Browse
Submit Data
Databases
API
Help

Dataset Information

21 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

On-surface isostructural transformation from a hydrogen-bonded network to a coordination network for tuning the pore size and guest recognition.

ABSTRACT: Rational manipulation of supramolecular structures on surfaces is of great importance and challenging. We show that imidazole-based hydrogen-bonded networks on a metal surface can transform into an isostructural coordination network for facile tuning of the pore size and guest recognition behaviours. Deposition of triangular-shaped benzotrisimidazole (H₃btim) molecules on Au(111)/Ag(111) surfaces gives honeycomb networks linked by double N-H⋯N hydrogen bonds. While the H₃btim hydrogen-bonded networks on Au(111) evaporate above 453 K, those on Ag(111) transform into isostructural [Ag₃(btim)] coordination networks based on double N-Ag-N bonds at 423 K, by virtue of the unconventional metal-acid replacement reaction (Ag reduces H⁺). The transformation expands the pore diameter of the honeycomb networks from 3.8 Å to 6.9 Å, giving remarkably different host-guest recognition behaviours for fullerene and ferrocene molecules based on the size compatibility mechanism.

SUBMITTER: Zhou DD

PROVIDER: S-EPMC8179111 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Construction of isostructural hydrogen-bonded organic frameworks: limitations and possibilities of pore expansion.

Project description:The library of isostructural porous frameworks enables a systematic survey to optimize the structure and functionality of porous materials. In contrary to metal-organic frameworks (MOFs) and covalent organic frameworks (COFs), a handful of isostructural frameworks have been reported for hydrogen-bonded organic frameworks (HOFs) due to the weakness of the bonds. Herein, we provide a rule-of-thumb to develop isostructural HOFs, where we demonstrate the construction of the third and fourth generation of isostructural HAT-based HOFs (TolHAT-1 and ThiaHAT-1) by considering three important structural factors, that are (1) directional H-bonding, (2) shape-fitted docking of the HAT core, and (3) modulation of peripheral moieties. Their structural and photo-physical properties including HCl vapor detection are presented. Moreover, TolHAT-1, ThiaHAT-1, and other isostructural HOFs (CPHAT-1 and CBPHAT-1) were thoroughly compared from the viewpoints of structures and properties. Importantly, molecular dynamics (MD) simulation proves to be rationally capable of evaluating the stability of isostructural HOFs. These results can accelerate the development of various isostructural molecular porous materials.

| S-EPMC8293819 | biostudies-literature

Hydrogen-bonded host-guest systems are stable in ionic liquids.

Project description:We show that H-bonded host-guest systems associate in ionic liquids (ILs), pure salts with melting point below room temperature, in which dipole-dipole electrostatic interactions should be negligible in comparison with dipole-charge interactions. Binding constants (Ka) obtained from titrations of four H-bonded host-guest systems in two organic solvents and two ionic liquids yield smaller yet comparable Ka values in ionic liquids than in organic solvents. We also detect the association event using force spectroscopy, which confirms that the binding is not solely due to (de)solvation processes. Our results indicate that classic H-bonded host-guest supramolecular chemistry takes place in ILs. This implies that strong H-bonds are only moderately affected by surroundings composed entirely of charges, which can be interpreted as an indication that the balance of Coulombic to covalent forces in strong H-bonds is not tipped towards the former.

| S-EPMC7508985 | biostudies-literature

Symmetry-breaking host-guest assembly in a hydrogen-bonded supramolecular system.

Project description:Bio-inspired self-assembly is invaluable to create well-defined giant structures from small molecular units. Owing to a large entropy loss in the self-assembly process, highly symmetric structures are typically obtained as thermodynamic products while formation of low symmetric assemblies is still challenging. In this study, we report the symmetry-breaking self-assembly of a defined C1-symmetric supramolecular structure from an Oh-symmetric hydrogen-bonded resorcin[4]arene capsule and C2-symmetric cationic bis-cyclometalated Ir complexes, carrying sterically demanding tertiary butyl (tBu) groups, on the basis of synergistic effects of weak binding forces. The flexible capsule framework shows a large structural change upon guest binding to form a distorted resorcin[4]arene hexameric capsule, providing an asymmetric cavity. Location of the chiral guest inside the anisotropic environment leads to modulation of its Electric Dipole (ED) and Magnetic Dipole (MD) transition moments in the excited state, causing an increased emission quantum yield, longer emission lifetime, and enhancement of the dissymmetry factor (glum) in the circularly polarized luminescence.

| S-EPMC9834293 | biostudies-literature

Geometric isotope effect of deuteration in a hydrogen-bonded host-guest crystal.

Project description:Deuteration of a hydrogen bond by replacing protium (H) with deuterium (D) can cause geometric changes in the hydrogen bond, known as the geometric H/D isotope effect (GIE). Understanding the GIEs on global structures and bulk properties is of great importance to study structure-property relationships of hydrogen-bonded systems. Here, we report a hydrogen-bonded host-guest crystal, imidazolium hydrogen terephthalate, that exemplifies striking GIEs on its hydrogen bonds, phases, and bulk dielectric transition property. Upon deuteration, the donor-acceptor distance in the O-H···O hydrogen bonds in the host structure is found to increase, which results in a change in the global hydrogen-bonded supramolecular structure and the emergence of a new phase (i.e., isotopic polymorphism). Consequently, the dynamics of the confined guest, which depend on the internal pressure exerted by the host framework, are substantially altered, showing a downward shift of the dielectric switching temperature.

| S-EPMC5797174 | biostudies-literature

Modulation of Water Vapor Sorption by Pore Engineering in Isostructural Square Lattice Topology Coordination Networks.

