Chiral octahedral bimetallic assemblies with Δ‐TRISPHAT as counter anion: Design, anion metathesis, and Cp*Ir as a probe for chiral recognition

Damas, Aurélie; Moussa, Jamal; Rager, Marie Noëlle; Amouri, Hani

doi:10.1002/chir.20882

Cited by 28 publications

(15 citation statements)

References 30 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Diastereomers possess distinguishable properties, therefore, they are widely employed in chiral resolution and recognition. [ 6‐7 ] Meggers and others have developed the chiral‐auxiliary‐mediated strategy to successfully synthesize enantiomeric complexes based on the diastereomeric discrepancy. [ 8‐9 ] To our knowledge, the discrepant reactivity between the diastereomers remains unexploited, [ 10 ] though the metal‐assisted oxidative dehydrogenation of amine complexes into imine complexes has been extensively studied.…”

Section: Background and Originality Contentmentioning

confidence: 99%

Diastereoselective Photoreaction of Ir(III) Amine Complexes for Generation of New Multidentate Ligands in situ via a Postcoordinated Interligand‐Coupling Strategy

Chen

Yao

et al. 2021

Chin. J. Chem.

View full text Add to dashboard Cite

Main observation and conclusion The diastereoselective photoreactions of Ir(III)‐amine and Ir(III)‐diamine complexes are observed in the presence of O2. The Ʌ‐[Ir(pq)2(R‐mapy)](PF6) (pq is 2‐phenylquinoline and mapy is 2‐(1‐aminoethyl)pyridine) diastereomer is dehydrogenatively oxidized into imine complex Ʌ‐[Ir(pq)2(mapy‐2H)](PF6) at room temperature, while the Ʌ‐[Ir(pq)2(S‐mapy)](PF6) diastereomer occurs interligand C—N cross‐coupling reaction at 60 °C, affording a new tetradentate complex Ʌ‐[Ir(pq)(S‐pqpe)] (PF6) (pqpe is 2‐phenyl‐N‐(1‐pyridin‐2‐yl)ethyl‐quinolin‐8‐amine). The identical cases are also observed in diamine complexes Ʌ‐[Ir(pq)2(R,R‐chda)](PF6) (chda is 1,2‐diaminocyclohexane), Ʌ‐[Ir(pq)2(R,S‐chda)](PF6), and Ʌ‐[Ir(pq)2(S,S‐chda)](PF6), where the R configuration ligand is dehydrogenatively oxidized into imine, while the S configuration is retentive and the bound nitrogen atom is coupling to the C8 of pq ligand, affording Ʌ‐[Ir(pq)2(chdi)](PF6) (chdi is 1,2‐diiminocyclohexane), Ʌ‐[Ir(pq)(S‐pqchim)](PF6) (pqchim is N‐(2‐iminocyclohexyl)‐2‐phenyl‐ quinolin‐8‐amine), and Ʌ‐[Ir(S,S‐pqchda)](PF6) (pqchda is N',N”‐bis(2‐phenylquinolin‐8‐yl)cyclohexane‐1,2‐diamine), respectively. These provide a new and useful protocol for the synthesis of multidentate ligands in situ via the postcoordinated interligand‐coupling strategy under mild conditions.

show abstract

Section: Background and Originality Contentmentioning

confidence: 99%

Diastereoselective Photoreaction of Ir(III) Amine Complexes for Generation of New Multidentate Ligands in situ via a Postcoordinated Interligand‐Coupling Strategy

Chen

Yao

et al. 2021

Chin. J. Chem.

View full text Add to dashboard Cite

show abstract

“…13 Cyclometalated iridium complexes are regarded as the most successful family of phosphors due to their relatively long excited-state lifetime, high phosphorescence efficiency and excellent color tunability. [15][16][17][18][19][20][21][22][23] This system was efficiently synthesized by coupling a neutral Ir(III) complex 1 bearing two 2phenylpyridyl (noted below as either ppy or (C^N)) and a pyridylcarboxylate (noted below as either pic or (O^N)) ancillary ligand and a unique pendant terminal alkynyl tethered to a Keggin type organotin POM hybrid bearing an iodoaryl moiety via Sonogashira coupling (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

