Noncovalent interactions in inorganic supramolecular chemistry based in heavy metals. Quantum chemistry point of view

Complexity is a concept that is being considered in chemistry as it has shown potential to reveal interesting phenomena. Thus, it is possible to study chemical phenomena in a new approach called systems chemistry. The systems chemistry has an organization and function, which are regulated by the interactions among its components. At the simplest level, noncovalent interactions between molecules can lead to the emergence of large structures. Consequently, it is possible to go from the molecular to the supramolecular systems chemistry, which aims to develop chemical systems highly complex through intra- and intermolecular forces. Proper use of the interactions previously mentioned allow a glimpse of supramolecular system chemistry in many tasks such as structural properties reflecting certain behaviors in the chemistry of materials, for example, electrical and optical, processes of molecular recognition and among others. In the last time, within this area, inorganic supramolecular systems chemistry has been developed. Those systems have a structural orientation which is defined by certain forces that predominate in the associations among molecules. It is possible to recognize these forces as hydrogen bonding, π-π stacking, halogen bonding, electrostatic, hydrophobic, charge transfer, metal coordination, and metallophilic interactions. The presence of these forces in supramolecular system yields certain properties such as light absorption and luminescence. The quantum theoretical modeling plays an important role in the designing of the supramolecular system. The goal is to apply supramolecular principles in order to understand the associated forces in many inorganic molecules that include heavy metals for instance gold, platinum, and mercury. Relevant systems will be studied in detail, considering functional aspects such as enhanced coordination of functionalized molecular self-assembly, electronic and optoelectronic properties.     

Superstructure-Induced Hierarchical Assemblies for Nanoconfined Photocatalysis

Most attempts to synthesize supramolecular nanosystems are limited to a single mechanism, often resulting in the formation of nanomaterials that lack diversity in properties. Herein, hierarchical assemblies with appropriate variety are fabricated in bulk via a superstructure-induced organic–inorganic hybrid strategy. The dynamic balance between substructures and superstructures is managed using covalent organic frameworks (COFs) and metal–organic frameworks (MOFs) as dual building blocks to regulate the performances of hierarchical assemblies. Significantly, the superstructures resulting from the controlled cascade between COFs and MOFs create highly active photocatalytic systems through multiple topologies. Our designed tandem photocatalysis can precisely and efficiently regulate the conversion rates of bioactive molecules (benzo[d]imidazoles) through competing redox pathways. Furthermore, benzo[d]imidazoles catalyzed by such supramolecular nanosystems can be isolated in yields ranging from 70 % to 93 % within tens of minutes. The multilayered structural states within the supramolecular systems demonstrate the importance of hierarchical assemblies in facilitating photocatalytic propagation and expanding the structural repertoire of supramolecular hybrids.     

From self-assembly to noncovalent synthesis of programmable porphyrins' arrays in aqueous solution

Self-organization is the driving force that led to the evolution of life. Rationalization of the spontaneous self-assembly paradigm will offer tremendous potentialities to obtain a wide variety of complex systems, having specific functionality and properties. Herein, we will propose an overview of the developments in non-covalent syntheses of multi-porphyrin supramolecular species in aqueous solution. This work took inspiration from the pioneering studies aimed at rationalizing the spontaneous aggregation processes, governed by conventional solution properties (i.e. pH, ionic strength, and concentration). The more recent chemical strategies, to hierarchically manipulate the cooperative nature of weak interactions to design and synthesize supramolecular entities having pre-determined structure and properties, demonstrate the feasibility to attain, in a reproducible manner, molecular organization to supramolecular levels. In particular, calixarene-porphyrin species represents concrete evidence of a quantitative complexation, governed by precise hierarchical rules, which together with a rational functionalization of the molecular components leads to supramolecular entities of well-defined and tunable stoichiometry. These systems, thus, represent fertile ground to envisage and implement controlled self-organization strategies as bottom up methodologies to obtain supramolecular nanostructures and smart nanomachines.     

