Chiroptical properties of 1,3-diphenylallene-anchored tetrathiafulvalene and its polymer synthesis

Abstract

SummaryA novel tetrathiafulvalene dimer, bridged by a chiral 1,3-diphenylallene framework, has been prepared as an optically active compound having strong chiroptical properties. Although a chiral allene bearing strong electron-donating group(s) often undergoes slow photoracemization even in daylight, the present allene is totally configurationally stable under ordinary conditions. Each isomer possesses pronounced chiroptical properties in its ECD spectra reflecting the chiral allene framework. Moreover, the elongation of the chiral main chain was also carried out by direct C–H activation of the TTF unit, and the chiroptical properties of the resulting polymer were also investigated.

Chiroptical inversion of a planar chiral redox-switchable rotaxane

“…38,[42][43][44][45][46][47][48][49][50] Apart from rotaxanes, TTF derivatives with covalently bound chiral substituents exhibited a chiroptical response to a change of their redox-state. [51][52][53][54][55][56][57] Hence, our switchable rotaxanes display ideal optoelectronic properties since they are air stable in their neutral and oxidised form and show a clear-cut optical output, 37 which is even visible by the naked eye.…”

Selective Ring Opening Allene Metathesis: Polymerization or Ruthenium Vinylidene Formation

“…7 A handful of reports that successfully incorporate allenes into the repeating structure of a material are known, however, these reports typically require specialized catalyst systems and only produce oligomers. [8][9][10][11][12] An alternative route to polyallenes was recently demonstrated via post-polymerization transformation. 13 In the report, the authors carried out a two-step Skattebøl rearrangement on cispoly(norbornene) resulting in allene incorporation at varying percentages (20-95%) along the backbone.…”

Catalytic C–H Arylation of Tetrathiafulvalenes for the Synthesis of Functional Materials

“…Hasegawa, Mazaki, and co-workers successfully applied the C-H arylation method to the synthesis of chiral (1,3-diphenylallene)-TTF-based copolymers (Scheme 13) and investigated the chiroptical properties of the resulting polymers. 48 Conventional cross-coupling reactions cannot be applied to the synthesis of such polymers given the difficulties associated with the preparation of doubly metalated 3,4-(MeS) 2 TTF.…”