconfinement conditions. Despite of this increased molecular structural complexity, dynamic nanoconfinement conditions lead to a clear bias in the formation of rotational domains, as well as partial chiral selection, although in a complex fashion. The factors that contribute to this bias are discussed. This highlights the significance of utilizing dynamic nanoconfinement conditions to control domain orientation and to disturb chirality equivalence, even for intricate systems.

Spatially Controlled Aryl Radical Grafting of Graphite Surfaces Guided by Self-Assembled Molecular Networks of Linear Alkane Derivatives: The Importance of Conformational Dynamics.

The covalent functionalization of carbon surfaces with nanometer-scale precision is of interest because of its potential in a range of applications. We herein report the controlled grafting of graphite surfaces using electrochemically generated aryl radicals templated by self-assembled molecular networks (SAMNs) of bisalkylurea derivatives. A bisalkylurea derivative having two butoxy units acts as a template for the covalent functionalization of aryl groups in between self-assembled rows of this molecule. In contrast, grafting occurs without a spatial order when an SAMN of bis(tetradecyl)urea was used as a template. This indicates that a degree of dynamics at the alkyl termini is required to favor controlled covalent attachment, a situation that is suppressed by strong intrarow intermolecular interactions resulting from the hydrogen bonding of the urea groups, but favored by terminal short alkoxy groups. The present information is useful for understanding the mechanism of the template-guided aryl radical grafting and the molecular design of new generations of template molecules.

Quantifying the Cooperative Process of Molecular Self-Assembly on Surfaces: A Case Study of Isophthalic Acids

Molecular self-assembly, a promising strategy for modifying surfaces on the nanometer scale, is essential for developing functional materials in electronics, catalysis, or two-dimensional (2D) crystal engineering. In this work, we are shifting attention to the physical chemistry of the process at a molecular level through a study of the effect of concentration on the overall process of self-assembled molecular network formation using scanning tunneling microscopy. The overarching idea is to correlate experimental results with analytical thermodynamic models to improve the understanding of supramolecular chemistry in two dimensions by obtaining quantitative data. For this purpose, a series of isophthalic acids have been chosen as a model system. The effect of the concentration on the adsorption behavior, focusing on the surface coverage, has been evaluated at the nanoscale. Our results confirm the existence of a critical concentration above which self-assembly occurs and that a change in the molecular structure (the length of the alkyl chain) has a remarkable impact on the value of this critical threshold. Finally, we report highly cooperative behavior in studied systems, which presents one of the rare examples of quantitative measurement of cooperative phenomena at the liquid/solid interface.

Solvent Mediated Nanoscale Quasi-Periodic Chirality Reversal in Self-Assembled Molecular Networks Featuring Mirror Twin Boundaries.

Grain boundaries in polycrystals have a prominent impact on the properties of a material, therefore stimulating the research on grain boundary engineering. Structure determination of grain boundaries of molecule-based polycrystals with submolecular resolution remains elusive. Reducing the complexity to monolayers has the potential to simplify grain boundary engineering and may offer real-space imaging with submolecular resolution using scanning tunneling microscopy (STM). Herein, the authors report the observation of quasi-periodic nanoscale chirality switching in self-assembled molecular networks, in combination with twinning, as revealed by STM at the liquid/solid interface. The width of the chiral domain structure peaks at 12-19nm. Adjacent domains having opposite chirality are connected continuously through interdigitated alkoxy chains forming a 1D defect-free domain border, reflecting a mirror twin boundary. Solvent co-adsorption and the inherent conformational adaptability of the alkoxy chains turn out to be crucial factors in shaping grain boundaries. Moreover, the epitaxial interaction with the substrate plays a role in the nanoscale chirality reversal as well.

Influence of core size on self-assembled molecular networks composed of C3h-symmetric building blocks through hydrogen bonding interactions: structural features and chirality.

The effect of the core size on the structure and chirality of self-assembled molecular networks was investigated using two aromatic carboxylic acid derivatives with frameworks displaying C3h symmetry, triphenylene derivative H3TTCA and dehydrobenzo[12]annulene (DBA) derivative DBACOOH, each having three carboxy groups per molecule. Scanning tunneling microscopy observations at the 1-heptanoic acid/graphite interface revealed H3TTCA exclusively forming a chiral honeycomb structure, and DBACOOH forming three structures (type I, II, and III structures) depending on its concentration and whether the system is subjected to annealing treatment. Hydrogen bonding interaction patterns and chirality were carefully analyzed based on a modeling study using molecular mechanics simulations. Moreover, DBACOOH forms chiral honeycomb structures through the co-adsorption of guest molecules. Structural diversity observed for DBACOOH is attributed to its relatively large core size, with this feature modulating the balance between molecule-molecule and molecule-substrate interactions.