肽基超分子胶体

肽基超分子胶体是基于肽分子间超分子作用,自发形成且具有有序分子排布及规整结构,兼具传统胶体及超分子特性的组装体系。利用超分子弱相互作用构筑功能性胶体,不仅是人们对生命组装进程深入理解的有效手段,也是实现优异的超分子材料的重要途径。肽分子具有组成明确、性能可调、生物安全性高及可降解等优势,是超分子化学、胶体与界面化学领域重要的组装基元。基于肽的超分子自组装,能够实现多尺度、多功能的生物胶体的构筑,被广泛应用于医药、催化、能源等领域。如何通过对肽序列的设计及分子间作用力的调控,实现对胶体结构和功能的精确控制,是近年来研究的重要课题之一。从分子尺度研究和揭示超分子胶体的组装过程及物理化学机制,探究胶体结构与功能的关系,是实现超分子结构和功能化的重要内容。本文基于"分子间作用的调控"及"结构与功能的关系"两个基本科学问题,系统地综述了肽基超分子胶体的组装机制、结构与功能,以及研究现状。     

The use of (metallo-)supramolecular initiators for living/controlled polymerization techniques

The introduction of supramolecular interactions in synthetic polymers seems to be a promising approach towards novel 'smart' materials that combine both the (reversible) supramolecular interactions and the properties of the polymers. In this tutorial review, the use of (metallo-)supramolecular initiators for the preparation of end-functionalized (metallo-)supramolecular polymers will be discussed in detail. The different polymerization techniques that have been applied as well as the different ligands and metal complexes that were used to initiate these polymerizations will be discussed together with the resulting polymer properties.     

Intramolecular d10-d10 interactions in heterometallic clusters of the transition metals

Weak attractive interactions between closed shell metal ions have been increasingly studied in the last few years and are generally designated as metallophilic interactions. They are best evidenced in the solid state where structural data obtained by X-ray diffraction provide precise information about the distance between the metals involved. The strength of such metal-metal interactions has been compared to that of hydrogen bonding (ca. 7-11 kcal mol(-1)) and is clearly sufficient to bring about novel bonding and structural features and confer interesting physical properties such as luminescence, polychromism, magnetism or one-dimensional electrical conductivity. The Cu(I)-Cu(I), Ag(I)-Ag(I) and Au(I)-Au(I) interactions have been increasingly observed and the latter have certainly been the most studied. Early qualitative analyses of the aurophilic attraction focused on Au-Au bonding originating from 6s, 6p and 5d orbital mixing. Numerous theoretical studies on metallophilic interactions continue to be carried out at various levels of sophistication which take into account relativistic and correlation effects to describe these van der Waals-type interactions. In this critical review, we would like to focus on the synthesis and structures of heterometallic clusters of the transition metals in which intra- rather than intermolecular d(10)-d(10) interactions are at work, in order to limit the role of packing effects. We wish to provide the reader with a comparative overview of the metal core structures resulting from or favoring metallophilic interactions but do not intend to provide a comprehensive coverage of the literature. We will first examine heterometallic clusters displaying homometallic and then heterometallic d(10)-d(10) interactions. Although the focus of this review is on d(10)-d(10) interactions involving metals from the group 11, we shall also briefly examine for comparison some complexes displaying intramolecular d(10)-d(10) interactions involving metals from other groups (188 references).     

Revisiting van der Waals Radii: From Comprehensive Structural Analysis to Knowledge-Based Classification of Interatomic Contacts

Weak noncovalent interactions are responsible for structure and properties of almost all supramolecular systems, such as nucleic acids, enzymes, and pharmaceutical crystals. However, the analysis of their significance and structural role is not straightforward and commonly requires model studies. Herein, we describe an efficient and universal approach for the analysis of noncovalent interactions and determination of van der Waals radii using the line-of-sight (LoS) concept. The LoS allows to unambiguously identify and classify the “direct” interatomic contacts in complex molecular systems. This approach not only provides an improved theoretical base to molecular “sizes” but also enables the quantitative analysis of specificity, anisotropy, and steric effects of intermolecular interactions.     

Highlights on the recent advances in gold chemistry--a photophysical perspective

The presence of inter- and/or intra-molecular aurophilic interactions among the closed-shell gold(i) centres in various systems has been studied from various aspects, including synthetic, spectroscopic and theoretical approaches. The employment of different ligands can impose a significant influence on these factors and give rise to new complexes with interesting structural and photophysical properties. In this tutorial review, a number of recent examples are selected to illustrate the fascinating properties and chemistry, as well as versatility of gold(i) in these aspects and their potential applications to newcomers in this field. An emerging class of luminescent gold(iii) complexes is also described.     

