In the article published by Jukić
I. Jukić
,
, 2021,
, 19537, the authors discovered a specific lifetime distribution of hydrogen bonds in some pure hydrogen-bonding liquids. The distribution derived ...by computer simulations in the range of 0-0.15 ps consists of three characteristic peaks. They call the first maximum the 'dimer peak', the second the 'cluster peak', and the third the 'topology peak'. In the article in question, mostly linear- and circular-cluster-forming mono-ols were simulated to show that the third peak is universal in these H-bonding substances. Moreover, the topology of the clusters, which was wrongly assumed to be detected in the tertiary lifetime peak, is instead seen in the distribution of the first maximum.
Hydrogen‐bonded polymers are a class of highly dynamic supramolecular aggregates, whose self‐assembly may be tuned by very mild external or internal stimuli. However, the rational design of chiral ...supramolecules remains challenging especially when flexible components are involved. The combination of the inherent weakness and dynamic nature of the intermolecular bonds that hold together such assemblies with unrestricted molecular motions introduces additional factors which may affect the self‐assembly process. In this report, the self‐assembly of four amino acid‐derived chiral biphenyldiimides into open‐chain 1D supramolecular polymers is presented. While the primary driving force, COOH···HOOC hydrogen bonding, is responsible for the polymer growth in all cases, the amino acid side chains play an important role in either stabilizing or destabilizing the assemblies obtained, as deduced from studies of the thermodynamics of the self‐assembly process. Furthermore, substantial differences in the structural factors governing the polymerization process between dynamic liquid and static solid are found. This work demonstrates the potential of the rather unexplored class of diimide‐based organic dyes in the formation of well‐organized chiral supramolecular assemblies with tunable properties.
Four amino acid‐derived biphenyldiimides are obtained, and their self‐assembly into open‐chain 1D supramolecular polymers is studied in solution and solid state. It is found that the polymer growth is driven solely by COOH∙∙∙HOOC hydrogen bonding, and proceeds via an isodesmic pathway unless competitive interactions between side chains and binding sites occur.
A hydrogen-bonded metallocyanide-based (AZE)
(H
O)Co(CN)
framework was obtained by introducing a hydronium cation to the A
B(1)B(2)CN
-type structure. Simple K
/H
O
substitution exchange the ...three-dimensional structure of the double-perovskite into two-dimensional layers containing open inorganic cages with a strongly discontinuous improper ferroelastic phase transition.
A versatile double‐network (DN) hydrogel with two noncovalent crosslinked networks is synthesized by multiple hydrogen bonding (H‐bonding) interactions. The DN hydrogels are synthesized via a ...heating–cooling photopolymerization process by adding all reactants of agar, N‐acryloyl glycinamide (NAGA) and N‐benzylacrylamide (NBAA) monomers, UV initiators to a single water pot. Poly(N‐acryloyl glycinamide‐co‐N‐benzyl acrylamide) (P(NAGA‐co‐NBAA)) with a triple amide in one side group is synthesized via UV‐light polymerization between NAGA and NBAA, forming a strong intermolecular H‐bonding network. Meanwhile, the intramolecular H‐bonding network is formed between P(NAGA‐co‐NBAA) and agars. The sol–gel phase transition of agars at 86 °C generates the molecular entanglement network. Such a double network enables the hydrogel high self‐healing efficiency (about 95%), good shape memory ability, and high mechanical strength (1.1 MPa). Additionally, the DN hydrogel is completely crosslinked by multiple hydrogen bonds (H‐bonds) and the physical crosslinking of agar without extra potential toxic chemical crosslinker. The DN hydrogels find extensive applications in the biomedical materials due to their excellent biocompatibility.
Poly(N‐acryloyl glycinamide‐co‐N‐benzyl acrylamide)/agar double‐network hydrogels crosslinked by multiple hydrogen bonds are synthesized. The double network gives the hydrogel high self‐healing efficiency (about 95%), high mechanical strength (1.1 MPa), and good shape memory ability.
C-H S hydrogen bonding interactions Fargher, Hazel A; Sherbow, Tobias J; Haley, Michael M ...
Chemical Society reviews,
02/2022, Letnik:
51, Številka:
4
Journal Article
Recenzirano
Odprti dostop
The short C-H S contacts found in available structural data for both small molecules and larger biomolecular systems suggest that such contacts are an often overlooked yet important stabilizing ...interaction. Moreover, many of these short C-H S contacts meet the definition of a hydrogen bonding interaction. Using available structural data from the Cambridge Structural Database (CSD), as well as selected examples from the literature in which important C-H S contacts may have been overlooked, we highlight the generality of C-H S hydrogen bonding as an important stabilizing interaction. To uncover and establish the generality of these interactions, we compare C-H S contacts with other traditional hydrogen bond donors and acceptors as well as investigate how coordination number and metal bonding affect the preferred geometry of interactions in the solid state. This work establishes that the C-H S bond meets the definition of a hydrogen bond and serves as a guide to identify C-H S hydrogen bonds in diverse systems.
The short C-H S contacts found in available structural data for both small molecules and larger biomolecular systems suggest that such contacts are an often overlooked yet important stabilizing interaction.
