Chiral transfer in coordination complexes: towards molecular materials

Crassous, Jeanne

doi:10.1039/b806203j

Cited by 383 publications

(216 citation statements)

References 156 publications

(156 reference statements)

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“…64,65 This is illustrated in the case of the tris chelate lanthanide complexes derived using the tridentate ligand L 4 . 66,67 As is apparent from Figure 1.13, this ligand is closely related to DPA in terms of its core structure and it is therefore not surprising that the ligands have been found to arrange around the lanthanide centre in a three bladed 'propeller-like' manner when used in complex formation.…”

Section: Selected Examples Of Chiral Lanthanide Complexesmentioning

confidence: 99%

Lanthanide complexes as chiral probes exploiting circularly polarized luminescence

2012

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The full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that:• a full bibliographic reference is made to the original source• a link is made to the metadata record in Durham E-Theses• the full-text is not changed in any wayThe full-text must not be sold in any format or medium without the formal permission of the copyright holders. Statement of CopyrightThe copyright of this thesis rests with the author. No quotations should be published without prior consent and information derived from it must be acknowledged. ABSTRACT -ii - ABSTRACTA series of studies has been undertaken to facilitate the identification and development of chiral lanthanide complexes that are able to report on changes in their local environment through modulation of the circular polarization of their emission. Reports of such systems remain relatively rare in the literature, notwithstanding the prevalence and importance of chirality in biological systems.The work described herein is separated into five chapters, the first of which comprises a discussion of relevant background information, along with a comprehensive review of responsive lanthanide-based CPL probes reported to date. A classification of these probes is built up, which informs the content of the following three chapters.Chapter 2 describes work undertaken in the pursuit of a novel lanthanide-based system for use as a CPL probe for the detection of proteins. The synthesis of an enantiopure lanthanide complex was undertaken and characterisation of this system carried out with reference to a structurally related racemic complex. A series of comparative investigations designed to probe the relative protein binding capability of these complexes was subsequently performed, which revealed that the observation of induced CPL from racemic lanthanide systems may be brought about by a change in complex constitution. This is the first example of such an effect from a well-defined racemic lanthanide complex in solution. Chapter 3 goes on to detail studies undertaken to demonstrate the utility of this racemic lanthanide system as a probe for chiral detection.Chapter 4 describes investigations carried out in an attempt to identify new systems exhibiting chiral quenching effects in solution. Initially, two pairs of enantiomeric electron-rich quenching species were assessed for their ability to quench the emission from an enantiopure DOTA-derived lanthanide complex differentially. Subsequently, investigations were focussed on examining the quenching of emission from novel enantiopure lanthanide complexes based on a 1,4,7-triazacyclononane framework, using cobalt complexes as the quenching species.Finally, Chapter 5 contains experimental procedures for each compound synthesised, as well as general experimental procedures.

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Section: Selected Examples Of Chiral Lanthanide Complexesmentioning

confidence: 99%

Lanthanide complexes as chiral probes exploiting circularly polarized luminescence

2012

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“…Over the last decades, chiral complexes have been an active area of research in coordination chemistry due to their diverse application in asymmetric catalysis, enantioselective synthesis, bioinorganic and supramolecular chemistry [3][4][5][6]. An effective and facile method to prepare such kind of complexes is the generating of chiral motifs in the target molecule.…”

Section: Discussionmentioning

confidence: 99%

Crystal structure of [(R,R)-6,6-dimethyl-3-pyridin-2-yl-5,6,7,8- tetrahydro-5,7-methanoisoquinoline]-tris[4,4,4-trifluoro-1-(2-thienyl)- butane-1,3-dionato]dysprosium(III), Dy(C17H18N2)(C8H4O2SF3)3

Li¹,

Xie²

2011

Zeitschrift Für Kristallographie - New Crystal Structures

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C 41 H 30 DyF 9 N 2 O 6 S 3 ,monoclinic, P2 1 (no. 4), a =10.174(2) Å, b =19.018(4) Å, c =12.037(2) Å, b =113.742(3)°, V =2131.9 Å 3 , Z =2,R gt (F) =0.048, wR ref (F 2 ) =0.112, T =291 K. Source of materialThe chiral ligand was prepared by the documented procedures [1] and Dy(tta) 3 · 2H2O( tta =4 ,4,4,-trifluoro-1-(2-thienyl)butane-1,3-dionato) was synthesized according to literature method [2]. As olution of Dy(tta) 3 · 2H 2 O( 87 mg, 0.1 mmol) in ethanol (5 mL) was added to as olution of chiral ligand (R,R)-6,6-dimethyl-3-pyridin-2-yl-5,6,7,8-tetrahydro-5,7-methanoisoquinoline (25 mg, 0.1 mmol) in acetone (5 mL). The mixture was kept at RT. Yellow single crystals of title complex, suitable for Xray analysis, were obtained in 73 %yield by slow evaporation of solvents over two weeks. Elemental analysis -found: C, 45.36 %; H, 3.02 %; N, 2.91 %; calculated for C 41 H 30 DyF 9 N 2 O 6 S 3 :C,45.75 %; H, 2.81 %; N, 2.60 %. Experimental detailsHatoms were included in calculated positions and treated as riding atoms with d(C-H) =0.93 Å (aromatic), 0.98 Å (tertiary), 0.97 Å (methylene) or 0.96 Å (methyl) and U iso(H) =1.2 or 1.5 U eq(C). The Flack parameter is 0.03(2). DiscussionOver the last decades, chiral complexes have been an active area of research in coordination chemistry due to their diverse application in asymmetric catalysis, enantioselective synthesis, bioinorganic and supramolecular chemistry [3][4][5][6]. An effective and facile method to prepare such kind of complexes is the generating of chiral motifs in the target molecule. Based on this strategy, as a continuance of our research [7], we employed ac hiral ligand (R,R)-6,6-dimethyl-3-pyridin-2-yl-5,6,7,8-tetrahydro-5,7-methanoisoquinoline to react with Dy(tta) 3 · 2H2O. Subsequently, the enantiomerically pure title compound was obtained. The unit cell of the title crystal structure contains two mononuclear neutral complexes. Each molecule is formed by three bdiketonate anions, ac hiral bipyridine derivative ligand and an eight-coordinated Dy(III) cation. The Dy(III) ion is coordinated with six Oatoms from three b-diketonate ligands. The other two coordination sites are occupied by two Na toms of ac hiral bipyridine derivative. The Dy-Ob ond lengthes range from 2.344(6) to 2.405(6) Å,w hile the Dy-Nb ond lengths are 2.527(7) and 2.567(7) Å.Eight bonds with different lengths give rise to astrongly distorted square antiprismatic environment of the Dy(III) ion. The two square planes are defined by O5, O6, N1, N2 and O1, O2, O3, O4 with the mean deviations of 0.024 and 0.030 Å,respectively. The dihedral angle is 3.38(1)°.

