Browse
Submit Data
Databases
API
Help

Dataset Information

20 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Construction of functionalized metallosupramolecular tetragonal prisms via multicomponent coordination-driven self-assembly.

ABSTRACT: A new approach for the construction of functionalized metallosupramolecular tetragonal prisms via multicomponent, coordination-driven, template-free self-assembly is described. The combination of tetra-(4-pyridylphenyl)ethylene, a 90° Pt(II) acceptor, and ditopic bipyridine or carboxylate ligands functionalized with hydroxyl or amine groups, hydrophobic alkyl chains, or electrochemically active ferrocene, yields a suite of seven self-assembled tetragonal prisms under mild conditions. These three-dimensional metallosupramolecules were characterized by multinuclear NMR ((31)P and (1)H) and mass spectrometry. Their shapes and sizes were established using Merck Molecular Force Field (MMFF) simulations. In addition, their approximate sizes were further supported by pulsed-field-gradient spin-echo (PGSE) NMR experiments.

SUBMITTER: Wang M

PROVIDER: S-EPMC3133929 | biostudies-literature | 2011 Jul

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Construction of functionalized metallosupramolecular tetragonal prisms via multicomponent coordination-driven self-assembly.

Wang Ming M Zheng Yao-Rong YR Cook Timothy R TR Stang Peter J PJ

Inorganic chemistry 20110602 13

A new approach for the construction of functionalized metallosupramolecular tetragonal prisms via multicomponent, coordination-driven, template-free self-assembly is described. The combination of tetra-(4-pyridylphenyl)ethylene, a 90° Pt(II) acceptor, and ditopic bipyridine or carboxylate ligands functionalized with hydroxyl or amine groups, hydrophobic alkyl chains, or electrochemically active ferrocene, yields a suite of seven self-assembled tetragonal prisms under mild conditions. These three ...[more]

PMID: 21634384

Similar Datasets

Metallosupramolecular tetragonal prisms via multicomponent coordination-driven template-free self-assembly.

Project description:We present a general strategy for the synthesis of stable 3-D metallosupramolecular tetragonal prisms in which multicomponent coordination-driven self-assembly allows for single supramolecular species to be formed. The appropriate stoichiometric combination of a tetraphenylethylene-based tetratopic donor (1), a linear dipyridine donor (2), and a 90 degrees platinum metal complex (3) affords tetragonal prisms (4) as single products. The compounds have been characterized by multinuclear NMR spectroscopy and electrospray ionization mass spectrometry. The size of the supramolecules was determined by pulsed-gradient spin-echo NMR and modeled with molecular force field simulation methods.

| S-EPMC2871951 | biostudies-literature

Construction of hexagonal prisms of variable size via coordination-driven multicomponent self-assembly.

Project description:The coordination-driven self-assembly of supramolecular hexagonal prisms has been achieved upon mixing a hexakis[4-(4-pyridyl)phenyl]benzene donor ligand and carboxylate donor ligands such as sodium terephthalate, sodium (1,1'-biphenyl)-4,4'-dicarboxylate, sodium 4,4'-(diazene-1,2-diyl)dibenzoate, and 4,4'-dipyridyl with cis-Pt(PEt(3))(2)(OTf)(2) in a 1:3:6 ratio. Four assembled hexagonal prisms have been characterized by (31)P and (1)H NMR multinuclear spectroscopy as well as electrospray ionization mass spectrometry. Molecular force-field simulations provide the possible conformation and size of each structure.

| S-EPMC2946450 | biostudies-literature

Post-self-assembly covalent chemistry of discrete multicomponent metallosupramolecular hexagonal prisms.

Project description:The multicomponent coordination-driven self-assembly of hexakis[4-(4-pyridyl)phenyl]benzene, cis-(PEt(3))(2)Pt(II)(OTf)(2), and amine- or maleimide-functionalized isophthalate forms discrete hexagonal prisms as single reaction products. The amino or maleimide groups decorating the isophthalate pillars of the prisms provide reactive sites for post-self-asssembly modifications. In this communication, we demonstrate that the hexagonal prisms can be functionalized without disrupting the prismatic cores, enabling the incorporation of new functionalities under mild conditions.

| S-EPMC3135717 | biostudies-literature

Construction of endo-functionalized two dimensional metallacycles via coordination-driven self-assembly.

