Straightforward access to mono- and bis-cycloplatinated helicenes displaying circularly polarized phosphorescence by using crystallization resolution methods

Shen, Chengshuo; Anger, Emmanuel; Srebro, Monika; Vanthuyne, Nicolas; Deol, Kirandeep K.; Jefferson, Truman D.; Muller, Gilles; Williams, J. A. Gareth; Toupet, Loı̈c; Roussel, Christian; Autschbach, Jochen; Réau, Régis; Crassous, Jeanne

doi:10.1039/c3sc53442a

Cited by 149 publications

(136 citation statements)

References 74 publications

(27 reference statements)

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“…(8) and (9) into the expression for the transition moments, the first-order contribution to the dipole transition moment between singlet and triplet states is shown to be written as (8) and (9) into the expression for the transition moments, the first-order contribution to the dipole transition moment between singlet and triplet states is shown to be written as…”

Section: Theorymentioning

confidence: 99%

A computational protocol for the study of circularly polarized phosphorescence and circular dichroism in spin-forbidden absorption

Kamiński

Cukras

Pecul

et al. 2015

Phys. Chem. Chem. Phys.

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We present a computational methodology to calculate the intensity of circular dichroism (CD) in spin-forbidden absorption and of circularly polarized phosphorescence (CPP) signals, a manifestation of the optical activity of the triplet-singlet transitions in chiral compounds. The protocol is based on the response function formalism and is implemented at the level of time-dependent density functional theory. It has been employed to calculate the spin-forbidden circular dichroism and circularly polarized phosphorescence signals of valence n → π* and n ← π* transitions, respectively, in several chiral enones and diketones. Basis set effects in the length and velocity gauge formulations have been explored, and the accuracy achieved when employing approximate (mean-field and effective nuclear charge) spin-orbit operators has been investigated. CPP is shown to be a sensitive probe of the triplet excited state structure. In many cases the sign of the spin-forbidden CD and CPP signals are opposite. For the β,γ-enones under investigation, where there are two minima on the lowest triplet excited state potential energy surface, each minimum exhibits a CPP signal of a different sign.

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Section: Theorymentioning

confidence: 99%

A computational protocol for the study of circularly polarized phosphorescence and circular dichroism in spin-forbidden absorption

Kamiński

Cukras

Pecul

et al. 2015

Phys. Chem. Chem. Phys.

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“…However, CSPC and CSPE immobilized at the3-N-position could not resolve the helicenes at all, indicating that the interaction of the original isoalloxazine ring of CSPA and CSPB with the polyaromatic helicenes may be the major driving force for their efficient chiral recognition of the helicenes rather [7]helicene (30) on CSPA and CSPB was identical to that on the reported riboflavin-coated silica gel CSP, 20 judging from the Cotton effect sign of the first-eluted enantiomer of 30 at 350 nm. 20,33 More interestingly, most of the helicene derivatives, in particular, the [6]helicene derivatives (25 and 27), [7]helicene (30), and an [8]helicene analog (31) were better resolved on the 3-Nbonded CSPD composed of the fully-acetylated ribityl residue, and 25 and 31 (Fig. 3C) were completely separated.…”

mentioning

confidence: 96%

“…The racemates were commercially available or were prepared by the usual or reported methods. [29][30][31] The synthesis of new [6]helicene derivatives (26-28) will be reported elsewhere. Porous spherical silica gel (Daiso gel SP-120-7P, N-silica) with a mean particle size of 7 µm and a mean pore diameter of 12 nm was kindly supplied from Daicel (Tokyo, Japan).…”

Section: Chemicals and Reagentsmentioning

confidence: 99%

“…It should be noted that the bulky aromatic racemic alcohols with an acidic hydroxy group 13 and 16 strongly interacted with the five CSPs in n-hexane-CH2Cl2, in particular on the CSPC and CSPD, 16 could not elute (k1 > 100) under the present conditions. Based on the above results together with the previously reported intriguing chiral recognition abilities of riboflavin 20 and FMN 21 for the racemic helicenes and SWCNTs, respectively, we employed 13 racemates (19-31) (Chart 1) including the cyclic dibenzamide (19) and dianilide (20), bulky aromatic racemic alcohols (21)(22)(23), and helicene derivatives including the [6] and [7]helicenes (24-30) and a metal-containing [8]helicene analog (31) to further evaluate the specific chiral recognition abilities of the riboflavin-based CSPs in n-hexane-2-propanol and nhexane-CH2Cl2 eluent systems; the chromatographic resolution results showing a more or less enantioselectivity ( > 1) on either CSP for the racemates are summarized in Table 1 and Table 2, respectively. For comparison, some resolution results in Tables S1 and S2 are also shown.…”

