Crystal structure and chiroptical spectra of sodium tetrakis (+)-hfbc Pr(III) complex

Shirotani, Dai; Suzuki, Takayoshi; Yamanari, Kazuaki; Kaizaki, Sumio

doi:10.1016/j.jallcom.2007.04.236

Cited by 22 publications

(53 citation statements)

References 28 publications

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“…It is interesting to note that the Na–La complex gives no CD couplet, but only a single positive CD in 2–0.02 mM EtOH and a CD couplet in 2 mM CHCl 3 , whereas other M I –La compounds show CD couplets in both 2 mM CHCl 3 and 2 mM EtOH. 47, 49, 50 The observation of a couplet CD indicates the existence of a chiral helical configuration, whereas a single CD suggests the disruption of the chiral configuration toward [Ln((+)–hfbc) 3 ] as a result of the facile solvation by EtOH. It is also interesting to note that the g lum values of M–Eu solutions are quite larger than those of [Eu((+)–hfbc) 3 ].…”

Section: Resultsmentioning

confidence: 99%

“…On the other hand, the CD intensities in the intraligand transition were concentration dependent in EtOH (going from a weaker CD couplet to a single CD band with lowering the concentration), while there is a smaller concentration dependence in CH 3 CN. 47, 49, 50 In our previous report, we showed that the variation in the CD couplet was due to the contribution of two different species present in solution, SAPR–8–Cs[Eu((+)–hfbc) 4 ] and [Eu((+)–hfbc) 3 ] or pseudo achiral DD–8–[Eu((+)-hfbc) 4 ]. 47 …”

Section: Resultsmentioning

confidence: 99%

“…49, 50 Luminescence spectra were measured on a Perkin-Elmer LB 50 spectrophotometer. Luminescence measurements were performed in CHCl 3 , CH 3 CN, and EtOH solutions.…”

Section: Methodsmentioning

confidence: 99%

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Chiroptical Spectra of a Series of Tetrakis((+)-3-heptafluorobutylyrylcamphorato)lanthanide(III) with an Encapsulated Alkali Metal Ion: Circularly Polarized Luminescence and Absolute Chiral Structures for the Eu(III) and Sm(III) Complexes

et al. 2011

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The luminescence and circularly polarized luminescence (CPL) spectra of MI[Eu((+)–hfbc)4] show a similar behavior to the exciton CD in the intraligand π–π* transitions when the alkali metal ions and solvents are manipulated. There is a difference in susceptibility in solvation toward the alkali metal ions but not toward the Eu(III) ion, as in the case of axially symmetric DOTA–type compounds. The remarkable CPL in the 4f–4f transitions provide much more information on stereospecific formation of chiral Eu(III) complexes, since CPL spectroscopy is limited to luminescent species and reflects selectively toward helicity of the local structural environment around the lanthanide(III). While in comparison, exciton CD reveals the chiral structural information from the helical arrangement of the four bladed chelates. Of special importance, the observation of the highest CPL activities measured to date for lanthanide(III)–containing compounds (i.e. Eu and Sm) in solution supports that the chirality of Lanthanide(III) in the excited state corresponds to that in the ground state, which was derived from the exciton CD.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Chiroptical Spectra of a Series of Tetrakis((+)-3-heptafluorobutylyrylcamphorato)lanthanide(III) with an Encapsulated Alkali Metal Ion: Circularly Polarized Luminescence and Absolute Chiral Structures for the Eu(III) and Sm(III) Complexes

et al. 2011

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“…78 Also, chiral tetrakis chelate complexes with four 3-heptafluorobutyryl-( þ )-camphorates (( þ )-hfbc), Na[Ln(( þ )-hfbc) 4 ] Á CH 3 CN, takes D-SAPR-8 configuration. 79,80 This complex is stabilized by interaction of the fluorocarbon moiety with the Na ion in CHCl 3 . The structure was determined on the basis of the exciton CD (see below), although the X-ray structure analysis showed only one pseudo-enantiomer with "pseudo-achiral D 2d configuration."…”

Section: Lanthanide Complexesmentioning

confidence: 99%

“…The structure was determined on the basis of the exciton CD (see below), although the X-ray structure analysis showed only one pseudo-enantiomer with "pseudo-achiral D 2d configuration." 79,80 There have also been a number of compounds formed with tetra-azo-cyclododecane-based ligands such as the tetraphosphinate complex shown in Figure 5.23. These complexes have approximate C 4 symmetry.…”

Section: Lanthanide Complexesmentioning

confidence: 99%

Absolute Chiral Structures of Inorganic Compounds

Riehl

Kaizaki

2010

Physical Inorganic Chemistry

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Chiral inorganic compounds play increasingly important roles in current research efforts concerned with asymmetric catalysis, biochemistry, and supramolecular chemistry. Although our ability to determine precise chiral structures of inorganic compounds and relate these structures to chemical phenomena is a relatively recent achievement, this area of research has been a central and fundamental subject since the beginning of modern chemistry. The realization that substances other than those containing tetrahedral carbon atoms could occur as nonsuperimposable mirrorimage forms was first made by the "father of coordination chemistry" Alfred Werner at the end of the nineteenth century. 1 A critical consequence of his octahedral coordination theory was that certain isomers of six-coordinate metal complexes should exist as enantiomeric pairs. As early as 1897, Werner was speculating on whether or not he could verify the existence of mirror-image compounds from sixcoordinate octahedral geometry, and the preparation and resolution of a chiral molecular metal complex was finally achieved by his research colleagues Ernst Scholze and Victor L. King with the publication of the separation of the optical isomers (enantiomers) of cis-bromoamminebis(ethylenediamine)cobalt(III) salts in 1911. 2 Figure 5.1 illustrates the structure of the two possible mirror-image structures for this complex. The separated complexes were shown to possess equal and opposite optical rotations (OR) confirming their mirror-image relationship. Alfred Werner received the Nobel Prize in Chemistry for his development of the coordination theory 2 years after the publication of this milestone work in 1913.Following the experimental results of Werner and his colleagues, a number of theoretical attempts were made to correlate the sign and magnitude of the optical rotation to the exact chiral molecular structure of metal complexes. These approaches have been summarized by Richardson. 3 The term "absolute structure" is sometimes limited to a discussion of the structure of noncentrosymmetric crystals, and the term Physical Inorganic Chemistry: Principles, Methods, and Models Edited by Andreja Bakac

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Applications of Electronic Circular Dichroism to Inorganic Stereochemistry

Kaizaki

2012

Comprehensive Chiroptical Spectroscopy

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Crystal structure and chiroptical spectra of sodium tetrakis (+)-hfbc Pr(III) complex

Cited by 22 publications

References 28 publications

Chiroptical Spectra of a Series of Tetrakis((+)-3-heptafluorobutylyrylcamphorato)lanthanide(III) with an Encapsulated Alkali Metal Ion: Circularly Polarized Luminescence and Absolute Chiral Structures for the Eu(III) and Sm(III) Complexes

Chiroptical Spectra of a Series of Tetrakis((+)-3-heptafluorobutylyrylcamphorato)lanthanide(III) with an Encapsulated Alkali Metal Ion: Circularly Polarized Luminescence and Absolute Chiral Structures for the Eu(III) and Sm(III) Complexes

Absolute Chiral Structures of Inorganic Compounds

Applications of Electronic Circular Dichroism to Inorganic Stereochemistry

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