(Invited, Digital Presentation) Molecular Self-assembly and Reactivity on 2D Layered Materials

In the first part, we will focus on the principles of self-assembled molecular network formation at the liquid-solid interface on surfaces such as graphite, MoS2, and graphene. Then we will discuss how lateral confinement, induced by covalent functionalization of graphite and graphene, affects self-assembly. Several strategies will be demonstrated to realize two-dimensional lateral confinement, all based on the covalent modification of the surface, making use of bottom-up approaches or a combination of bottom-up and top-down approaches. The impact of these various types of confinement on the formation of self-assembled molecular networks will be discussed, including aspects such as nucleation and growth, directional self-assembly, on-surface chirality, polymorphism, and reactivity.In a second part, we will focus on the formation of porous two-dimensional covalent organic frameworks at the liquid-solid interface, and reveal various interesting aspects at the molecular level such as nucleation and growth mechanisms, and the impact local electric fields may have on (de)polymerization processes.The relevance and importance of scanning probe microscopes to investigate (and control) self-assembly and reactivity on surfaces will be illustrated. C. Rodríguez González, A. Leonhardt, H. Stadler, S. Eyley, W. Thielemans, S. De Gendt, K. S. Mali, S. De Feyter, ACS Nano, 2021, 15, 10618–10627Verstraete, S. De Feyter, Chem. Soc. Rev., Chemical Society Reviews, 2021, 50, 5884–5897Bragança, A. Minoia, R. Steeno, J. Seibel, B. E. Hirsch, L. Verstraete, O. Ivasenko, K. Müllen, K. S. Mali, R. Lazzaroni, S. De Feyter, J. Am. Chem. Soc., 2021, 143, 11080–11087Tahara, Y. Kubo, S. Hashimoto, T. Ishikawa, H. Kaneko, A. Brown, B. E. Hirsch, S. De Feyter, Y. Tobe, J. Am. Chem. Soc., 2020, 142, 7699–7708Zhan, Z.-F. Cai, M. Martínez-Abadía, A. Mateo-Alonso, S. De Feyter, J. Am. Chem. Soc. 2020, 142, 5964–5968

From 2D to 3D: Bridging Self-Assembled Monolayers to a Substrate-Induced Polymorph in a Molecular Semiconductor

In this study, a new bottom-up approach is proposed to predict the crystal structure of the substrate-induced polymorph (SIP) of an archetypal molecular semiconductor. In spite of intense efforts, the formation mechanism of SIPs is still not fully understood, and predicting their crystal structure is a very delicate task. Here, we selected lead phthalocyanine (PbPc) as a prototypical molecular material because it is a highly symmetrical yet nonplanar molecule and we demonstrate that the growth and crystal structure of the PbPc SIPs can be templated by the corresponding physisorbed self-assembled molecular networks (SAMNs). Starting from SAMNs of PbPc formed at the solution/graphite interface, the structural and energetic aspects of the assembly were studied by a combination of in situ scanning tunneling microscopy and multiscale computational chemistry approach. Then, the growth of a PbPc SIP on top of the physisorbed monolayer was modeled without prior experimental knowledge, from which the crystal structure of the SIP was predicted. The theoretical prediction of the SIP was verified by determining the crystal structure of PbPc thin films using X-ray diffraction techniques, revealing the formation of a new polymorph of PbPc on the graphite substrate. This study clearly illustrates the correlation between the SAMNs and SIPs, which are traditionally considered as two separate but conceptually connected research areas. This approach is applicable to molecular materials in general to predict the crystal structure of their SIPs.

Evidence of One-Dimensional Channels in Hydrogen-Bonded Organic Porous Thin Films Fabricated at the Air/Liquid Interface.

Visualization of periodically aligned pores in organic frameworks is a key to the understanding of their structural control. Comparing to monolayer-thick self-assembled molecular networks, real-space nanoscale characterization of thicker films, especially obtaining information on the stacking manner of molecules is challenging. Here, we report an atomic force microscopy study of hydrogen-bonded thin films fabricated at the air/liquid interface. The presence of one-dimensional channels is evidenced by resolving honeycomb structures over the films with the thickness variation of more than several nanometers. We also demonstrate that the film thickness can be controlled by the ratio of mixed solvent rather than the surface pressure during the fabrication at the air/liquid interface.