3-Pyrenylacrylates: Synthetic, Photophysical, Theoretical and Electrochemical Investigations

Abstract

The Mizoroki-Heck coupling of 1-bromopyrene with acrylates provides a convenient access to a variety of 3-pyrenylacrylates in very good yields (up to 93 %). Their photophysical properties combined with solvatochromic effects were studied. In addition, electrochemical oxidation potentials were determined by DPV (differential pulse voltammetry) measurements. The fine structure of the absorbance spectra obtained from photophysical measurements are compared with the results of theoretical calculations performed by time dependent TD-B3LYP methods using the 6-31G* basis set.

Aerobic Palladium(II)-Catalyzed Dehydrogenative Heck Reaction in the Synthesis of Pyrenyl Fluorophores. A Photophysical Study of β-Pyrenyl Acrylates in Solution and in the Solid State

“…The major reaction product 2a was isolated from the reaction mixture by fractional crystallization and identified by a comparison with a sample obtained via the classical Heck reaction from 1-bromopyrene and ethyl acrylate . However, we were unable to isolate 3a in pure form.…”

“…The major reaction product 2a was isolated from the reaction mixture by fractional crystallization and identified by a comparison with a sample obtained via the classical Heck reaction from 1-bromopyrene and ethyl acrylate. 10 However, we were unable to isolate 3a in pure form. Therefore, we synthesized this compound via Heck reaction 10 from 4bromopyrene 30 (Scheme 2) and demonstrated that the 1 H NMR spectrum of the mixture of products is identical with the spectrum of a 6:1 mixture of 2a and 3a prepared from pure components (Figure 1).…”

“…Despite their simplicity and environmentally friendly character, the DCC reactions found so far only little use in structural modifications of pyrene, with reported examples being limited to arylation and borylation [25][26][27][28] In our first attempts we applied the experimental conditions described earlier for alkenylation of ferrocene 29 , i.e. 10 However, we were unable to isolate 3a in pure form. However, by performing this reaction at 70 °C we obtained only a trace amount of alkenylated pyrenes, which is in line with the lower nucleophilic reactivity of pyrene than ferrocene.…”

“…Pyrene and its derivatives are important and thoroughly investigated organic fluorophores that have found various applications in molecular electronics and photovoltaic cells and as fluorescent probes and sensors. − Alkenylpyrenes have been used as monomers for the synthesis of polymers containing fluorescent groups attached to the polymer backbone and as probes to monitor polymerization . It has been found that the conjugation of alkenyl groups with the pyrenyl moiety strongly influences the electronic structure and luminescent properties of such compounds. − Until now, a general route to alkenylpyrenes has been a classical cross-coupling reaction starting from corresponding bromo- or iodopyrenes. − …”

“…[1][2][3][4][5][6] Alkenylpyrenes have been used as monomers for the synthesis of polymers containing fluorescent groups attached to the polymer backbone 7 and as probes to monitor polymerization. [9][10][11] Up until now a general route to alkenylpyrenes have been the classical crosscoupling reactions starting from corresponding bromo-or iodopyrenes. [9][10][11] Up until now a general route to alkenylpyrenes have been the classical crosscoupling reactions starting from corresponding bromo-or iodopyrenes.…”