Stereoselective Synthesis of Hexacoordinated Mononuclear Cyclometalated Rhodium(III) Complexes − Transfer of Chirality from the Metal Center to the Ligand

Ghizdavu, Liana; Zelewsky, Alex von; Stœckli-Evans, Helen

doi:10.1002/1099-0682(200104)2001:4<993::aid-ejic993>3.3.co;2-v

Cited by 4 publications

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“…Indeed, the CD spectra of ΔRh(thpy) and ΔRh(phpy) show the same strong positive Cotton effect at the longest absorption wavelength (Figure ). Their CD spectra have the same shapes as those of the ΔΔ precursors and the reported spectra of other optically active Δ[Rh(thpy4,5p( R,R )py) 2 (N∧N)]Cl complexes . Moreover, ΔRh(thpy) and ΛRh(thpy) are enantiomers as well as they show mirror images in their CD spectra.…”

Section: Resultssupporting

confidence: 62%

“…The absorption bands that occur up to 340 nm are due to ligand centered (π−π*) transitions . In the broad intense bands of lower energy between 350 and 380 nm (see Experimental Section), a charge transfer (CT) contribution could be present since no absorptions are observed for the free ligands in this wavelength region. , …”

Section: Resultsmentioning

confidence: 99%

“…TD-DFT calculations have been carried out to rationalize the emission behaviors. We choose the stereoselective synthesis developed by von Zelewsky and co-workers for the preparation of the optically active compounds. ,, Stereoselective synthesis appears indeed to be one of the most promising approaches for the development of optically pure complexes. According to this method, the chirality at the metal center (Δ or Λ) is controlled by the choice of the enantiomerically pure chiral bidentate ligands that are used.…”

Section: Introductionmentioning

confidence: 99%

“…Upon cleavage of the μ-dichloro bridge of these dimers with bidentate ligands, mononuclear complexes are obtained. It has been shown that this type of cleavage reaction occurs under retention of configuration 1 …”

Section: Introductionmentioning

confidence: 99%

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Synthesis and Characterization of Optically Active and Racemic Forms of Cyclometalated Rh(III) Complexes. An Experimental and Theoretical Emission Study

et al. 2003

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The optically active cyclometalated Rh(III) complexes, delta[Rh(thpy4,5p(R,R)py)(2)TAP]Cl, lambda[Rh(thpy4,5p(S,S)py)(2)TAP]Cl, and delta[Rh(phpy4,5p(R,R)py)(2)TAP]Cl (where TAP = 1,4,5,8-tetraazaphenanthrene, thpy4,5p(R,R)py = (8R,10R)-2-(2'-thienyl)-4,5-pinenopyridine and phpy4,5p(R,R)py = (8R,10R)-2-(2'-phenyl)-4,5-pinenopyridine) have been prepared and characterized. Their photophysics has been examined in parallel with that of rac[Rh(thpy)(2)TAP]Cl and rac[Rh(phpy)(2)TAP]Cl. Their behaviors have been rationalized from results of TD-DFT calculations. The complexes with thienylpyridine (thpy) as cyclometalating ligands exhibit (3)CT (from thpy to TAP) and (3)LC(pi-pi) (centered on thpy) emissions in a solvent matrix at 77 K and one (3)CT luminescence at room temperature. In contrast, with phenylpyridine (phpy), the complexes show only one (3)CT emission (from phpy to TAP) at both temperatures.

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Section: Resultssupporting

confidence: 62%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Synthesis and Characterization of Optically Active and Racemic Forms of Cyclometalated Rh(III) Complexes. An Experimental and Theoretical Emission Study

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“…Other suitable candidates for this approach include rhenium(I), 14,15,27,28 platinum(II), 22,29,30 osmium(II), 12 and rhodium(III). [31][32][33] Excited-State Characteristics. 3 MLCT and 3 π-π* ligandcentered transitions are commonly observed in a vast majority of the presently investigated mixed-ligand transition-metal complexes.…”

Section: Resultsmentioning

confidence: 99%

Accelerated Luminophore Discovery through Combinatorial Synthesis

Lowry

Hudson²,

Pascal³

et al. 2004

J. Am. Chem. Soc.

502

486

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A method for accelerating the discovery of ionic luminophores using combinatorial techniques is reported. The photophysical properties of the resulting transition-metal-based chromophores were compared against a series of analogous, traditionally prepared species. The strong overlap between these two sets confirms the identity of the parallel synthesis products and supports the truthfulness of the combinatorial results. Further support for the combinatorial method comes from the adherence of these complexes to the energy gap law. The relationship between the structure of a complex and its photophysical properties was also considered, and static DFT calculations were used to assess whether it is feasible to predict the luminescent behavior of novel materials.

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Magnetism of [Ni(dmit)₂] Salts with [Meso- and (1S, 2S)-Diphenyl-1,2-Ethanediammonium]([18]crown-6)₂ Supramolecular Cations

et al. 2005

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Meso- and (1S, 2S)-diphenyl-1,2-ethanediammonium (DPEDA2+) complexed with [18]crown-6 were introduced into [Ni(dmit)2]-based magnetic salts as countercations. The configurational difference of DPEDA2+ modulated the crystal structure and magnetic behavior of the salts. A two-dimensional (2D) Heisenberg antiferromagnetic square lattice was observed in (meso-diphenyl-1,2-ethane diammonium2+)([18]crown-6)2[Ni(dmit)2](-)2, which was the first example of a 2D magnetic lattice in [Ni(dmit)2]- salts.

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Stereoselective Synthesis of Hexacoordinated Mononuclear Cyclometalated Rhodium(III) Complexes − Transfer of Chirality from the Metal Center to the Ligand

Cited by 4 publications

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Synthesis and Characterization of Optically Active and Racemic Forms of Cyclometalated Rh(III) Complexes. An Experimental and Theoretical Emission Study

Synthesis and Characterization of Optically Active and Racemic Forms of Cyclometalated Rh(III) Complexes. An Experimental and Theoretical Emission Study

Accelerated Luminophore Discovery through Combinatorial Synthesis

Magnetism of [Ni(dmit)₂] Salts with [Meso- and (1S, 2S)-Diphenyl-1,2-Ethanediammonium]([18]crown-6)₂ Supramolecular Cations

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Stereoselective Synthesis of Hexacoordinated Mononuclear Cyclometalated Rhodium(III) Complexes − Transfer of Chirality from the Metal Center to the Ligand

Cited by 4 publications

References 0 publications

Synthesis and Characterization of Optically Active and Racemic Forms of Cyclometalated Rh(III) Complexes. An Experimental and Theoretical Emission Study

Synthesis and Characterization of Optically Active and Racemic Forms of Cyclometalated Rh(III) Complexes. An Experimental and Theoretical Emission Study

Accelerated Luminophore Discovery through Combinatorial Synthesis

Magnetism of [Ni(dmit)2] Salts with [Meso- and (1S, 2S)-Diphenyl-1,2-Ethanediammonium]([18]crown-6)2 Supramolecular Cations

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Product

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Magnetism of [Ni(dmit)₂] Salts with [Meso- and (1S, 2S)-Diphenyl-1,2-Ethanediammonium]([18]crown-6)₂ Supramolecular Cations