Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Cobaloximes as Building Blocks in Halogen-Bonded Cocrystals.

ABSTRACT: In this work, we explore the halogen-bonded cocrystallization potential of cobaloxime complexes in the synthesis of cocrystals with perhalogenated benzenes. We demonstrate a strategy for synthesizing halogen-bonded metal-organic cocrystals by utilizing cobaloximes whose pendant bromide group and oxime oxygen enable halogen bonding. By combining three well-known halogen bond donor molecules differing in binding geometry and composition with three cobaloxime units, we obtained a total of four previously unreported cocrystals. Single crystal X-ray diffraction experiments showed that the majority of obtained cocrystals exhibited the formation of the targeted I···O and I···Br motives. These results illustrate the potential of cobaloximes as halogen bond acceptors and indicate that this type of halogen bond acceptors may offer a novel route to metal-organic halogen-bonded cocrystals.

SUBMITTER: Bedekovic N

PROVIDER: S-EPMC7287722 | biostudies-literature | 2020 May

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Cobaloximes as Building Blocks in Halogen-Bonded Cocrystals.

Bedeković Nikola N Martinez Valentina V Topić Edi E Stilinović Vladimir V Cinčić Dominik D

Materials (Basel, Switzerland) 20200521 10

In this work, we explore the halogen-bonded cocrystallization potential of cobaloxime complexes in the synthesis of cocrystals with perhalogenated benzenes. We demonstrate a strategy for synthesizing halogen-bonded metal-organic cocrystals by utilizing cobaloximes whose pendant bromide group and oxime oxygen enable halogen bonding. By combining three well-known halogen bond donor molecules differing in binding geometry and composition with three cobaloxime units, we obtained a total of four prev ...[more]

PMID: 32455679

Similar Datasets

Uracil Derivatives for Halogen-Bonded Cocrystals.

Project description:Among non-covalent interactions, halogen bonding is emerging as a new powerful tool for supramolecular self-assembly. Here, along with a green and effective method, we report three new halogen-bonded cocrystals containing uracil derivatives and 1,2,4,5-tetrafluoro-3,6-diiodobenzene as X-bond donor coformer. These multicomponent solids were prepared both by solvent-drop grinding and solution methods and further characterized by powder and single-crystal X-ray diffraction, Fourier-transformed infrared spectroscopy, and thermal methods (TGA-DSC). In order to study the relative importance of hydrogen versus halogen bonds in the crystal packing, computational methods were applied.

| S-EPMC8508742 | biostudies-literature

Conservation of the Hydrogen-Bonded Pyridone Homosynthon in Halogen-Bonded Cocrystals.

Project description:Seven cocrystals of pyridone and perfluorinated halocarbons have been prepared. In all cases pairs of pyridone molecules are connected into dimers by two N-H···O hydrogen bonds, forming the characteristic pyridone homosynthon of R2 2(8) topology. These dimers further act as acceptors of halogen bonds through the two pyridone oxygen atoms, forming two (in six cases) or three (in one case) halogen bonds with the donor molecules. The stoichiometry of the cocrystals obtained and the overall topology of the supramolecular architecture depend primarily on the topicity of the halogen bond donor, with the monotopic donor yielding a cocrystal of 1:1 stoichiometry comprising discrete supramolecular complexes, the ditopic donors cocrystals of 1:2 stoichiometry comprising chains, and the tritopic donor a cocrystal of 1:2 stoichiometry comprising hydrogen- and halogen-bonded layers. The results indicate that the pyridone homosynthon is a robust and reliable supramolecular synthon that is conserved in halogen-bonded cocrystals of pyridone.

| S-EPMC8861932 | biostudies-literature

Halogen-Bonded Supramolecular Parallelograms: From Self-Complementary Iodoalkyne Halogen-Bonded Dimers to 1:1 and 2:2 Iodoalkyne Halogen-Bonded Cocrystals

Project description: Not available

| S-EPMC10885002 | biostudies-literature

Supramolecular Sandwiches: Halogen-Bonded Coformers Direct [2+2] Photoreactivity in Two-Component Cocrystals.

