Exploring Optically Fueled Dissipative Self-Assembly of a Redox-Active Perylene Diimide Scaffold

Abstract

Dissipative self-assembly is ubiquitous in nature and underlie many complex structures and functions in natural systems, primarily enabled by the consumption of chemical fuels. However, dissipative self-assembly fueled by light have also been parallelly developed. Photoswitchable molecules have been widely investigated as prototypical molecular systems for light driven dissipative self-assembly. Elucidation of optically fueled dissipative self-assembly by a photo-responsive yet non-photoswitchable molecule however remains elusive. This contribution thus demonstrates the first ever report of an optically fueled dissipative self-assembly arising from a redox active perylene diimide scaffold (DIPFPDI). Photo-reduction of neutral DIPFPDI in a poor solvent DMF affords its radical anion and batches of optical re-fueling leads to an increased concentration of radical anion, inducing the construction of an H-type aggregate. Nevertheless, when the influx of visible light is adjourned, the radical anions are converted to their neutral precursors and thus the self-assembled state is no longer sustained. Signature of H-type aggregation is deduced from steady-state UV-Vis, fluorescence as well as time-resolved fluorescence spectroscopy. Theoretical insights reveal that dimerization is more feasible in the charged states because of greater delocalization of the excess charge in the charged states.

Structure-Dependent Triplet State Formation in Fluorinated Perylenediimide Single Crystal Polymorphs

“…The triplet exciton yield calculated by using spectral deconvolution is 88%, which indicates a substantial triplet exciton population available to undergo TTA at longer times. This triplet exciton yield is also consistent with the yield estimated from a kinetic analysis of the decay of the mixed S 1 –CT state from the TRFM data compared to the emissive lifetimes of similar PDI H-aggregates (∼6 ns). , …”

“…This triplet exciton yield is also consistent with the yield estimated from a kinetic analysis of the decay of the mixed S 1 −CT state from the TRFM data compared to the emissive lifetimes of similar PDI H-aggregates (∼6 ns). 39,40 We observe a similar phenomenon for the FPDI-β polymorph in that the first emissive species from TRFM decays in τ = 120 ± 20 ps, which is in good agreement with the decay of the S 1 -CT mixed state observed by fsTAM (τ = 142 ps). A weak emissive component is also observed with a τ = 1.0 ± 0.1 ns time constant, which is similar to the τ = 4.4 ns component in the FPDI-α polymorph, where the low intensity suggests that they may both originate from surface defects or trap sites.…”

A coronene diimide based radical anion for detection of picomolar H2O2: a biochemical assay for detection of picomolar glucose in aqueous medium

“…29 Additionally, wherever necessary, the PDI based radical anions have been stabilized either using the steric protection effect via forming a host-guest complex or inclusion in a metalorganic framework and using other supramolecular approaches such as gelation or supramolecular assembly to increase the stability of the radical anions. [30][31][32][33][34] Although many reports are available for the generation of radical anions of PDI with or without the aid of stabilizers, mostly they are limited to photoreduction of aryl halides or Ag + ions. [35][36][37] To the best of our knowledge, rare reports are available for the generation of CDI based radical anions in aqueous medium with prolonged stability and development of biochemical assay for the detection of picomolar levels of glucose.…”

Perylene-Based Smart Fluoroprobe with Dual Function: Ratiometric Response toward Hazardous Organic Peroxides and Pure White Light Generation via Self-Assembly

“…However, the generation of WL via selfassembly of the organic molecules/molecular system has gained tremendous attention, as self-assemblies offer great advantages of optical tunability, solution processability, and a variety of supramolecular structures. 15 Various non-covalent interactions, including H-bonding, dipole−dipole interactions, π−π stacking, van der Waals forces, etc., play a key role in selfassembly processes. Perylene-based dyes with a large π-surface area and their exceptional properties, such as near-unity emission quantum yield, tunable optical properties, and excellent photostability, are an obvious choice for constructing advanced optical materials.…”

“…Several strategies have been reported for WL generation, such as the host–guest interaction, − Forster resonance energy transfer, excited-state proton transfer, photo-induced electron transfer, self-assembly, , etc. However, the generation of WL via self-assembly of the organic molecules/molecular system has gained tremendous attention, as self-assemblies offer great advantages of optical tunability, solution processability, and a variety of supramolecular structures . Various non-covalent interactions, including H-bonding, dipole–dipole interactions, π – π stacking, van der Waals forces, etc., play a key role in self-assembly processes.…”