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confidence: 99%

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Enantioseparation on Riboflavin Derivatives Chemically Bonded to Silica Gel as Chiral Stationary Phases for HPLC

et al. 2015

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Acetylated and/or 3,5-dimethylphenylcarbamated riboflavins were prepared and the resulting riboflavin derivatives as well as natural riboflavin were regioselectively immobilized on silica gel through chemical bonding at the 5'-O-or 3-N-position of the riboflavin to develop novel chiral stationary phases (CSPs) for enantioseparation by high-performance liquid chromatography (HPLC). The chiral recognition abilities of the obtained CSPs were significantly dependent on the structures of the riboflavin derivatives, the position of the chemical bonding on the silica gel, and the structures of the racemic compounds. The CSPs bonded at the 5'-O-position on the silica gel tended to well separate helicene derivatives, while the CSPs bonded at the 3-N-position composed of acetylated and 3,5-dimethylphenylcarbamated riboflavins showed a better resolving ability toward helicene derivatives and bulky aromatic racemic alcohols, respectively, and some of them were completely separated into the enantiomers. The observed difference in the chiral recognition abilities of these riboflavin-based CSPs is discussed based on the difference in their structures, including the substituents of riboflavin and the positions immobilized on the silica gel.

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“…[140] Moreover a CP screen reduces the perceived distortion found at some angles when the display is viewed through a LP filter, like polarized sunglasses, allowing for enhanced outdoor viewing of laptops or smartphones. Recently Brandt et al [140] used a helicene-Pt complex [141] as active material in light-emitting diodes (LEDs) reaching a polarization degree [2] g EL = 0.35 through Pt-centered phosphorescence. Furthermore, Zinna et al developed a proof-of-concept device based on a chiral Eu(III) complex emitter, reached the highest reported g EL value for any CPOLED close to |0.8| at 595 nm.…”

Section: Applications To Organic Light Emission Diodes Technologymentioning

confidence: 99%

Materials and 3D Designs of Helix Nanostructures for Chirality at Optical Frequencies

Passaseo

Esposito

Cuscunà

et al. 2017

Advanced Optical Materials

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The capability to fully control the chiro‐optical properties of metamaterials has drawn considerable attention due to developments in metamaterial fabrication techniques and a deeper understanding of the light–matter interaction, enabling a number of applications from integrated photonics to life sciences. From simple geometrical studies on single helix shaped metamaterials, both the design complexity and nanofabrication capability are steadily increasing allowing to extend their properties to the visible regime and beyond. In this work, helix‐shaped micro‐ and nanostructures are reviewed, which have the possibility to modulate their optical response in the linear regime at optical frequencies by spatial arrangement or by constitutive material. An overview of different theories describing the general optical operation of chiral media and a discussion on experimental results obtained by the state‐of‐the‐art helix structures realized by different fabrication techniques is provided. Finally, advanced designs for improved functionality envisaged to match practical applications or to enable new optical multifunctionalities are compared. Even if many applications have been envisaged only theoretically, the continuous effort and progress shown by the research community engaged in this field suggests that helical chiral metamaterials could represent a disruptive breakthrough for advanced optical devices.

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Straightforward access to mono- and bis-cycloplatinated helicenes displaying circularly polarized phosphorescence by using crystallization resolution methods

Cited by 149 publications

References 74 publications

A computational protocol for the study of circularly polarized phosphorescence and circular dichroism in spin-forbidden absorption

A computational protocol for the study of circularly polarized phosphorescence and circular dichroism in spin-forbidden absorption

Enantioseparation on Riboflavin Derivatives Chemically Bonded to Silica Gel as Chiral Stationary Phases for HPLC

Materials and 3D Designs of Helix Nanostructures for Chirality at Optical Frequencies

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