Topic
TRISPHAT
About: TRISPHAT is a research topic. Over the lifetime, 77 publications have been published within this topic receiving 2296 citations.
Papers published on a yearly basis
Papers
TL;DR: The association of heptamethine cyanine cation 1(+) with various counterions A (A = Br(-), I(-), PF(6)(-), SbF(6), B(C(6)F(5)), TRISPHAT) was realized, and their absorption properties were studied in polar (DCM) and apolar (toluene) solvents.
Abstract: The association of heptamethine cyanine cation 1(+) with various counterions A (A = Br(-), I(-), PF(6)(-), SbF(6)(-), B(C(6)F(5))(4)(-), TRISPHAT) was realized. The six different ion pairs have been characterized by X-ray diffraction, and their absorption properties were studied in polar (DCM) and apolar (toluene) solvents. A small, hard anion (Br(-)) is able to strongly polarize the polymethine chain, resulting in the stabilization of an asymmetric dipolar-like structure in the crystal and in nondissociating solvents. On the contrary, in more polar solvents or when it is associated with a bulky soft anion (TRISPHAT or B(C(6)F(5))(4)(-)), the same cyanine dye adopts preferentially the ideal polymethine state. The solid-state and solution absorption properties of heptamethine dyes are therefore strongly correlated to the nature of the counterion.
168 citations
TL;DR: Photophysical measurements and NMR spectroscopy carried out in acetone (CD(3)COCD(3)) and acetonitrile solutions reveal that the much larger TRISPHAT(-) anion favors predominantly the encirclement of the green site by the blue box.
80 citations
TL;DR: Both enantiomers of TRISPHAT anion can be obtained on a multigram scale through a novel resolution procedure and are prepared as the cinchonidinium derivative and Lambda-1, respectively.
Abstract: Both enantiomers of TRISPHAT anion can be obtained on a multigram scale through a novel resolution procedure. The Lambda enantiomer is isolated as the tri-n-butylammonium salt, [(n)()Bu(3)NH][Lambda-1], which is soluble in pure CHCl(3) and CH(2)Cl(2). The Delta enantiomer is prepared as the cinchonidinium derivative, which is only soluble in polar solvent mixtures (>7.5% DMSO in CHCl(3)).
74 citations
TL;DR: In this paper, a chiral recognition between the Δ-Trisphat anion and a single enantiomer cation was achieved through a π−π interaction.
Abstract: The racemic triangular supramolecular host [Cp*Rh(5-chloro-2,3-dioxopyridine)]3 (1) was prepared in high yield. Treatment with LiCl followed by addition of silver salt AgOTf gave the triflate salt species [Li⊂{Cp*Rh(5-chloro-2,3-dioxopyridine)}3][OTf] (2). Subsequent anion metathesis using the optically pure chiral shift reagent [Cinchonidinium][Δ-Trisphat] produced a pair of diastereomers [Li⊂(R,R,R)-{Cp*Rh(5-chloro-2,3-dioxopyridine)}3][Δ-Trisphat] (3a) and [Li⊂(S,S,S)-{Cp*Rh(5-chloro-2,3-dioxopyridine)}3][Δ-Trisphat] (3b). The resolution of these diastereomers was achieved by fractional crystallization, and their stereochemistry relationship was established by circular dichroism studies. The X-ray molecular structure of 3a is reported and shows as an outstanding feature a chiral recognition between the Δ-Trisphat anion and a single enantiomer cation [Li⊂(R,R,R)-{Cp*Rh(5-chloro-2,3-dioxopyridine)}3]+ manifested through a π−π interaction. 1H NMR and circular dichroism studies in solution support the soli...
68 citations
TL;DR: 1H, (19)F and (31)P pulsed field gradient spin-echo (PGSE) diffusion studies on chiral organic salts that contain hexacoordinate phosphate anions, namely tris(tetrachlorobenzenediolato)phosphate(V) (TRISPHAT) and bis(tTrisphAT)mono([1,1']binaphthalenyl-2,2'diolato)-phosphates(V
Abstract: 1H, (19)F and (31)P pulsed field gradient spin-echo (PGSE) diffusion studies on chiral organic salts that contain hexacoordinate phosphate anions, namely tris(tetrachlorobenzenediolato)phosphate(V) (TRISPHAT) and bis(tetrachlorobenzenediolato)mono([1,1']binaphthalenyl-2,2'diolato)-phosphate(V) (BINPHAT), are reported. The first example of the dependence of a diffusion value on diastereomeric structure is presented. Marked solvent and concentration effects on the diffusion constants (D) of these salts are noted and the question of ion pairing is discussed.
60 citations
Related Topics (5)
Performance Metrics
| Year | Papers |
|---|---|
| 2020 | 1 |
| 2018 | 1 |
| 2017 | 2 |
| 2016 | 1 |
| 2015 | 1 |
| 2014 | 1 |