Project description:The synthesis of three endofunctionalized two-dimensional supramolecular metallacycles including two [2 + 2] rhomboids (5 and 6) and a [3 + 3] hexagon (7) is reported. The resulting self-assembled supramolecular structures, containing several nitrobenzyl moieties at their interior surface, have been fully characterized by multinuclear NMR ((31)P and (1)H) and electrospray ionization mass spectrometry. A significant C-H...O hydrogen bonding between the nitrobenzyl acceptor and the edge molecules of the supramolecular architecture is observed in the small rhomboid 5 and this interaction gradually decreases upon the enlargement of the resulting polygonal structures from a small rhomboid 5 through a large rhomboid 6 to a hexagon 7. Molecular modeling with the MMFF force field gives a possible conformation of each self-assembly in different solvents and shows that the hydrophilic nitrobenzyl moiety prefers to be buried in the cavity of the resulting polygonal structures in nonpolar solvents, thus forming hydrogen bonds with the peripheral component building units.

| S-EPMC2802277 | biostudies-literature

Multicomponent supramolecular systems: self-organization in coordination-driven self-assembly.

Project description:The self-organization of multicomponent supramolecular systems involving a variety of two-dimensional (2 D) polygons and three-dimensional (3 D) cages is presented. Nine self-organizing systems, SS(1)-SS(9), have been studied. Each involves the simultaneous mixing of organoplatinum acceptors and pyridyl donors of varying geometry and their selective self-assembly into three to four specific 2 D (rectangular, triangular, and rhomboid) and/or 3 D (triangular prism and distorted and nondistorted trigonal bipyramidal) supramolecules. The formation of these discrete structures is characterized using NMR spectroscopy and electrospray ionization mass spectrometry (ESI-MS). In all cases, the self-organization process is directed by: 1) the geometric information encoded within the molecular subunits and 2) a thermodynamically driven dynamic self-correction process. The result is the selective self-assembly of multiple discrete products from a randomly formed complex. The influence of key experimental variables--temperature and solvent--on the self-correction process and the fidelity of the resulting self-organization systems is also described.

| S-EPMC2765196 | biostudies-literature

Coordination-driven face-directed self-assembly of trigonal prisms. Face-based conformational chirality.

Project description:The coordination-driven self-assembly of four different trigonal prisms from 3 equiv of one of four different tetrapyridyl star connectors and 6 equiv of a platinum linker dication in nitromethane is presented. This face-directed approach affords high yields without template assistance. The prisms have been characterized by multinuclear and DOSY NMR and dual ESI-FT-ICR mass spectrometry. The use of a conformationally chiral star connector leads to a conformationally chiral prism when connector arm ends attached to a vertex have a strongly correlated twist sense and chirality is communicated across polyhedral faces, edges, and vertices. Molecular mechanics results suggest that in the smallest prism 3d collective effects dominate and the all-P and all-M conformers are strongly favored. NMR data prove that the two edges of the pyridine rings in the triflate salts of 3a-3d are distinct. An Eyring plot of rates obtained from line-shape analysis and 1-D EXCHSY NMR yields an activation enthalpy DeltaH(double dagger) of approximately 12 kcal/mol and activation entropy DeltaS(double dagger) of approximately -15 cal/mol x K for the edge interconversion process, compatible with pyridine rotation around the Pt-N bond. For 3c, this behavior is observed only up to approximately 318 K. At higher temperatures, the Eyring plot is again linear but follows a very different straight line, with a DeltaH(double dagger) of approximately 35 kcal/mol and DeltaS(double dagger) of approximately 60 cal/mol x K. This highly unusual result is further investigated and discussed in the following companion paper.

| S-EPMC5827968 | biostudies-literature

Construction of multifunctional cuboctahedra via coordination-driven self-assembly.

