Macrocyclic Donor–Acceptor Dyads Composed of a Perylene Bisimide Dye Surrounded by Oligothiophene Bridges

Abstract

Two macrocyclic architectures comprising oligothiophene strands that connect the imide positions of a perylene bisimide (PBI) dye have been synthesized via a platinum‐mediated cross‐coupling strategy. The crystal structure of the double bridged PBI reveals all syn‐arranged thiophene units that completely enclose the planar PBI chromophore via a 12‐membered macrocycle. The target structures were characterized by steady‐state UV/Vis absorption, fluorescence and transient absorption spectroscopy, as well as cyclic and differential pulse voltammetry. Both donor–acceptor dyads show ultrafast Förster Resonance Energy Transfer and photoinduced electron transfer, thereby leading to extremely low fluorescence quantum yields even in the lowest polarity cyclohexane solvent.

Advances in Molecular Design and Photophysical Engineering of Perylene Bisimide-Containing Polyads and Multichromophores for Film-Based Fluorescent Sensors

“…An incoherent electron transport from the donor to the acceptor occurred in this kind of molecular system; however, any exciplex intermediates can rarely be observed. Such a phenomenon is precisely predicted by Scholes. , Würthner et al recently reported two PBI derivatives modified in the imide positions with oligothiophene strands, forming the macrocyclic aesthetic PBI dyads 5T-PBI and (5T) 2 -PBI (Figure a) . Both donor–acceptor dyads featured ultrafast Förster resonance energy transfer from the oligothiophene to the PBI scaffold.…”

“…(b) Representative examples of PBI-containing polyads in FFSs applications. Panel (a) reproduced with permission from ref . Copyright 2021 The Authors.…”

“…19,20 Wurthner et al recently reported two PBI derivatives modified in the imide positions with oligothiophene strands, forming the macrocyclic aesthetic PBI dyads 5T-PBI and (5T) 2 -PBI (Figure 2a). 21 Both donor−acceptor dyads featured ultrafast Forster resonance energy transfer from the oligothiophene to the PBI scaffold. As expected, their UV/vis spectra showed a simple superposition of the subunits, where the PBI moiety always showed the characteristic S 0 −S 1 transition with well-resolved vibronic progression.…”

Rescuing the solid-state fluorescence of perylene diimide dyes by host–guest isolation

“…Other strategies such as incorporating PDI into cyclic scaffolds or other rigid frames were presented. 1,24–30 These strategies also require sophisticated design and synthesis which sometimes can endow PDI dyes with properties beyond luminescence. Quarantining PDI molecules through host–guest recognition represents another useful yet less reported strategy.…”

POSS-containing polynorbornene with pendant perylene diimide: from a unique supramolecular structure to tunable luminescence properties

“…Perylene diimide (PDI) derivatives are a class of important chromophore groups, whose extended π-conjugation systems lead to many optical and electronic applications. 1–10 To develop functional polymer materials with different nanostructures and photovoltaic performance, much research has been focused toward introducing PDI molecules to main-chain polymers or block copolymers. 11–15 Moreover, the PDI side-chain polymer has more potential to combine the desirable photoelectric properties of PDIs with the mechanical strength and film forming properties of polymers due to their self-assembling ability.…”