The delicate interplay between functional-driven and density-driven errors in density functional theory (DFT) has hindered traditional density functional approximations (DFAs) from providing an ...accurate description of water for over 30 years. Recently, the deep-learned DeepMind 21 (DM21) functional has been shown to overcome the limitations of traditional DFAs as it is free of delocalization error. To determine if DM21 can enable a molecular-level description of the physical properties of aqueous systems within Kohn-Sham DFT, we assess the accuracy of the DM21 functional for neutral, protonated, and deprotonated water clusters. We find that the ability of DM21 to accurately predict the energetics of aqueous clusters varies significantly with cluster size. Additionally, we introduce the many-body MB-DM21 potential derived from DM21 data within the many-body expansion of the energy and use it in simulations of liquid water as a function of temperature at ambient pressure. We find that size-dependent functional-driven errors identified in the analysis of the energetics of small clusters calculated with the DM21 functional result in the MB-DM21 potential systematically overestimating the hydrogen-bond strength and, consequently, predicting a more ice-like local structure of water at room temperature.
ortho-Quinone methides have emerged recently as useful electrophiles in metal-free catalysis. New strategies to access these species in situ that are compatible with simultaneous nucleophile ...generation have provided a suite of innovative and selective transformations accessing heterocycles for use in organic synthesis.
Single atom catalysts (SACs) comprised of nitrogen‐coordinated transition metal (TM–N–C) moieties show encouraging performance towards the oxygen reduction reaction (ORR). Nevertheless, for the ...reactions involving multiple intermediates, single‐atom sites fail to satisfactorily optimize the adsorption of all intermediates. Here, a facile strategy is reported to construct Fe, P dual‐atom sites in multimodal porous carbon (Fe,P‐DAS@MPC), and its superiority in synergistically boosting ORR is demonstrated. Fe,P‐DAS@MPC exhibits excellent ORR performance with substantially positive onset potential (Eonset = 1.02 V) and half‐wave potential (E1/2 = 0.92 V). Theoretical analysis unveils the cooperative effect of dual‐atom sites composed of adjacent P and Fe atoms, and the aiding of hydrogen bonding interaction can promote the adsorption/desorption of intermediates. Additionally, a Zn–air battery based on the Fe,P‐DAS@MPC shows a high peak power density and exceptional cycling stability. These findings provide a novel avenue towards the design of electrocatalysts with dual‐atom sites for practical energy conversion applications.
A novel two‐step strategy is introduced to sequentially immobilize P and Fe atoms towards dual‐atom sites in multimodal porous carbon (Fe,P‐DAS@MPC). The cooperative effect of adjacent P and Fe single atoms endows Fe,P‐DAS@MPC with enhanced electrochemical oxygen reduction reaction (ORR) performance. The theoretical studies reveal that the hydrogen bonding interaction can promote the adsorption/desorption of ORR intermediates from dual‐atom sites.
Conspectus Hydrogen-bonded organic framework (HOF) materials have provided a new dimension and bright promise as a new platform for developing multifunctional materials. They can be readily ...self-assembled from their corresponding organic molecules with diverse functional sites such as carboxylic acid and amine groups for their hydrogen bonding and aromatic ones for their weak π···π interactions to stabilize the frameworks. Compared with those established porous materials such as zeolites, metal–organic frameworks (MOFs), and covalent–organic frameworks (COFs), it is much more difficult to stabilize HOFs and thus establish their permanent porosities given the fact that hydrogen bonds are typically weaker than ionic, coordination, and covalent bonds. But it provides the uniqueness of HOF materials in which they can be easily recovered and regenerated through simple recrystallization. HOF materials can also be easily and straightforwardly processed and very compatible with the biomolecules, making them potentially very useful materials for industrial and biomedical applications. The reversible and weak bonding nature of the hydrogen bonds can be readily utilized to construct flexible porous HOF materials in which we can tune the temperature and pressure to control their porosities and, thus, their diverse applications, for example, on gas separations, gas storage, drug delivery, and sensing. Some specific organic functional groups are quite directional for the hydrogen bond formations; for example, carboxylic acid prefers to form a directional dimer, which has enabled us to readily construct reticular porous HOF materials whose pores can be systematically tuned. In this Account, we outline our journey of exploring this new type of porous material by establishing one of the first porous HOFs in 2011 and thus developing its diverse applications. We have been able to use organic molecules with different functional sites, including 2,4-diaminotriazine (DAT), carboxylic acid (COOH), aldehyde (CHO), and cyano (CN), to construct porous HOFs. Through tuning the pore sizes, introducing specific binding sites, and making use of the framework flexibility, we have realized a series of HOF materials for the gas separations of C2H2/C2H4, C2H4/C2H6, C3H6/C3H8, C2H2/CO2, CO2/N2, and Xe/Kr and enantioselective separation of alcohols. To make use of optically active organic molecules, we have developed HOF materials for their luminescent sensing and optical lasing. Our research endeavors on multifunctional HOF materials have initiated extensive research in this emerging research topic among chemistry and materials sciences communities. We foresee that not only many more HOF materials will be developed but novel functions will be fulfilled beyond our imaginations soon.
Hydrogen-bonded organic frameworks (HOFs) represent an interesting type of polymeric porous materials that can be self-assembled through H-bonding between organic linkers. To realize permanent ...porosity in HOFs, stable and robust open frameworks can be constructed by judicious selection of rigid molecular building blocks and hydrogen-bonded units with strong H-bonding interactions, in which the framework stability might be further enhanced through framework interpenetration and other types of weak intermolecular interactions such as π π interactions. Owing to the reversible and flexible nature of H-bonding connections, HOFs show high crystallinity, solution processability, easy healing and purification. These unique advantages enable HOFs to be used as a highly versatile platform for exploring multifunctional porous materials. Here, the bright potential of HOF materials as multifunctional materials is highlighted in some of the most important applications for gas storage and separation, molecular recognition, electric and optical materials, chemical sensing, catalysis, and biomedicine.
This review provides an overview of development in the design, synthesis, and application of multifunctional porous hydrogen-bonded organic framework (HOF) materials.