Mechanistic Insights into the Luminescent Sensing of Organophosphorus Chemical Warfare Agents and Simulants Using Trivalent Lanthanide Complexes

Organophosphorus chemical warfare agents (OP CWAs) are potent acetylcholinesterase inhibitors that can cause incapacitation and death within minutes of exposure, and furthermore are largely undetectable by the human senses. Fast, efficient, sensitive and selective detection of these compounds is therefore critical to minimise exposure. Traditional molecular‐based sensing approaches have exploited the chemical reactivity of the OP CWAs, whereas more recently supramolecular‐based approaches using non‐covalent interactions have gained momentum. This is due, in part, to the potential development of sensors with second‐generation properties, such as reversibility and multifunction capabilities. Supramolecular sensors also offer opportunities for incorporation of metal ions allowing for the exploitation of their unique properties. In particular, trivalent lanthanide ions are being increasingly used in the OP CWA sensing event and their use in supramolecular sensors is discussed in this Minireview. We focus on the fundamental interactions of simple lanthanide systems with OP CWAs and simulants, along with the development of more elaborate and complex systems including those containing nanotubes, polymers and gold nanoparticles. Whilst literature investigations into lanthanide‐based OP CWA detection systems are relatively scarce, their unique and versatile properties provide a promising platform for the development of more efficient and complex sensing systems into the future.     

Molecular Links and Knots from Naphthalenediimide: A Balance of Weak Interactions

Owing to its unique structural, electronic, spectroscopic, and redox properties, naphthalenediimide (NDI) is a versatile building block for the construction of a wide variety of supramolecular assemblies with diverse structures, properties, and functions. In this Minireview, the synthesis of topologically nontrivial molecular links and knots based on naphthalenediimide‐derived building blocks will be discussed. In particular, the supramolecular forces that contribute to the formation of these molecular links and knots and their interactions will be discussed.     

Design of molecular ferromagnets

A large variety of molecular ferromagnets have been synthesized since the discovery of the first organic ferromagnets, including pure organic compounds, organometallic charge-transfer complexes, metal complex-organic radical compounds, and transition metal complexes coupled to organic radicals. Besides, there are many reports on the observation of ferromagnetism in polymers and organic matrix composites. Molecular ferromagnets have great potential in different areas of technology such as low frequency magnetic shielding, magnetic imaging, magneto-optics and information storage. We provide a brief review on the current strategies for the design of molecular (organic) ferromagnets. This includes exploiting the inherent advantages of molecular systems, such as the ability to fine-tune the properties at the molecular level, and to control dimensionality, supramolecular structuring and hierarchy of spin interactions etc. for carrying out structural modifications and chemical functionalisations of stable open-shell molecules in order to generate supramolecular structures in which the natural prediction for antiparallel spin alignment (antiferromagnetism) is avoided.     

基于氢键作用结合的超分子聚合物

非共价键结合的超分子聚合物由于其特殊的结构及性能引起了广泛的关注。本文在介绍超分子化学、氢键及超分子聚合物的基础上,主要综述了以氢键为结合力的多重氢键作用、羧基（D）与吡啶基（A）作用以及氢键与其它非共价键协同作用形成的超分子聚合物体系,并对超分子聚合物的研究现状及前景进行了评述。     

The Power of Confocal Laser Scanning Microscopy in Supramolecular Chemistry: In situ Real-time Imaging of Stimuli-Responsive Multicomponent Supramolecular Hydrogels

Multicomponent supramolecular hydrogels are promising scaffolds for applications in biosensors and controlled drug release due to their designer stimulus responsiveness. To achieve rational construction of multicomponent supramolecular hydrogel systems, their in-depth structural analysis is essential but still challenging. Confocal laser scanning microscopy (CLSM) has emerged as a powerful tool for structural analysis of multicomponent supramolecular hydrogels. CLSM imaging enables real-time observation of the hydrogels without the need of drying and/or freezing to elucidate their static and dynamic properties. Through multiple, selective fluorescent staining of materials of interest, multiple domains formed in supramolecular hydrogels (e. g. inorganic materials and self-sorting nanofibers) can also be visualized. CLSM and the related microscopic techniques will be indispensable to investigate complex life-inspired supramolecular chemical systems.     

Cucurbit[10]uril-based chemistry

With the biggest cavity in the cucurbit[n]urils (CB[n]s) family, CB[10] has shown its unique molecular recognition properties. This review gives a brief summary of the research progresses in the CB[10]-based chemistry, involving its purification and applications in fields such as molecular recognition and molecular assembly.     