Project description:The halogen-bond (X-bond) donors 1,3- and 1,4-diiodotetrafluorobenzene (1,3-di-I-tFb and 1,4-di-I-tFb, respectively) form cocrystals with trans-1,2-bis(2-pyridyl)ethylene (2,2'-bpe) assembled by N···I X-bonds. In each cocrystal, 2(1,3-di-I-tFb)·2(2,2'-bpe) and (1,4-di-I-tFb)·(2,2'-bpe), the donor molecules support the C=C bonds of 2,2'-bpe to undergo an intermolecular [2+2] photodimerization. UV irradiation of each cocrystal resulted in stereospecific and quantitative conversion of 2,2'-bpe to rctt-tetrakis(2-pyridyl)cyclobutane (2,2'-tpcb). In each case, the reactivity occurs via face-to-face ?-stacked columns wherein nearest-neighbor pairs of 2,2'-bpe molecules lie sandwiched between X-bond donor molecules. Nearest-neighbor C=C bonds are stacked criss-crossed in both cocrystals. The reactivity was ascribed to the olefins undergoing pedal-like motion in the solid state. The stereochemistry of 2,2'-tpcb is confirmed in cocrystals 2(1,3-di-I-tFb)·(2,2'-tpcb) and (1,4-di-I-tFb)·(2,2'-tpcb).

| S-EPMC7070622 | biostudies-literature

Computational evaluation of halogen-bonded cocrystals enables prediction of their mechanochemical interconversion reactions.

Project description:Periodic density-functional theory (DFT) calculations were used to predict the thermodynamic stability and the likelihood of interconversion between a series of halogen-bonded cocrystals. The outcomes of mechanochemical transformations were in excellent agreement with the theoretical predictions, demonstrating the power of periodic DFT as a method for designing solid-state mechanochemical reactions prior to experimental work. Furthermore, the calculated DFT energies were compared with experimental dissolution calorimetry measurements, marking the first such benchmark for the accuracy of periodic DFT calculations in modelling transformations of halogen-bonded molecular crystals.

| S-EPMC10033997 | biostudies-literature

Fluorinated azobenzenes as supramolecular halogen-bonding building blocks.

Project description:ortho-Fluoroazobenzenes are a remarkable example of bistable photoswitches, addressable by visible light. Symmetrical, highly fluorinated azobenzenes bearing an iodine substituent in para-position were shown to be suitable supramolecular building blocks both in solution and in the solid state in combination with neutral halogen bonding acceptors, such as lutidines. Therefore, we investigate the photochemistry of a series of azobenzene photoswitches. Upon introduction of iodoethynyl groups, the halogen bonding donor properties are significantly strengthened in solution. However, the bathochromic shift of the ???* band leads to a partial overlap with the n??* band, making it slightly more difficult to address. The introduction of iodine substituents is furthermore accompanied with a diminishing thermal half-life. A series of three azobenzenes with different halogen bonding donor properties are discussed in relation to their changing photophysical properties, rationalized by DFT calculations.

| S-EPMC6720338 | biostudies-literature

Practical Synthesis and Application of Halogen-Doped Pyrrole Building Blocks.

Project description:A practical access to four new halogen-substituted pyrrole building blocks was realized in two to five synthetic steps from commercially available starting materials. The target compounds were prepared on a 50 mg to 1 g scale, and their conversion to nanomolar inhibitors of bacterial DNA gyrase B was demonstrated for three of the prepared building blocks to showcase the usefulness of such chemical motifs in medicinal chemistry.

| S-EPMC8047689 | biostudies-literature

Building blocks for recognition-encoded oligoesters that form H-bonded duplexes.

