Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Versatile supramolecular reactivity of zinc-tetra(4-pyridyl)porphyrin in crystalline solids: Polymeric grids with zinc dichloride and hydrogen-bonded networks with mellitic acid.

ABSTRACT: Crystal engineering studies confirm that the zinc-tetra(4-pyridyl)porphyrin building block reveals versatile supramolecular chemistry. In this work, it was found to be reactive in the assembly of both (a) a 2D polymeric array by a unique combination of self-coordination and coordination through external zinc dichloride linkers and (b) an extended heteromolecular hydrogen-bonded network with mellitic acid sustained by multiple connectivity between the component species.

SUBMITTER: Lipstman S

PROVIDER: S-EPMC2839495 | biostudies-literature | 2009 Dec

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Versatile supramolecular reactivity of zinc-tetra(4-pyridyl)porphyrin in crystalline solids: Polymeric grids with zinc dichloride and hydrogen-bonded networks with mellitic acid.

Lipstman Sophia S Goldberg Israel I

Beilstein journal of organic chemistry 20091211

Crystal engineering studies confirm that the zinc-tetra(4-pyridyl)porphyrin building block reveals versatile supramolecular chemistry. In this work, it was found to be reactive in the assembly of both (a) a 2D polymeric array by a unique combination of self-coordination and coordination through external zinc dichloride linkers and (b) an extended heteromolecular hydrogen-bonded network with mellitic acid sustained by multiple connectivity between the component species. ...[more]

PMID: 20300498

Similar Datasets

Reverse Anti-solvent Crystallization Process for the Facile Synthesis of Zinc Tetra(4-pyridyl)porphyrin Single Crystalline Cubes.

Project description:Synthesis of morphologically well-defined crystals of metalloporphyrin by direct crystallization based on conventional anti-solvent crystallization method without using any additives has been rarely reported. Herein, we demonstrate an unconventional and additive-free synthetic method named reverse anti-solvent crystallization method to achieve well-defined zinc-porphyrin cube crystals by reversing the order of the addition of solvents. The extended first solvation shell effect mechanism is therefore suggested to support the synthetic process by providing a novel kinetic route for reaching the local supersaturation environment depending on the order of addition of solvents, which turned out to be critical to achieve clean cube morphology of the crystal. We believe that our work not only extends fundamental knowledge about the kinetic process in binary solvent systems, but also enables great opportunities for shape-directing crystallization of various organic and organometallic compounds.

| S-EPMC5451467 | biostudies-literature

Computational materials design of crystalline solids.

Project description:The modelling of materials properties and processes from first principles is becoming sufficiently accurate as to facilitate the design and testing of new systems in silico. Computational materials science is both valuable and increasingly necessary for developing novel functional materials and composites that meet the requirements of next-generation technology. A range of simulation techniques are being developed and applied to problems related to materials for energy generation, storage and conversion including solar cells, nuclear reactors, batteries, fuel cells, and catalytic systems. Such techniques may combine crystal-structure prediction (global optimisation), data mining (materials informatics) and high-throughput screening with elements of machine learning. We explore the development process associated with computational materials design, from setting the requirements and descriptors to the development and testing of new materials. As a case study, we critically review progress in the fields of thermoelectrics and photovoltaics, including the simulation of lattice thermal conductivity and the search for Pb-free hybrid halide perovskites. Finally, a number of universal chemical-design principles are advanced.

| S-EPMC5103860 | biostudies-literature

Interacting Quantum Atoms Method for Crystalline Solids.

Project description:An implementation of the Interacting Quantum Atoms method for crystals is presented. It provides a real space energy decomposition of the energy of crystals in which all energy components are physically meaningful. The new package ChemInt enables one to compute intra-atomic and inter-atomic energies, as well as electron population measures used for quantitative description of chemical bonds in crystals. The implementation is tested and applied to characteristic molecular and crystalline systems with different types of bonding.

| S-EPMC8521528 | biostudies-literature

Path planning for the Platonic solids on prescribed grids by edge-rolling.

Project description:The five Platonic solids-tetrahedron, cube, octahedron, dodecahedron, and icosahedron-have found many applications in mathematics, science, and art. Path planning for the Platonic solids had been suggested, but not validated, except for solving the rolling-cube puzzles for a cubic dice. We developed a path-planning algorithm based on the breadth-first-search algorithm that generates a shortest path for each Platonic solid to reach a desired pose, including position and orientation, from an initial one on prescribed grids by edge-rolling. While it is straightforward to generate triangular and square grids, various methods exist for regular-pentagon tiling. We chose the Penrose tiling because it has five-fold symmetry. We discovered that a tetrahedron could achieve only one orientation for a particular position.

| S-EPMC8171926 | biostudies-literature

Supramolecular allosteric cofacial porphyrin complexes.