Self-Complementary Quadruple Hydrogen-Bonding Motifs as a Functional Principle: From Dimeric Supramolecules to Supramolecular Polymers

The self-association of individual molecules can lead to the formation of highly complex and fascinating supramolecular aggregates. However, for binding motifs which rely only on hydrogen bonds, a combination of several such weak interactions is necessary to observe self-association in solution. Systems based on four hydrogen bonds in a linear array can be obtained which efficiently aggregate at least in chloroform. Besides the physical-organic characterization of these aggregates and the factors influencing their stability, such quadruple hydrogen-bonding motifs can also be used in the field of materials science to synthesize, for the first time, supramolecular polymers through the self-association of self-complementary monomers. As the formation of noncovalent interactions is reversible and their strength depends significantly on the chemical environment (for example, solvent, temperature), the macroscopic properties of such polymers can be controlled by variation of these parameters; hence a first step towards intelligent materials with tailor-made properties is made.     

Azobenzene-based Photochromic Delivery Vehicles for Ions and Small Molecules

Molecular switches have been used as delivery vehicles for various molecular and ionic species. The ones that reversibly operate with light are arguably the best candidates for the purpose as they can be operated using light. The two states of these photoswitchable systems often possess remarkable differences in terms of their structural features and electronic properties. Photochromic systems with the appropriate embellishment of functionalities at suitable positions have thus been used as photoresponsive receptors. The use of light-driven alterations of the structural features has led to differential molecular recognition with these switchable host molecules. In this article, we discuss the use of such supramolecular systems as the delivery vehicles for ions and molecules that started with the pioneering work by Shinkai back in 1979. This review will explicitly cover the development from 2001 to 2022 with some past background and the future prospects of the field.     

Modeling of Supramolecular Structure and Physicochemical Properties of the Propanone–Methanol Mixture

The results on modeling of the supramolecular organization and physicochemical properties of the propanone-methanol mixture are presented. An analysis of the excess thermodynamic functions (Gibbs energy, enthalpy, and entropy) and the permittivity of mixtures have been performed in the whole range of compositions and temperatures. It has been demonstrated that the model of supramolecular structure, taking into account the chain and cyclic association of methanol molecules and complexation of alcohol aggregates with propanone, describes the properties of the mixture. It established that both specific and universal interactions contribute to the positive deviations from the thermodynamic ideal solution behavior. Positive deviation of the dipole correlation factor from unity is due to a predominantly parallel orientation of the dipoles of the molecules in methanol aggregates and their complexes with propanone. The thermodynamic parameters of aggregation and structural parameters of aggregates have been determined. The cooperativity of H bonding was established. Distribution functions of the aggregate, according to size and structure, are presented. The manifestations of the supramolecular ordering on the physicochemical properties of the mixture are discussed.     

Peptide Nanomaterials Designed from Natural Supramolecular Systems

Natural supramolecular assemblies exhibit unique structural and functional properties that have been optimized over the course of evolution. Inspired by these natural systems, various bio‐nanomaterials have been developed using peptides, proteins, and nucleic acids as components. Peptides are attractive building blocks because they enable the important domains of natural protein assemblies to be isolated and optimized while retaining the original structures and functions. Furthermore, the peptide subunits can be conjugated with exogenous molecules such as peptides, proteins, nucleic acids, and metal nanoparticles to generate advanced functions. In this personal account, we summarize recent progress in the construction of peptide‐based nanomaterial designed from natural supramolecular systems, including (1) artificial viral capsids, (2) self‐assembled nanofibers, and (3) protein‐binding motifs. The peptides inspired by nature should provide new design principles for bio‐nanomaterials.     

Liquid crystals from hydrogen-bonded amphiphiles

Liquid crystals originating from hydrogen-bonded amphiphiles will be discussed, highlighting the structural features of the amphiphilic components that lead to supramolecular systems exhibiting liquid crystalline character. Liquid crystalline phases derived from two types of hydrogen-bonded amphiphiles will be presented: (a) liquid crystalline phases originating from multihydroxylated amphiphiles; and (b) liquid crystalline phases resulting from combined hydrogen bonding and ionic interactions.     

Gold nanoparticles in organic capsules: a supramolecular assembly of gold nanoparticles and cucurbituril

Gold nanoparticles (相似文献