Supramolecular self-assemblies as functional nanomaterials (original) (raw)
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Functional supramolecular assemblies have emerged as candidates for nanosystems because of their potential for efficient, green, and costeffective fabrication, as well as the capacity for tunability at molecular and atomic scales. Recent advances in the synthesis and characterization of supramolecular assemblies have already pointed to many opportunities ahead. While the practical integration of supramolecular assemblies into device manufacturing remains out of reach, learning to design the precise interactions between molecules and to control (and to predict) their structures will drive excitement, interest, and advances in bottom-up approaches to new materials and devices. This review discusses several key advances in the preparation of (and applications for) functional supramolecular assemblies, upcoming challenges, and our approaches toward the analysis of and precise control over functional supramolecular assemblies.
Design of supramolecular nanomaterials : from molecular recognition to hierarchical self-assembly
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In the present thesis, are reported new strategies for the design of nanostructures to partly address environmental issues. The work carried out has been divided into three parts: the design of cyclodextrin (CD)-based polymeric materials, the molecular engineering of a pyrene derivative for the formation of self-assembled nanostructures and the design of smart nanocarriers. Considerable efforts have been devoted to the design of molecular receptors capable of specific recognition of a wide variety of targets ranging from small inorganic ions to large biomolecules. These molecular receptors have been widely used to produce (nano)materials with superior molecular recognition properties. While these materials have been extensively studied for biomedical applications, their use in environmental sciences or biotechnology has been, to some extent, neglected. Supramolecular materials, because of their superior molecular recognition properties may find a wealth of new applications for the s...
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Journal of the American Chemical Society, 2011
A novel, interlocked, self-assembled (M 2 L 2 ) 2 molecular architecture (3) was constructed from arene-Ru acceptor 1 and 1,4-di(pyridine-4-yl)buta-1,3-diyne donor 2. Two M 2 L 2 units, with cavities of ~7.21 Å, spontaneously interlock with one unit encapsulating a twin in a non-catenane fashion. The dimeric host-guest complex thus formed is unique among two dimensional selfassemblies and is stabilized by π-π interactions between the M 2 L 2 units.
Solvent‐Driven Supramolecular Wrapping of Self‐Assembled Structures
Angewandte Chemie International Edition, 2021
Self-assembly relies on the ability of smaller and discrete entities to spontaneously arrange into more organized systems by means of the structure-encoded information. Herein, we show that the design of the media can playarole even more important than the chemical design. The media not only determines the self-assembly pathway at as ingle-component level, but in avery narrowsolvent composition, asupramolecular homo-aggregate can be non-covalently wrapped by as econd component that possesses ad ifferent crystal lattice. Such ap rocess has been followed in real time by confocal microscopyt hanks to the different emission colors of the aggregates formed by two isolated Pt II complexes.This coating is reversible and controlled by the media composition. Singlecrystal X-ray diffraction and molecular simulations based on coarse-grained (CG) models allowed the understanding of the properties displayed by the different aggregates.Such findings could result in an ew method to construct hierarchical supramolecular structures.
Journal of Pharmacy and Pharmacology Research, 2023
Supramolecular chemistry is a captivating and interdisciplinary field that explores the interactions between molecules to form complex and functional assemblies through non-covalent forces. This review paper presents an indepth exploration of the fundamental concepts, supramolecular assemblies and structures, applications in nanotechnology and biology, as well as challenges and future perspectives in supramolecular chemistry. The paper begins by elucidating the fundamental principles of supramolecular chemistry, emphasizing the significance of weak, non-covalent interactions such as hydrogen bonding, van der Waals forces, and π-π interactions. Molecular recognition, self-assembly, and host-guest interactions are highlighted as key concepts shaping the field. Subsequently, the review delves into various supramolecular assemblies and structures, showcasing the diversity of nanoscale architectures that arise from self-assembly processes. From nanotubes and nanofibers to metal-organic frameworks and dynamic supramolecular systems, each structure's properties and potential applications are explored. The application of supramolecular chemistry in nanotechnology and biology is a central focus of the paper. It covers the design of supramolecular materials for drug delivery, nanoelectronics, nanosensors, and biomimetic systems. Additionally, the integration of supramolecular approaches in biology, including molecular recognition, enzyme mimics, and bioimaging, is discussed in detail. Furthermore, the challenges faced by supramolecular chemistry, such as predictability, stability, and scalability, are addressed. The paper also looks into the future perspectives of the field, envisioning adaptive materials, supramolecular machines, and data-driven design as exciting prospects. Overall, this comprehensive review offers a thorough understanding of the captivating world of supramolecular chemistry and its potential to revolutionize various scientific and technological domains. Through interdisciplinary efforts and a focus on sustainability, supramolecular chemistry holds promise for addressing real-world challenges and shaping a future defined by innovative materials and transformative applications.
Nearly-freestanding supramolecular assembly with tunable structural properties
Scientific Reports, 2023
The synthesis and design of two-dimensional supramolecular assemblies with specific functionalities is one of the principal goals of the emerging field of molecule-based electronics, which is relevant for many technological applications. Although a large number of molecular assemblies have been already investigated, engineering uniform and highly ordered two-dimensional molecular assemblies is still a challenge. Here we report on a novel approach to prepare wide highly crystalline molecular assemblies with tunable structural properties. We make use of the high-reactivity of the carboxylic acid functional moiety and of the predictable structural features of non-polar alkane chains to synthesize 2D supramolecular assemblies of 4-(decyloxy)benzoic acid (4DBA;C 17 H 26 O 3) on a Au(111) surface. By means of scanning tunneling microscopy, density functional theory calculations and photoemission spectroscopy, we demonstrate that these molecules form a self-limited highly ordered and defect-free two-dimensional single-layer film of micrometer-size, which exhibits a nearly-freestanding character. We prove that by changing the length of the alkoxy chain it is possible to modify in a controlled way the molecular density of the "floating" overlayer without affecting the molecular assembly. This system is especially suitable for engineering molecular assemblies because it represents one of the few 2D molecular arrays with specific functionality where the structural properties can be tuned in a controlled way, while preserving the molecular pattern. Complex molecular architectures are usually constructed by connecting molecular building blocks through non-covalent bonding, allowing for a variety of different supramolecular structures and phases to emerge 1-6. When solid surfaces are used as supports, the molecular self-assembly can be regarded as a two-dimensional (2D) process, and the structural and electronic properties, such as molecular packing, the number and typologies of domains, and the binding energy of the molecular levels, strongly depend on the interplay between the intermolecular forces and the interaction between the adsorbate and the underlying support 7-9. A suitable choice of molecular building blocks and supporting substrates would enable, in principle, synthesizing and designing 2D supramolecular assemblies with specific functionalities, disclosing exciting new opportunities in many areas of science and technology 10-13. Key steps to these accomplishments are (a) to understand how molecules self-arrange, and (b) to master the growth of homogeneous, highly ordered and defect-free films with tunable properties 14,15 .