Project description:We report a crystal-engineering study conducted upon a platform of three mixed-linker square lattice (sql) coordination networks of general formula [Zn(Ria)(bphy)] [bphy = 1,2-bis(pyridin-4-yl)hydrazine, H2Ria = 5-position-substituted isophthalic acid, and R = -Br, -NO2, and -OH; compounds 1-3]. Analysis of single-crystal X-ray diffraction data of 1-2 and the simulated crystal structure of 3 revealed that 1-3 are isomorphous and sustained by bilayers of sql networks linked by hydrogen bonds. Although similar pore shapes and sizes exist in 1-3, distinct isotherm shapes (linear and S shape) and uptakes (2.4, 11.6, and 13.3 wt %, respectively) were observed. Ab initio calculations indicated that the distinct water sorption properties can be attributed to the R groups, which offer a range of hydrophilicity. Calculations indicated that the significantly lower experimental uptake in compound 1 can be attributed to a constricted channel. The calculated water-binding sites provide insights into how adsorbed water molecules bond to the pore walls, with the strongest interactions, water-hydroxyl hydrogen bonding, observed for 3. Overall, this study reveals how pore engineering can result in large variations in water sorption properties in an isomorphous family of rigid porous coordination networks.

| S-EPMC11232023 | biostudies-literature

Linear free energy relationships reveal structural changes in hydrogen-bonded host-guest interactions.

Project description:Hydrogen bond strength in host-guest systems is modulated by many factors including preorganization, steric effects, and electronic effects. To investigate how electronic effects impact barbiturate binding in bifurcated Hamilton receptors, a library of receptors with differing electronic substituents was synthesized and (1)H NMR titrations were performed with diethyl barbital. The Hammett plot revealed a clear break between the different electronic substituents suggesting a change in binding conformation. The titration data were complimented with computational studies confirming the change in structure.

| S-EPMC4260963 | biostudies-literature

Coordination diversity in hydrogen-bonded homoleptic fluoride-alcohol complexes modulates reactivity.

Project description:The nucleophilic reactivity of fluoride ion is altered in the presence of hydrogen-bond donors, including alcohols. Relatively little is known about the coordination involved; to rectify this, the X-ray structures of fourteen novel fluoride-alcohol complexes with tetrabutylammonium as the counterion have been determined. The coordination number varies from two to four depending on the steric bulk of the alcohol and is closely linked to trends in reactivity. This diversity in coordination stoichiometry is unprecedented but significant, as it implies differences in the ability of the fluoride-alcohol complexes to dissociate in solution with release of a more active and/or selective fluoride source.

| S-EPMC5669313 | biostudies-literature

Mechanical measurement of hydrogen bonded host-guest systems under non-equilibrium, near-physiological conditions.

Project description:Decades after the birth of supramolecular chemistry, there are many techniques to measure noncovalent interactions, such as hydrogen bonding, under equilibrium conditions. As ensembles of molecules rapidly lose coherence, we cannot extrapolate bulk data to single-molecule events under non-equilibrium conditions, more relevant to the dynamics of biological systems. We present a new method that exploits the high force resolution of optical tweezers to measure at the single molecule level the mechanical strength of a hydrogen bonded host-guest pair out of equilibrium and under near-physiological conditions. We utilize a DNA reporter to unambiguously isolate single binding events. The Hamilton receptor-cyanuric acid host-guest system is used as a test bed. The force required to dissociate the host-guest system is ∼17 pN and increases with the pulling rate as expected for a system under non-equilibrium conditions. Blocking one of the hydrogen bonding sites results in a significant decrease of the force-to-break by 1-2 pN, pointing out the ability of the method to resolve subtle changes in the mechanical strength of the binding due to the individual H-bonding components. We believe the method will prove to be a versatile tool to address important questions in supramolecular chemistry.

| S-EPMC5625567 | biostudies-literature

Chiral Self-Discrimination and Guest Recognition in Helicene-Based Coordination Cages.

Project description:Chiral nanosized confinements play a major role for enantioselective recognition and reaction control in biological systems. Supramolecular self-assembly gives access to artificial mimics with tunable sizes and properties. Herein, a new family of [Pd2 L4 ] coordination cages based on a chiral [6]helicene backbone is introduced. A racemic mixture of the bis-monodentate pyridyl ligand L1 selectively assembles with PdII cations under chiral self-discrimination to an achiral meso cage, cis-[Pd2 L1P 2 L1M 2 ]. Enantiopure L1 forms homochiral cages [Pd2 L1P/M 4 ]. A longer derivative L2 forms chiral cages [Pd2 L2P/M 4 ] with larger cavities, which bind optical isomers of chiral guests with different affinities. Owing to its distinct chiroptical properties, this cage can distinguish non-chiral guests of different lengths, as they were found to squeeze or elongate the cavity under modulation of the helical pitch of the helicenes. The CD spectroscopic results were supported by ion mobility mass spectrometry.

| S-EPMC6563462 | biostudies-literature

Sodium 2-nitro-cinnamate dihydrate: a one-dimensional hydrogen-bonded coordination polymer.

Project description:The title compound catena-poly[aqua-sodium-μ(2)-aqua-μ(3)-2-nitro-cinnamato], [Na(C(9)H(6)NO(4))(H(2)O)(2)](n), the sodium salt of trans-2-nitro-cinnamic acid, is a one-dimensional coordination polymer based on six-coordinate octa-hedral NaO(6) centres, comprising three facially related monodentate carboxyl-ate O-atom donors from separate ligands (all bridging) [Na-O = 2.4370 (13)-2.5046 (13) Å], and three water mol-ecules (two bridging and one monodentate) [Na-O = 2.3782 (13)-2.4404 (17) Å]. The structure is also stabilized by intra-chain water-carboxyl-ate and water-nitro O-H⋯O hydrogen bonds.

| S-EPMC2969855 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data