Synthesis, Structure, and Spectroelectrochemistry of Ferrocenyl–Meldrum’s Acid Donor–Acceptor Systems

Abstract

The synthesis of two new donor−acceptor ferrocenyl derivatives with Meldrum's acid based nonplanar acceptor substituents is presented. Both compounds are obtained in high yields in a simple reaction protocol under mild conditions using either 1-acetyl-or 1,1′-diacetylferrocene and Meldrum's acid. Both products have been characterized spectroscopically, by single-crystal X-ray structure analysis, by electrochemical and UV/vis/IR spectroelectrochemical measurements, and by (TD)-DFT calculations. The spectroelectrochemical measurements disclose that the 2,2-dimethyl-1,3-dioxane-4,6-dione moiety is a moderately strong electron acceptor. Article pubs.acs.org/Organometallics

Ferrocenyl GNA Nucleosides: A Bridge between Organic and Organometallic Xeno‐nucleic Acids

“…The spectra show intense UV absorption bands below 300 nm, a less intense near‐UV band at 330 nm and relatively weak absorptions in the visible region with the maximum at 438 nm (Table ). Such a pattern of the absorption spectra corroborates with the literature spectroscopic data for ferrocene derivatives …”

“…As expected for the low‐spin ferrocene derivative, the three highest lying occupied molecular orbitals HOMO, HOMO‐1 and HOMO‐2 in ( R , S )‐ 2 dominantly correspond to the iron‐centered d , d xy and d atomic orbitals . The lowest unoccupied molecular orbital (LUMO) of ( R , S )‐ 2 has π‐character and is delocalized over the thymine moiety.…”

Synthesis, crystal structures and electrochemical properties of ferrocenyl imidazole derivatives

“…The spectra obtained in acetonitrile show bands at approximately 328 and 438 nm. The bands at 328 nm represent π-π* transitions from the ferrocenyl to the imidazole moiety, while the bands at 438 nm are ascribed to d - d transitions, probably mixed with d -π* transitions [41]. There is a shift of the π-π* band of compounds 2 and 5 , at 328 nm bathochromically to 331 nm, attributed to the stronger electron-withdrawing effect of the nitro group on the imidazole moiety [42, 43].…”

D–A dyads and A–D–A triads based on ferrocene: push–pull dyes with unusual behaviours in solution

“…[45][46][47][48][49][50][51][52][53][54][55] Conversely, acceptor-donoracceptor (A-D-A) triads based on ferrocene have only been scarcely examined in the literature (See Figure 1). [56][57][58][59][60][61] Especially, photophysical properties of A-D-A triads based on ferrocene have only been examined in details in the case of Meldrum's derivatives (UV-visible absorption, fluorescence spectroscopy and spectroelectrochemistry). Ferrocene possesses a low oxidation potential (0.52, 0.44 and 0.43 V vs SCE in dichloromethane, acetonitrile, or DMF) 62 and can be thus oxidized as ferrocenium by a one-electron oxidation process.…”