Project description:Competition from intramolecular folding is a major challenge in the design of synthetic oligomers that form intermolecular duplexes in a sequence-selective manner. One strategy is to use very rigid backbones that prevent folding, but this design can prejudice duplex formation if the geometry is not exactly right. The alternative approach found in nucleic acids is to use bases (or recognition units) that have different dimensions. A long-short base-pairing scheme makes folding geometrically difficult and is compatible with the flexible backbones that are required to guarantee duplex formation. A monomer building block equipped with a long hydrogen bond donor (phenol, D) recognition unit and a monomer building block equipped with a short hydrogen bond acceptor (phosphine oxide, A) recognition unit were prepared with differentially protected alcohol and carboxylic acid groups. These compounds were used to synthesise the homo and hetero-sequence 2-mers AA, DD and AD. 19F and 31P NMR experiments were used to characterize the assembly properties of these compounds in toluene solution. AA and DD form a stable doubly-hydrogen-bonded duplex with an effective molarity of 20 mM for formation of the second intramolecular hydrogen bond. AD forms a duplex of similar stability. There is no evidence of intramolecular folding in the monomeric state of this compound, which shows that the long-short base-pairing scheme is effective. The ester coupling chemistry used here is an attractive method for the synthesis of long oligomers, and the properties of the 2-mers indicate that this molecular architecture should give longer mixed sequence oligomers that show high fidelity sequence-selective duplex formation.

| S-EPMC6385898 | biostudies-other

Self-Assembly of Supramolecular Architectures Driven by σ-Hole Interactions: A Halogen-Bonded 2D Network Based on a Diiminedibromido Gold(III) Complex and Tribromide Building Blocks.

Project description:The reaction of the complex [Au(phen)Br2](PF6) (phen = 1,10-phenanthroline) with molecular dibromine afforded {[Au(phen)Br2](Br3)}∞ (1). Single crystal diffraction analysis showed that the [Au(phen)Br2]+ complex cations were bridged by asymmetric tribromide anions to form infinite zig-zag chains featuring the motif ···Au-Br···Br-Br-Br···Au-Br···Br-Br-Br···. The complex cation played an unprecedented halogen bonding (XB) donor role engaging type-I and type-II XB noncovalent interactions of comparable strength with symmetry related [Br3]- anions. A network of hydrogen bonds connects parallel chains in an infinite 2D network, contributing to the layered supramolecular architecture. DFT calculations allowed clarification of the nature of the XB interactions, showing the interplay between orbital mixing, analyzed at the NBO level, and electrostatic contribution, explored based on the molecular potential energy (MEP) maps of the interacting synthons.

| S-EPMC9571214 | biostudies-literature

Halogen-bonded shape memory polymers.

Project description:Halogen bonding (XB), a non-covalent interaction between an electron-deficient halogen atom and a Lewis base, is widely adopted in organic synthesis and supramolecular crystal engineering. However, the roadmap towards materials applications is hindered by the challenges in harnessing this relatively weak intermolecular interaction to devise human-commanded stimuli-responsive soft materials. Here, we report a liquid crystalline network comprising permanent covalent crosslinks and dynamic halogen bond crosslinks, which possess reversible thermo-responsive shape memory behaviour. Our findings suggest that I···N halogen bond, a paradigmatic motif in crystal engineering studies, enables temporary shape fixation at room temperature and subsequent shape recovery in response to human body temperature. We demonstrate versatile shape programming of the halogen-bonded polymer networks through human-hand operation and propose a micro-robotic injection model for complex 1D to 3D shape morphing in aqueous media at 37 °C. Through systematic structure-property-performance studies, we show the necessity of the I···N crosslinks in driving the shape memory effect. The halogen-bonded shape memory polymers expand the toolbox for the preparation of smart supramolecular constructs with tailored mechanical properties and thermoresponsive behaviour, for the needs of, e.g., future medical devices.

| S-EPMC9723116 | 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