Synthesis and Isolation of a Stable Perylenediimide Radical Anion and Its Exceptionally Electron-Deficient Precursor

Abstract

The synthesis and isolation of an ambient stable perylenediimide radical anion is reported, and its precursor is established as one of the strongest electron acceptors. The radical anion shows absorption up to 1400 nm and is stable in mixed aqueous solution. Interestingly, the radical anion can organize two electron-deficient molecules over its surface to form a π-stacked array. Calculations revealed weak spin polarization via noncovalent interactions. Such interactions are of significance for magnetic exchange and catalysis.

Tuning phenoxyl-substituted diketopyrrolopyrroles from quinoidal to biradical ground states through (hetero-)aromatic linkers

“…S12, S13, ESI † ), which, however, could not be isolated. Nevertheless, the result proves that comproportionation of (extended) quinones and bisphenoxides offers an efficient and convenient access to highly desirable radical anions 71 in appropriately functionalised chromophores.…”

Consecutive Charging of a Perylene Bisimide Dye by Multistep Low‐Energy Solar‐Light‐Induced Electron Transfer Towards H2 Evolution

“…Owing to the very strong electron‐withdrawing carbonyl groups, PBIs possess low frontier energy levels and can be reduced into radical anions and dianions readily by moderately strong reductive agents such as hydrazine hydrate or by very weak reductive agents with photo excitation like triethylamine . The corresponding reduced products were shown to be stable in the absence of oxygen especially in polar solvents . Interestingly, the PBI radical anions and dianions show even stronger absorption bands and cover a different absorption range compared to the neutral molecule, thereby enabling additional solar light harvesting.…”

“…[20,21] The corresponding reduced products were shown to be stable in the absence of oxygen especially in polar solvents. [22][23][24][25] Interestingly, the PBI radical anions and dianions show even stronger absorption bands and cover a different absorption range compared to the neutral molecule, thereby enabling additional solar light harvesting. As a consequence, in the presence of a weak reducing agent PBI-bound high energy electrons with a strong reducing ability may be generated by means of multiple photon absorption.…”

Electron-Reservoir Effect on a Perylene Diimide Tethered Rhenium Bipyridine Complex for CO2 Reduction

“…As expected for a PDI-based organic radical, the singly reduced species exhibited an axial resonance with gper = 2.0009, gpar = 2.0037, and no observable hyperfine splitting (Figure S14). 75,76 The EPR spectrum of the triply reduced species displayed a small hyperfine coupling between the bpy-based radical and the rhenium metal center [a( 183,185 Re) = 1.65 mT] (Figure S15), which would only be observed if line-broadening contributions from 35,37 Cl were removed. Previous interpretations of related paramagnetic Re(bpy) complexes have ascribed this type of coupling pattern to an equilibrium process between the chloro-associated (6-coordinate) and chloro-dissociated (5-coordinate) species.…”