Chiroptical photoswitches are of increasing interest for their potential in advanced information technologies. Herein, an achiral bis-β-diketonate ligand (o-L) with a photoresponsive diarylethene moiety as a linker was designed, which co-assembled with Eu ions and R- and S-bis(diphenylphosphoryl)-1,10-binaphthyl (R/S-BINAPO) as chiral ancillaries to form dinuclear triple-stranded helicates, [Eu(o-L)(R/S-BINAPO)]. The helicates in the enantiopure form were confirmed by H, F, P NMR and DOSY NMR analyses. Furthermore, the mirror-image CD and CPL spectra also demonstrate the existence of stable ground- and excited-state chiralities in solution. When exposed to alternate ultraviolet and visible light, the helicates showed reversible color variations from colorless to purple, followed by the presence of light-triggered quadruple optical and chiroptical outputs, named CD, PL, CPL and g switches. With these light-modulated optical outputs, the possibility for the fabrication of IMPLICATION and INHIBIT logic gates was discussed.
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http://dx.doi.org/10.1039/d1dt00251a | DOI Listing |
Highly diastereoselective self-assembly reactions give both enantiomers (Λ and Δ) of anti-parallel triple-stranded bimetallic Co(ii) and Co(iii) cationic helices, without the need for resolution; the first such reaction for Co. The complexes are water soluble and stable, even in the case of Co(ii). Studies in a range of cancer and healthy cell lines indicate high activity and selectivity, and substantial differences between enantiomers.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2023
School of Chemistry, University of Birmingham Edgbaston, Birmingham, B15 2TT, UK.
Metal-organic cages (MOCs) are popular host architectures assembled from ligands and metal ions/nodes. Assembling structurally complex, low-symmetry MOCs with anisotropic cavities can be limited by the formation of statistical isomer libraries. We set out to investigate the use of primary coordination-sphere engineering (CSE) to bias isomer selectivity within homo- and heteroleptic Pd L cages.
View Article and Find Full Text PDFChem Sci
July 2023
Univ Lyon, Univ Lyon 1, CNRS, INSA, CPE, ICBMS F-69622 Lyon France
The diastereoselective assembly of achiral constituents through a single spontaneous process into complex covalent architectures bearing multiple stereogenic elements still remains a challenge for synthetic chemists. Here, we show that such an extreme level of control can be achieved by implementing stereo-electronic information on synthetic organic building blocks and templates and that non-directional interactions (, electrostatic and steric interactions) can transfer this information to deliver, after self-assembly, high-molecular weight macrocyclic species carrying up to 16 stereogenic elements. Beyond the field of supramolecular chemistry, this proof of concept should stimulate the on-demand production of highly structured polyfunctional architectures.
View Article and Find Full Text PDFACS Catal
September 2022
Department of Chemistry, Emory University, 1515 Dickey Drive, Atlanta, GA 30322.
The synthesis and evaluation of six C-symmetric bowl-shaped dirhodium tetracarboxylate catalysts are described. These elaborate high symmetry catalysts are readily generated by means of the self-assembly of four C-symmetric ligands around the dirhodium core. These catalysts are capable of highly site-selective, diastereoselective and enantioselective C-H functionalization reactions by means of donor/acceptor carbene-induced C-H insertions.
View Article and Find Full Text PDFChem Asian J
April 2023
Organic and Medicinal Chemistry Division, CSIR Indian Institute of Chemical Biology, 4 Raja S C Mullick Road, Kolkata, 700031, India.
Chiral self-sorting during the formation of cage-like molecules continues to fascinate and advance our understanding of the phenomenon in general. Herein, we report the chiral self-sorting in the Pd L -type metal-organic cages. When a racemic mixture of axially chiral bis-pyridyl ligands undergo coordination-driven self-assembly with Pd(II) ions to form Pd L -type cages, the system has the option of chiral self-sorting to afford any of at least 70 pairs of (one homochiral and 69 heterochiral) enantiomers and 5 meso isomers or a statistical mixture of everything.
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