The synthesis of a new 120 degree diplatinum(II) acceptor unit and the self-assembly of a series of two-dimensional metallacyclic polypseudorotaxanes that utilize both metal-ligand and crown ether-dialkylammonium noncovalent interactions are described. Judiciously combining complementary diplatinum(II) acceptors with bispyridyl donor building blocks, with an acceptor and/or donor possessing a pendant dibenzo[24]crown-8 (DB24C8) moiety, allows for the formation of three new rhomboidal bis-DB24C8, one new hexagonal tris-DB24C8, and four new hexakis-DB24C8 metallacyclic polygons in quantitative yields. The size and shape of each assembly, as well as the location and stoichiometry of the DB24C8 macrocycle, can be precisely controlled. Each polygon is able to complex two, three, or six dibenzylammonium ions without disrupting the underlying metallacyclic polygons, thus producing eight different poly[2]pseudorotaxanes and demonstrating the utility and scope of this orthogonal self-assembly technique. The assemblies are characterized with one-dimensional multinuclear ((1)H and (31)P) and two-dimensional ((1)H-(1)H COSY and NOESY) NMR spectroscopy as well as mass spectrometry (ESI-MS). Further analysis of the size and shape of each assembly is obtained through molecular force-field simulations. (1)H NMR titration experiments are used to establish thermodynamic binding constants and poly[2]pseudorotaxane/dibenzylammonium stoichiometries. Factors influencing the efficiency of poly[2]pseudorotaxane formation are discussed.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/ja711502t | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Conformer-dependent self-assembled metallacycles with photo-reversible response.
Chem Sci
May 2019
Key Laboratory for Advanced Materials , Institute of Fine Chemicals , Shanghai Key Laboratory of Functional Materials Chemistry , Joint International Research Laboratory of Precision Chemistry and Molecular Engineering , Feringa Nobel Prize Scientist Joint Research Center , School of Chemistry and Molecular Engineering , East China University of Science and Technology, Shanghai 200237 , China . Email:
Discrete, well-defined metallacycles and metallacages with stimuli-responsive behaviors have been largely predominated by the organic donor/metal acceptor paradigm with spontaneous formation of coordination bonds. However, light-driven self-assembly systems usually show relatively low utilization yield of photons and low fatigue resistance. Given that almost no example illustrates the different self-assembly behaviors of antiparallel and parallel conformers in the traditional photochromic diarylethene (DAE) system, here we have for the first time constructed a unique series of photoactive conformer-dependent metallacycles, focusing on the characterization and comparison of self-assembly behavior in different ligand conformers with different di-platinum(ii) acceptors.
View Article and Find Full Text PDFConstruction of Stimuli-Responsive Functional Materials via Hierarchical Self-Assembly Involving Coordination Interactions.
Acc Chem Res
November 2018
Shanghai Key Laboratory of Green Chemistry and Chemical Processes, Chang-Kung Chuang Institute, School of Chemistry and Molecular Engineering , East China Normal University, Shanghai 200062 , People's Republic of China.
Supramolecular self-assembly, which creates the ordered structures as a result of spontaneous organization of building blocks driven by noncovalent interactions (NCIs), is ubiquitous in nature. Recently, it has become increasingly clear that nature often builds up complex structures by employing a hierarchical self-assembly (HSA) strategy, in which the components are brought together in a stepwise process via multiple NCIs. Inspired by the dedicated biological structures in nature, HSA has been widely explored to construct well-defined assemblies with increasing complexity.
View Article and Find Full Text PDFImmobilizing Tetraphenylethylene into Fused Metallacycles: Shape Effects on Fluorescence Emission.
J Am Chem Soc
October 2016
Department of Chemistry, University of Utah, 315 South 1400 East, Room 2020, Salt Lake City, Utah 84112, United States.
Herein, we describe the selective formation of a discrete fused metallarhomboid and a triangle by the careful control of the shape and stoichiometry of the building blocks. A tetraphenylethylene (TPE)-based tetrapyridyl donor is exploited as the bridging component, and coordination immobilization of the TPE unit within the rigid metallacyclic frameworks efficiently suppresses its intramolecular rotational motions. As a result, the fused polygons are innately emissive in dilute solution, representing an alternative to aggregation-induced emission.
View Article and Find Full Text PDFSupramolecular architectures with π-acidic 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine cavities: role of anion-π interactions in the remarkable stability of Fe(II) metallacycles in solution.
J Am Chem Soc
February 2013
Department of Chemistry, Texas A&M University, College Station, Texas 77843, USA.
The comprehensive investigation reported herein provides compelling evidence that anion-π interactions are the main driving force in the formation of self-assembled Fe(II)-templated metallacycles with bptz [3,6-bis(2-pyridyl)-1,2,4,5-tetrazine] in high yields. It was demonstrated by X-ray crystallography, (1)H NMR, solution and solid-state MAS (19)F NMR spectroscopies, CV and MS studies that the anions [X](-) = [BF(4)](-), [ClO(4)](-) and the anions [Y](-) = [SbF(6)](-), [AsF(6)](-), [PF(6)](-) template molecular squares [Fe(4)(bptz)(4)(CH(3)CN)(8)][X](8) and pentagons [Fe(5)(bptz)(5)(CH(3)CN)(10)][Y](10), respectively. The X-ray structures of [{Fe(4)(bptz)(4)(CH(3)CN)(8)}⊂BF(4)][BF(4)](7) and [{Fe(5)(bptz)(5)(CH(3)CN)(10)}⊂2SbF(6)][SbF(6)](8) revealed that the [BF(4)](-) and [SbF(6)](-) anions occupy the π-acidic cavities, establishing close directional F···C(tetrazine) contacts with the tetrazine rings that are by ~0.
View Article and Find Full Text PDFExperimental and theoretical study on the photophysical properties of 90° and 60° bimetallic platinum complexes.
J Phys Chem A
October 2012
State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, People's Republic of China.
The 90° and 60° bimetallic platinum complexes with special structures are widely used in coordination-driven self-assembled metallosupramolecular architectures, and these complexes are the key components of triangular, rectangular, and polygonal metallacycle and metallocage supramolecules. Therefore, spectroscopic techniques and quantum chemistry calculations were employed in this article to investigate the photophysical properties of these bimetallic platinum complexes. Compared with spectra for the ligands, the absorption spectra of these Pt complexes are red-shifted, and the fluorescence spectra become wider and are also red-shifted.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!