The Ugi four-component reaction as a concise modular synthetic tool for photo-induced electron transfer donor-anthraquinone dyads.

Sarah Bay,Thomas J J Müller,Gamall Makhloufi,Christoph Janiak

doi:10.3762/bjoc.10.100

Abstract

Phenothiazinyl and carbazolyl-donor moieties can be covalently coupled to an anthraquinone acceptor unit through an Ugi four-component reaction in a rapid, highly convergent fashion and with moderate to good yields. These novel donor–acceptor dyads are electronically decoupled in the electronic ground state according to UV–vis spectroscopy and cyclic voltammetry. However, in the excited state the inherent donor luminescence is efficiently quenched. Previously performed femtosecond spectroscopic measurements account for a rapid exergonic depopulation of the excited singlet states into a charge-separated state. Calculations of the Gibbs energy of photo-induced electron transfer from readily available UV–vis spectroscopic and cyclovoltammetric data applying the Weller approximation enables a quick evaluation of these novel donor–acceptor dyads. In addition, the X-ray structure of a phenothiazinyl–anthraquinone dyad supports short donor–acceptor distances by an intramolecular π-stacking conformation, an important assumption also implied in the calculations of the Gibbs energies according to the Weller approximation.

Highlights

Chromophores, fluorophores, and electrophores, are functional organic materials [1] and constitute active components in molecular electronics [2], photonics [3], and bioanalytics [4,5,6]
We have recently employed the Ugi 4CR as a one-step process to simultaneously introduce a phenothiazinefunctionalized amine and an anthraquinone-substituted aldehyde together with acetic acid and tert-butyl isocyanide for rapidly assembling a donor–acceptor conjugate 1 displaying a photo-induced electron transfer leading to a charge-separated state with a lifetime of >2 ns (Figure 1), as elucidated by femtosecond transient absorption spectroscopy [56]
We present the synthetic versatility of this multicomponent approach to Do–anthraquinone dyads, as exemplified by phenothiazinyl and carbazole moieties as donors, and comprehensive physical organic studies of electronic and electrochemical properties investigated by steady state UV–vis and fluorescence spectroscopy as well as cyclic voltammetry

Summary

Introduction

Chromophores, fluorophores, and electrophores, are functional organic materials [1] and constitute active components in molecular electronics [2], photonics [3], and bioanalytics [4,5,6]. We have recently employed the Ugi 4CR as a one-step process to simultaneously introduce a phenothiazinefunctionalized amine and an anthraquinone-substituted aldehyde together with acetic acid and tert-butyl isocyanide for rapidly assembling a donor–acceptor conjugate 1 displaying a photo-induced electron transfer leading to a charge-separated state with a lifetime of >2 ns (Figure 1), as elucidated by femtosecond transient absorption spectroscopy [56].

Results

Conclusion