Long lived charge separation in iridium(iii)-photosensitized polyoxometalates: synthesis, photophysical and computational studies of organometallic–redox tunable oxide assemblies

et al. 2013

Self Cite

View full text Add to dashboard Cite

Keggin and Dawson-type polyoxometalates (POMs) covalently grafted to heteroleptic cyclometalated iridium(III) complexes (POM-[Ir] dyads) have been prepared by postfunctionalization of organosilyl and organotin POM derivatives. Electronic properties of these 4 photosensitized POM-[Ir] dyads were evaluated by electrochemical measurements and theoretical calculations. These studies reveal that the electron acceptor character of the POMs vary with structural class (Keggin vs. Dawson) and chemical anchorage (organosilyl vs. organotin); they reveal the poor electronic interaction between the POMs and the chromophores. Combined transient absorption and spectroelectrochemical measurements provide evidence for the formation of photoinduced electron transfer from the chromophore to the POM. The lifetimes of the charge-separated states (ranging from ns to hundreds of ns) are the longest values reported for covalently bonded photosensitized POMs. The functionalization of the heteroleptic cyclometalated iridium(III) on the picolinate ligand provides directionality to the photoinduced electron transfer by enhancing charge separation and delaying charge recombination The kinetics of the photoinduced electron transfers are rationalized by Marcus theory. We conclude that the charge separation and charge recombination respectively occur in the Marcus normal and inverted regions.

show abstract

“…Later, in 2006 we described the synthesis of the first stable iridium p -dithiobenzoquinone complex p -[Cp*Ir(η 4 -C 6 H 4 S 2 )] and also the related ortho congener o -[Cp*Ir(η 4 -C 6 H 4 S 2 )] . Both compounds were used as successful organometallic linkers to construct functional coordination assemblies . More recently we reported the synthesis and the X-ray molecular structure of the p -diselenobenzoquinone as metal complex p -[Cp*Ir(η 4 -C 6 H 4 Se 2 )] ( 2 ) (Chart ) …”

Section: Introductionmentioning

confidence: 99%

Dinuclear Platinum(II) Terpyridyl Complexes with a para-Diselenobenzoquinone Organometallic Linker: Synthesis, Structures, and Room-Temperature Phosphorescence

et al. 2013

Self Cite

View full text Add to dashboard Cite

We report the synthesis of a unique class of luminescent heterotrinuclear complexes of the general formulas [Pt(terpy){Cp*Ir-p-(η 4 -C 6 H 4 Se 2 )}Pt(terpy)][X] 4 (X = OTf, 3a; PF 6 , 3b; BF 4 , 3c; ClO 4 , 3d; BPh 4 , 3e). In these coordination assemblies two Pt(terpy) moieties are held by a stable η 4 -diseleno-p-benzoquinone complex [Cp*Ir-p-(η 4 -C 6 H 4 Se 2 )]. The molecular structures of solvates of 3a and 3b were ascertained by single-crystal X-ray diffraction study and confirmed the formation of the target molecules. The solidstate packing of two of these complexes confirms the presence of π−π and Pt•••Pt interactions among individual units providing a 1D supramolecular chain for 3a, while a dimer species is obtained for 3b, illustrating the effect of the counterion on directing the crystal packing of the individual molecules. All compounds show phosphorescence in the red region (685−705 nm) in fluid solution and in the solid state at room temperature, unlike the analogous compound Pt(terpy){Cp*Ir-p-(η 4 -C 6 H 4 S 2 )}Pt-(terpy)][CF 3 SO 3 ] 4 obtained with a dithiobenzoquinone organometallic linker, which is only luminescent at low temperature.

show abstract

Chiral octahedral bimetallic assemblies with Δ‐TRISPHAT as counter anion: Design, anion metathesis, and Cp*Ir as a probe for chiral recognition

Cited by 28 publications

References 30 publications

Diastereoselective Photoreaction of Ir(III) Amine Complexes for Generation of New Multidentate Ligands in situ via a Postcoordinated Interligand‐Coupling Strategy

Diastereoselective Photoreaction of Ir(III) Amine Complexes for Generation of New Multidentate Ligands in situ via a Postcoordinated Interligand‐Coupling Strategy

Long lived charge separation in iridium(iii)-photosensitized polyoxometalates: synthesis, photophysical and computational studies of organometallic–redox tunable oxide assemblies

Dinuclear Platinum(II) Terpyridyl Complexes with a para-Diselenobenzoquinone Organometallic Linker: Synthesis, Structures, and Room-Temperature Phosphorescence

Contact Info

Product

Resources

About