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“…Chiral lanthanide complexes have attracted considerable attention of research in thefield of coordinationchemistry, material scienceand life sciencedue to theirdiverse applications in asymmetric catalysis, enantioselective synthesis, medical diagnotic and therapy [3][4][5][6][7]. Among them,t he Gd-based complexes are commonly used as chiral shift reagents for resolving NMR spectra [8].…”

Section: Discussionmentioning

confidence: 99%

Crystal structure of tris(dibenzoylmethanato)-[(R,R)-6,6-dimethyl-3- pyridin-2-yl-5,6,7,8-tetrahydro-5,7-methanoisoquinoline)]- gadolinium(III), Gd(C15H11O2)3(C17H18N2)

Li¹,

Niu²

2011

Zeitschrift Für Kristallographie - New Crystal Structures

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Source of materialThe chiral ligand (R,R)-6,6-dimethyl-3-pyridin-2-yl-5,6,7,8-tetrahydro-5,7-methanoiso-quinoline was prepared by the procedures [1] and Gd(dbm) 3 ·2H 2 Owas synthesized according to [2]. As olution of Gd(dbm) 3 ·2 H 2 O( 86 mg, 0.1 mmol) in ethanol (10 mL) was addedt oas olution of chiral ligand (25 mg, 0.1 mmol) in acetone (10 mL). The mixture was stirred 10 minutes and kepta tR T. Yellow single crystals of title complex suitable for X-ray analysis were obtained in 73 %yield by slow evaporation of the solvent over two weeks. Experimental detailsHa toms were included in calculated positions and treated as riding atomswith d(C-H) =0.93 (aromatic), 0.97 (methylene) or 0.96 (methyl) Åa nd U iso (H) =1 .2 or 1.5 U eq (C). TheF lack parameter is 0.02(1). DiscussionChiral lanthanide complexes have attracted considerable attention of research in thefield of coordinationchemistry, material scienceand life sciencedue to theirdiverse applications in asymmetric catalysis, enantioselective synthesis, medical diagnotic and therapy [3][4][5][6][7]. Among them,t he Gd-based complexes are commonly used as chiral shift reagents for resolving NMR spectra [8]. The introduction of the chiral bipyridine derivative ligand results in the chirality of the title compound, which crystallizes with space group P2 1 .The chirality is dominated by the two centers C12 and C14 of the bipyridine derivative. the Gd(III)ion is coordinated by six oxygen atomsfrom three b-diketonate ligands and two nitrogen atomsofchiral pinene bipyridine. The arrangement of O 6 N 2 donors can be best approximated as ad istorted square antiprism.T he bond lengths d (Gd-O) are in the range of 2.328(5) -2.386(7) Åand d(Gd-N) are 2.574(5) and 2.599(5) Å, respectively. TheO3, O4, O5, O6 (bottom plane) and O1, O2, N1, N2 atoms(top plane) comprise the two square-basic planes of the antiprism with mean deviations of 0.072(3)and 0.113(3)Åfrom each plane, their dihedral angle is 1.7(2)°.

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Chiral transfer in coordination complexes: towards molecular materials

Cited by 383 publications

References 156 publications

Lanthanide complexes as chiral probes exploiting circularly polarized luminescence

Lanthanide complexes as chiral probes exploiting circularly polarized luminescence

Crystal structure of [(R,R)-6,6-dimethyl-3-pyridin-2-yl-5,6,7,8- tetrahydro-5,7-methanoisoquinoline]-tris[4,4,4-trifluoro-1-(2-thienyl)- butane-1,3-dionato]dysprosium(III), Dy(C17H18N2)(C8H4O2SF3)3

Crystal structure of tris(dibenzoylmethanato)-[(R,R)-6,6-dimethyl-3- pyridin-2-yl-5,6,7,8-tetrahydro-5,7-methanoisoquinoline)]- gadolinium(III), Gd(C15H11O2)3(C17H18N2)

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