Energy Transfer in Calixarene-Based Cofacial-Positioned Perylene Bisimide Arrays

Abstract

The synthesis of multichromophoric perylene bisimide-calix[4]arene arrays with up to five perylene units (containing orange, violet, and green perylene bisimide chromophores) and of monochromophoric model compounds was achieved by subsequent imidization of mono-Boc functionalized calix[4]arene linkers with three different types of perylene bisimide dye units. The optical properties of all compounds were studied with UV/vis absorption and steady state and time-resolved fluorescence spectroscopy. Upon excitation of the inner orange dye at 490 nm of array 3, strong fluorescence emission of the outer green perylene bisimide (PBI) chromophore at 744 nm is observed. The fluorescence excitation spectra of compounds 3 and 4 (lambdadet = 850 nm) show all absorption bands of the parent chromophores (e.g., all perylene units contribute to the emission from S1 state of the green PBI). Thus, the fluorescence emission and excitation spectra as well as time-resolved data of fluorescence lifetimes in the absence (tauD = 5.1 ns) and in the presence of an acceptor (tauDA = 0.8 ns) suggest efficient energy transfer processes between the perylene bisimide dye units. For the bichromophoric array 4, the energy transfer rate is calculated to a value of 1.05 x 109 s-1. These results demonstrate highly efficient energy transfer in cofacially assembled dye arrays.

Perylene Bisimide Dye Assemblies as Archetype Functional Supramolecular Materials

“…170,171 Moreover, photophysical properties of multichromophoric PBI-calix [4]arene arrays containing up to five PBI chromophores have been investigated with the results that these arrays exhibit sequential fluorescence-resonance energy transfer (FRET) processes ( Figure 10). 88,172 …”

Energy Transfer Pathways in a Rylene‐Based Triad

“…[11] Mimicking these photosynthetic functions by using artificial models with well-defined molecular architectures not only furthers our understandings of the role and interplay of different mechanisms involved in biological photosynthesis systems but also opens perspectives for technological advances in materials for solar energy conversion, and electronic or optoelectronic devices. [12][13][14][15][16][17][18] In this context, a variety of designed architectures has been recently suggested, such as rigid linear arrays of chromophores linked by spacer units, [19][20][21][22][23][24][25][26][27][28][29][30] branched, [31,32] square or circular systems [33][34][35] or dendrimers. [36,37] The large interest in the dendritic structures decorated with different types of chromophores arises from the possibility of efficient energy migration through their large structure from the peripheral units to the central chromophore or among the units at the dendrimer surface.…”

Emission properties of cyclodextrin dimers linked with perylene diimide—effect of cyclodextrin tumbling

“…[5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21] In particular, supramolecular assemblies based on calixarenePDI conjugates show efficient energy and electron transfer properties due to the well-defined rigid and electron-rich scaffolds of calixarenes. [22][23][24][25][26][27] We have prepared PDI derivatives with a high emission property in aqueous solutions.Generally, PDI derivatives have low solubilities in aqueous solutions. Even if PDI derivatives are dissolved in aqueous solutions by introducing a hydrophilic group, the emission of PDI derivatives exhibit self-quenching in aqueous solutions due to the formation of supramolecular assemblies and folders.…”