Variously substituted coordinating rigid rods have been synthesized which incorporate a central 4,7-phenanthroline nucleus attached to two 2-pyridyl groups via its 3 and 8 positions, so as to yield bis-bidentate chelates, the two-coordinating axes of the chelates being parallel to one another. Regardless of the nature of the substituents borne by the rods, the copper(I)-induced threading reaction of two such rods through the rings of two bis-macrocycles affords in a quantitative yield the 4-copper(I) threaded assembly. The [2]pseudorotaxane tetramers thus obtained have been fully characterized in solution and, for one of them, an X-ray structure could be obtained, confirming the threaded nature of the complex and providing important structural information.
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http://dx.doi.org/10.1021/ja801924y | DOI Listing |
Acc Chem Res
June 2018
Department of Chemistry , National Taiwan University, No. 1, Sec. 4, Roosevelt Road , Taipei , Taiwan.
In 1987, Pedersen, Cram, and Lehn were awarded the Nobel Prize in Chemistry to honor their achievements in, among other things, the selective recognition of alkali metal ions by synthetic hosts. Almost three decades later, the 2016 Nobel Prize went to Stoddart, Sauvage, and Feringa for the development of artificial molecular machines, in which interlocked molecules play a significant role. Surprisingly, although many rotaxane- and catenane-based molecular machines have been constructed using various templating approaches, alkali metal ions, which are good templates for crown ether synthesis, have only rarely been applied as templates for the assembly of these interlocked molecules.
View Article and Find Full Text PDFChemistry
July 2015
Laboratory of Nuclear Energy Chemistry and Key Laboratory for Biomedical Effects of Nanomaterials and Nanosafety, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (P.R. China).
Introduction of mechanically interlocked components into actinide-based metal-organic materials such as polyrotaxanes will generate an entirely new type of inorganic-organic hybrid materials showing more supramolecular encapsulation-based dynamics. In this work, tetranuclear uranyl-directed polyrotaxanes (UO2 )4 O2 -C5A3-CB6 (1) and (UO2 )4 O2 -C6A3-CB6 (2), which are the first actinide pseudorotaxanes with high-nuclearity uranium centers, were obtained through systematic extension of the string spacer in pseudorotaxane ligands from 1,4-butylene (C4) to 1,5-pentylene (C5) and 1,6-hexylene (C6). Both of the as-synthesized tetranuclear uranyl polyrotaxanes were structurally characterized and analyzed.
View Article and Find Full Text PDFChemistry
May 2011
Laboratoire de Chimie Organo-Minérale, Institut de Chimie, Université de Strasbourg-CNRS/UMR 7177, 4, rue Blaise Pascal, 67070 Strasbourg-Cedex, France.
By using the "gathering-and-threading" effect of copper(I) with rigid ring-and-string conjugates, daisy-chain-type [3]- and [4]pseudorotaxanes could be prepared in high yields. The organic fragment used consisted of a 2,9-diphenyl-1,10-phenanthroline (dpp)-containing ring attached to a coordinating filament capable of threading through the ring of another molecule by coordination to copper(I). The bidentate chelate introduced in the axis was also a 1,10-phenanthroline (phen) derivative with two methyl groups ortho to the nitrogen atoms of the phen unit.
View Article and Find Full Text PDFOrg Biomol Chem
September 2008
Institute for Materials Chemistry and Engineering, Kyushu University, Moto-oka 744, Fukuoka 819-0395, Japan.
Rotaxane-type receptors, which were composed of anionic cyclophane-based resorcinarene tetramers as the wheel and a 2,6-disubstituted naphthalene derivative having two fluorophore moieties, such as fluorescein and rhodamine residues, as the axle ( and , respectively), were prepared. Rotaxane-type receptors and bound histone, a small basic protein component of eukaryotic chromatins, with binding constants of 2.3 x 10(6) and 9.
View Article and Find Full Text PDFJ Am Chem Soc
August 2008
Laboratoire de Chimie Ogano-Minerale, LC3 UMR 7177 du CNRS, Universite Louis Pasteur, Institut de Chimie, 4 rue Blaise Pascal, 67070 Strasbourg Cedex, France.
Variously substituted coordinating rigid rods have been synthesized which incorporate a central 4,7-phenanthroline nucleus attached to two 2-pyridyl groups via its 3 and 8 positions, so as to yield bis-bidentate chelates, the two-coordinating axes of the chelates being parallel to one another. Regardless of the nature of the substituents borne by the rods, the copper(I)-induced threading reaction of two such rods through the rings of two bis-macrocycles affords in a quantitative yield the 4-copper(I) threaded assembly. The [2]pseudorotaxane tetramers thus obtained have been fully characterized in solution and, for one of them, an X-ray structure could be obtained, confirming the threaded nature of the complex and providing important structural information.
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