A Chiral and Colorful Redox Switch: Enhanced π Acidity in Action

Abstract

Deep blue diving: π Acidities up to a new record of −4.74 eV are made possible with simple sulfur redox chemistry (see scheme). This attractive method is able to generate exceptional electron affinities and anion transport efficiencies for applications in optoelectronic devices, medicinal chemistry, and anion–π catalysis

Experimental investigation of anion–π interactions – applications and biochemical relevance

“…An extended study of the same group introduced sulfur redox chemistry into the NDIs showing an enhanced p-acidity. 60 Oxidation of the thioether substituted NDI 52 by meta-chloroperbenzoic acid (mCPBA) leads to the chiral sulfoxide 53, which might be useful in anion-p actuated asymmetric catalysis. Further oxidation to the corresponding tetrasulfone 54 yielded the most p-acidic compound reported so far as proven by optoelectronic properties and computational studies (Fig.…”

“…A series of new amphiphilic anion receptors based on tetraoxacalix[2]arene[2]triazine (60) was investigated in respect to its self-assembling into stable vesicles in a mixture of THF and water (Fig. 35).…”

“…Molecular structures of the thioether, sulfoxide and sulfone substituted NDIs as reported by Matile and coworkers 60. …”

Dithienothiophenes at Work: Access to Mechanosensitive Fluorescent Probes, Chalcogen-Bonding Catalysis, and Beyond

“…At that time, the reversible oxidation of sulfides into sulfoxides and sulfones was already recognized as a universal, most convenient redox switch. [2][3][4][5] Interestingly, with DTTs, reversibility, that is the existence of a redox switch has never been clearly explored because the reduction of DTTO2 3 was of little interest. Closely related endocyclic "sulfones" have been reduced back to sulfides.…”

Dipolar vinyl sulfur fluorescent dyes. Synthesis and photophysics of sulfide, sulfoxide and sulfone based D–π–A compounds

“…[26][27][28][29][30] Concerning those functional groups, the organosuldes allow a tuneable electronic behavior that can be easily modulated through a single step oxidation to the respective sulfoxides or sulfones, which are effective electron acceptor groups. [31][32][33][34][35][36][37][38] In this regard, our continuous interests in the synthesis of organochalcogen compounds prompted us to access symmetrical and unsymmetrical vinyl suldes by a straightforward approach, using a Wittig-Horner reaction, as precursors of products carrying a higher oxidation state on sulfur. 39,40 In this sense, photoactive divinyl suldes and sulfones have been obtained.…”