Global Chirality in Rigid Decametallic Ruthenium Dendrimers

Kim, Mahn Jong; MacDonnell, Frederick M.; Gimon-Kinsel, Mary E.; Bois, Thomas Du; Asgharian, Niloofar; Griener, James C.

doi:10.1002/(sici)1521-3773(20000204)39:3<615::aid-anie615>3.0.co;2-3

Cited by 43 publications

(34 citation statements)

References 29 publications

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“…27 3 ] 2+ units to form the large supramolecular system shown in Figure 1. Previously reported semiempirical (PM3) computation and spectroscopic characterization of this decamer 21 confirm that the molecule is planar, highly symmetric, and rigid with respect to molecular fluctuation. While all of the Ru centers lie in a plane, the complex is 3D with a thickness of 0.9 nm.…”

Section: Introductionmentioning

confidence: 99%

Binding of Rigid Dendritic Ruthenium Complexes to Carbon Nanotubes

Chaturvedi

Poler

2006

J. Phys. Chem. B

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Single-walled carbon nanotubes (SWNTs) bind strongly to rigid ruthenium metallodendrimers. High valence ions effectively coagulate these nanotubes from stable dispersions in N,N-dimethylforamide. While ruthenium salts and small [Ru(diimine)(3)](2+) complexes also coagulate the nanotubes, they require much higher concentrations and are easily extracted from the nanotubes with acetonitrile. Enantiomerically pure ruthenium metallodendrimer [Lambda(6)Delta(3)Lambda-Ru(10)](20+)[PF(6)(-)](20) is shown to bind strongly and specifically to the SWNTs. Most of the nanotube's ends are functionalized with this large (5.8 nm), optically active, rigid supramolecular complex. We study the binding capacity with UV-vis and atomic absorption spectroscopy. Imaging the functionalized nanotubes with scanning electron microscopy and atomic force microscopy (AFM) yields direct confirmation of end functionalization. Statistical analysis of the AFM images shows the morphology of the functionalized ends is consistent with the nanotubes binding to one of the endo- or exoreceptors around the dendrimer. Implications of these results toward efficient nanomanufacturing of carbon nanotube devices are discussed.

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Section: Introductionmentioning

confidence: 99%

Binding of Rigid Dendritic Ruthenium Complexes to Carbon Nanotubes

Chaturvedi

Poler

2006

J. Phys. Chem. B

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“…The design and synthesis of ruthenium(II) complexes consisting of polypyridyl ligands have attracted great interest in recent years because of their possible applications in photochemical and electrochemical molecular devices, such as molecular wires, artificial antenna systems, and photoswitches, due to their unique electrochemical and photophysical properties 1–8. In addition, trisbidentate ruthenium (Ru) complexes have a great advantage: they can be optically active because of the helical arrangement of the ligands around the metal ion, and so enantiomerically pure Ru complexes have been used as chiral modified electrodes,9, 10 catalysts for asymmetric synthesis,11, 12 and chiral stationary phases in high‐performance liquid chromatography13 as well as chiral building blocks for supramolecular architectures 14–22. On the other hand, a number of metallopolymers bearing Ru complexes as the side‐group or main‐chain components have been prepared 21, 23, 24.…”

Section: Introductionmentioning

confidence: 99%

“…Meyer and coworkers25, 26 reported the synthesis of a series of metallopolymers with Ru metal complexes as the side groups and investigated their electrochemical and photochemical properties. However, the syntheses and characterizations of metallopolymers and dendrimers containing enantiomerically pure Ru complexes are still limited 18, 20–22…”

Section: Introductionmentioning

confidence: 99%

Synthesis and property of helical poly(phenylacetylene)s bearing chiral ruthenium complexes and real space imaging of meso‐ and nanoscopic structures by atomic force microscopy

Sakurai

Ohira

Fujito

et al. 2004

J. Polym. Sci. A Polym. Chem.

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Novel sets of helical poly(phenylacetylene)s bearing a chiral ruthenium (Ru) complex with opposite chirality (Δ and Λ forms) as a bulky pendant (poly‐1 and poly‐2) were synthesized through the polymerization of the corresponding optically pure phenylacetylenes with a rhodium catalyst, and their structures in solution and morphology on solid substrates were investigated with NMR, ultraviolet–visible, and circular dichroism (CD) spectroscopies and with atomic force microscopy (AFM), respectively. The obtained cis–transoidal polymers (poly‐1 and poly‐2) showed characteristic Cotton effects in the region of metal‐to‐ligand charge transfer of the chiral Ru pendants. Poly‐1 and poly‐2 were thought to have a predominantly one‐handed helical conformation induced by the chiral pendants. However, the apparent Cotton effects derived from the helically twisted π‐conjugated polymer backbone could not be observed, probably because of the strong chiral chromophoric pendants. However, in the AFM images, the helical polymers adsorbed on mica could be easily discerned as isolated strands, and the visualization and discrimination of the right‐ and left‐handed helical structures of the chiral polymers were achieved by high‐resolution AFM imaging. On the basis of the AFM observations together with the CD measurements and computational calculation results, possible structures of poly‐1 and poly‐2 were examined. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4621–4640, 2004

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“…The CSP was not irreversibly altered when changing from one mobile phase mode to another. Previous papers [22,[26][27][28] also indicate that the stereochemistry at these ruthenium centers is very robust and these compounds are not easily racemized or decomposed in ordinary protic or aprotic solvents.…”

Section: Evaluation Of the Csp Prepared Via Aldehyde Binding Methodsmentioning

confidence: 99%

Development of New LC Chiral Stationary Phases Based on RutheniumTris(diimine) Complexes

Perera

MacDonnell

Armstrong

2009

Journal of Liquid Chromatography & Related Technologies

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Enantiopure ruthenium(II) tris(diimine) complexes have been covalently bonded to silica and evaluated as chiral stationary phases for LC. Three binding chemistries were tested and the CSP synthesized by reductive amination of the aldehyde-functionalized silica provided the largest enantioselectivity. The Ru complex bonded CSP showed selectivity toward a variety of racemic compounds. Circular dichroism (CD) detection was used to confirm the enantiomeric separations. This CSP worked especially well for the enantiomeric separation of binaphthyl type compounds in the normal phase mode and appeared to be selective for acidic compounds in the polar organic mode. Effects of mobile phase composition on the enantioseparations were also studied.

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Global Chirality in Rigid Decametallic Ruthenium Dendrimers

Cited by 43 publications

References 29 publications

Binding of Rigid Dendritic Ruthenium Complexes to Carbon Nanotubes

Binding of Rigid Dendritic Ruthenium Complexes to Carbon Nanotubes

Synthesis and property of helical poly(phenylacetylene)s bearing chiral ruthenium complexes and real space imaging of meso‐ and nanoscopic structures by atomic force microscopy

Development of New LC Chiral Stationary Phases Based on RutheniumTris(diimine) Complexes

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