Project description:Nature routinely uses cooperative interactions to regulate cellular activity. For years, chemists have designed synthetic systems that aim toward harnessing the reactivity common to natural biological systems. By learning how to control these interactions in situ, one begins to allow for the preparation of man-made biomimetic systems that can efficiently mimic the interactions found in Nature. To this end, we have designed a synthetic protocol for the preparation of flexible metal-directed supramolecular cofacial porphyrin complexes which are readily obtained in greater than 90% yield through the use of new hemilabile porphyrin ligands with bifunctional ether-phosphine or thioether-phosphine substituents at the 5 and 15 positions on the porphyrin ring. The resulting architectures contain two hemilabile ligand-metal domains (RhI or CuI sites) and two cofacially aligned porphyrins (ZnII sites), offering orthogonal functionalities and allowing these multimetallic complexes to exist in two states, "condensed" or "open". Combining the ether-phosphine ligand with the appropriate RhI or CuI transition-metal precursors results in "open" macrocyclic products. In contrast, reacting the thioether-phosphine ligand with RhI or CuI precursors yields condensed structures that can be converted into their "open" macrocyclic forms via introduction of additional ancillary ligands. The change in cavity size that occurs allows these structures to function as allosteric catalysts for the acyl transfer reaction between X-pyridylcarbinol (where X = 2, 3, or 4) and 1-acetylimidazole. For 3- and 4-pyridylcarbinol, the "open" macrocycle accelerates the acyl transfer reaction more than the condensed analogue and significantly more than the porphyrin monomer. In contrast, an allosteric effect was not observed for 2-pyridylcarbinol, which is expected to be a weaker binder and is unfavorably constrained inside the macrocyclic cavity.

| S-EPMC2525615 | biostudies-literature

Self-complementary double-stranded porphyrin arrays assembled from an alternating pyridyl-porphyrin sequence.

Project description:Oligomeric porphyrin arrays with an alternating pyridyl-porphyrin sequence were synthesized to explore double-strand formation through self-complementary pyridyl-to-zinc axial coordination bonds. Competitive titration experiments revealed the thermodynamic aspects involved in the zipper effect within double-strand formation. Multiple axial coordination bonds defined the stacked conformation, despite a marginal contribution to the stability of the double-strands. Thus, the zipper cooperativity was the dominant factor for the remarkable stability. Moreover, the dimeric and trimeric porphyrin arrays were independently assembled into double-strands by self-sorting from a binary mixture. Double-strand formation engineered discretely stacked π-systems. Successive slipped-cofacial stacks of the porphyrin rings progressively extended the π-system via exciton coupling over the double-strand while keeping a relatively high fluorescence quantum yield.

| S-EPMC6054142 | biostudies-literature

Molecule-displacive ferroelectricity in organic supramolecular solids.

Project description:Ferroelectricity is essential to many forms of current technology, ranging from sensors and actuators to optical or memory devices. In this circumstance, organic ferroelectrics are of particular importance because of their potential application in tomorrow's organic devices, and several pure organic ferroelectrics have been recently developed. However, some problems, such as current leakage and/or low working frequencies, make their application prospects especially for ferroelectric memory (FeRAM) not clear. Here, we describe the molecule-displacive ferroelectricity of supramolecular adducts of tartaric acid and 1,4-diazabicyclo[2.2.2]octane N,N'-dioxide. The adducts show large spontaneous polarization, high rectangularity of the ferroelectric hysteresis loops even at high operation frequency (10?kHz), and high performance in polarization switching up to 1 × 10? times without showing fatigue. It opens great perspectives in terms of applications, especially in organic FeRAM.

| S-EPMC3718360 | biostudies-literature

Effect of zinc cations on the kinetics of supramolecular assembly and the chirality of porphyrin J-aggregates.

Project description:Dilute aqueous solutions of anionic meso-4-sulfonatophenyl-porphyrin (TPPS) extract zinc(ii) ions from glass or quartz surfaces at room temperature and efficiently form the corresponding metal complex (ZnTPPS). The partial or complete formation of ZnTPPS has been probed by UV/Vis spectroscopy and both static and time-resolved fluorescence. The source of zinc(ii) ions has been clearly identified through inductively coupled plasma optical emission spectrometry. The presence of increasing amounts of ZnTPPS slows down the rate of TPPS J-aggregate formation in acid solution. This influences the nucleation step and has a profound impact on the onset of chirality in these species. This evidence indicates the important role of this adventitious metal ion in the interpretation of various spectroscopic and kinetic data for the self-assembly of the TPPS porphyrin and provides some insights into controversial findings on their chirality. The use of this metal derivative as the starting compound for in situ formation of monomeric TPPS is suggested.

| S-EPMC5354048 | biostudies-literature

Supramolecular anion recognition in water: synthesis of hydrogen-bonded supramolecular frameworks.

Project description:The interaction of tetratopic amidinium-containing receptors with terephthalate anions leads to porous framework materials assembled through charge-assisted hydrogen bonds. The frameworks form in good yield within minutes in water at room temperature, but no framework material is obtained if other anions (Cl-, Br-, NO3-, SO42- or isophthalate2-) are used in place of terephthalate. Two forms of the framework can be prepared: one with a connected pore network, and a more dense phase with discrete voids. We demonstrate that these are the kinetic and thermodynamic products, respectively. Either framework can be prepared independently and can be converted to the other form in response to stimuli. Furthermore, the frameworks can be controllably disassembled and reassembled in response to acid/base triggers suggesting that this new class of materials may have applications in the selective encapsulation and release of guests.

| S-EPMC5380882 | biostudies-literature

Tris(ethyl-enediamine)zinc(II) dichloride monohydrate.

Project description:The asymmetric unit of the title compound, [Zn(C(2)H(8)N(2))(3)]Cl(2)·H(2)O, contains a discrete [Zn(C(2)H(8)N(2))(3)](2+) cation with a distorted octa-hedral geometry around Zn, two uncoordinated chloride ions and one water mol-ecule. The crystal structure exhibits N-H⋯O, N-H⋯Cl and O-H⋯O hydrogen bonds.

| S-EPMC2959473 | 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