A Bichromophore Based on Perylene and Terrylene for Energy Transfer Studies at the Single-Molecule Level

Abstract

A functionalized dialkylperylene and a modified terrylenetetracarboxdiimide (TTCDI) were joined together by a hexanediyl spacer. The resulting bichromophoric molecule 4 is a suitable model system for donor ± acceptor energy transfer studies at the single-molecule level. With its absorption and fluorescence maximum at shorter wavelengths (l max 450 nm, l fl 458 nm) the dialkylperylene acts as the donor, while the TTCDI with l max 665 nm and l fl 705 nm is the acceptor molecule. The synthetic route to the new bichromophoric molecule and its optical properties (UV/Vis, fluorescence spectroscopy) are presented herein. Energy transfer from the perlyene to the terrylene moiety was confirmed by conventional ensemble fluorescence excitation and emission spectroscopy. Single bichromophores 4 embedded in polyvinylbutyral were imaged with a scanning confocal optical microscope at room temperature by selectively exciting the perylene chromophore and detecting the terrylene emission.

Synthesis of perylene-porphyrin dyads for light-harvesting studies

“…Perylene-monoimides are known to undergo bromination selectively at the 1-, 6-, and 9-positions [25,28,30]. Treatment of mono-bromo perylene 6 with excess bromine in refluxing chloroform afforded the tetrabromo perylene derivative 11 in 59% yield.…”

“…(4) Perylene-imides or their precursors are available for use in a modular building block approach due to the pioneering research of Langhals [19,24], Müllen [25][26][27][28][29], and Wasielewski [30][31][32][33][34]. Perhaps the only drawback to perylene dyes is their limited solubility.…”

“…The chief limitation to such studies is the availability of the requisite perylene-monoimide building blocks. Indeed, routes for incorporating perylene-monoimide dyes in multipigment architectures have had to rely on (1) perylene-monoimides bearing a halogen or ethyne at the 9-position for use in metal-mediated coupling reactions [10,13,19,25,26,[28][29][30][31][32], or (2) perylene-monoanhydrides that upon reaction with an amine yield the perylene-monoimide [30][31][32]. While the latter compounds afford arrays wherein the linker is attached via the N-imide site, the conditions for constructing the linker can be quite forcing.…”

Principles of Single Molecule Multiparameter Fluorescence Spectroscopy

“…Given the strong dependence of FRET efficiency on the donor-acceptor distance, the effect can be used as "spectroscopic ruler". This makes FRET a key technique in SMFS for determination of molecular geometries and for detecting conformational dynamics in a range from 2 to 10 nm [7][8][9][10]. With a larger donor-acceptor distance FRET efficiency is so little that the presence of the acceptor can be determined by additional direct excitation only.…”

Photoinduced electron and energy transfer from coumarin 153 to perylenetetracarboxylic diimide in bmimPF6/TX-100/water microemulsions

“…They showed great potential of realistic application as organic field-effect transistors [23][24][25], light-harvesting solar cells [26][27][28][29][30][31], and light-emitting diodes [32][33][34][35][36]. Furthermore, PDI chromophores offered broad spectral coverage and large extinction coefficient in near-infrared range, therefore, they were frequently employed in single molecule spectroscopic studies [37][38][39][40][41] and construction of multichromophoric arrays for energy and electron-transfer studies [42,43]. Recently, energy and electron transfer involving PDIs had been investigated in organic solvents, molecular aggregates and even in solid-states [44][45][46][47].…”