Project description:We present a general strategy for the synthesis of stable, multifunctional cuboctahedral complexes in which coordination-driven self-assembly allows for precise control over positioning of either ferrocene or crown ether functionalities. The appropriate stoichiometric combination of functionalized 120 degree diplatinum acceptor units with tritopic donor units afforded supramolecular cuboctahedra with covalently linked functional groups. The compounds are characterized by multinuclear NMR spectroscopy, electrospray ionization mass spectrometry, and electrochemistry.

| S-EPMC2775065 | biostudies-literature

Synthesis and photophysical studies of self-assembled multicomponent supramolecular coordination prisms bearing porphyrin faces.

Project description:Multicomponent self-assembly, wherein two unique donor precursors are combined with a single metal acceptor instead of the more common two-component assembly, can be achieved by selecting Lewis-basic sites and metal nodes that select for heteroligated coordination spheres. Platinum(II) ions show a thermodynamic preference for mixed pyridyl/carboxylate coordination environments and are thus suitable for such designs. The use of three or more unique building blocks increases the structural complexity of supramolecules. Herein, we describe the synthesis and characterization of rectangular prismatic supramolecular coordination complexes (SCCs) with two faces occupied by porphyrin molecules, motivated by the search for new multichromophore complexes with promising light-harvesting properties. These prisms are obtained from the self-assembly of a 90° Pt(II) acceptor with a meso-substituted tetrapyridylporphyrin (TPyP) and dicarboxylate ligands. The generality of this self-assembly reaction is demonstrated using five dicarboxylate ligands, two based on a rigid central phenyl ring and three alkyl-spaced variants, to form a total of five free-base and five Zn-metallated porphyrin prisms. All 10 SCCs are characterized by (31)P and (1)H multinuclear NMR spectroscopy and electrospray ionization mass spectrometry, confirming the structure of each self-assembly and the stoichiometry of formation. The photophysical properties of the resulting SCCs were investigated revealing that the absorption and emission properties of the free-base and metallated porphyrin prisms preserve the spectral features associated with free TPyP.

| S-EPMC4084423 | biostudies-literature

Model-driven optimization of multicomponent self-assembly processes.

Project description:Here, we report an engineering approach toward multicomponent self-assembly processes by developing a methodology to circumvent spurious, metastable assemblies. The formation of metastable aggregates often hampers self-assembly of molecular building blocks into the desired nanostructures. Strategies are explored to master the pathway complexity and avoid off-pathway aggregates by optimizing the rate of assembly along the correct pathway. We study as a model system the coassembly of two monomers, the R- and S-chiral enantiomers of a ?-conjugated oligo(p-phenylene vinylene) derivative. Coassembly kinetics are analyzed by developing a kinetic model, which reveals the initial assembly of metastable structures buffering free monomers and thereby slows the formation of thermodynamically stable assemblies. These metastable assemblies exert greater influence on the thermodynamically favored self-assembly pathway if the ratio between both monomers approaches 1:1, in agreement with experimental results. Moreover, competition by metastable assemblies is highly temperature dependent and hampers the assembly of equilibrium nanostructures most effectively at intermediate temperatures. We demonstrate that the rate of the assembly process may be optimized by tuning the cooling rate. Finally, it is shown by simulation that increasing the driving force for assembly stepwise by changing the solvent composition may circumvent metastable pathways and thereby force the assembly process directly into the correct pathway.

| S-EPMC3808594 | biostudies-literature

Coordination-driven self-assembly of three-dimensional supramolecular dendrimers.

Project description:The design and synthesis of novel three-dimensional (3-D) supramolecular dendrimers is described. The coordination-driven self-assembly of a 120 degrees diplatinum acceptor and tritopic pyridyl donors bearing [G-0]-[G-3] Fréchet-type dendrons results in a series of supramolecular dendrimers under mild conditions, possessing a robust adamantanoid core of well-defined shape and size. The assemblies were identified using multinuclear ((31)P and (1)H) NMR spectroscopy and electrospray ionization mass spectrometry, as well as pulsed-field-gradient spin-echo (PGSE) NMR measurement together with computational simulations. Isotopically resolved mass spectral data support the existence of the [6 + 4] assembly of adamantanoid dendrimers, and the NMR results are consistent with the formation of these symmetrical assemblies. PGSE NMR measurements together with MMFF force-field modeling clearly reveal the structural feature of the 3-D supramolecular dendrimers with varying sizes.

| S-EPMC2895422 | 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