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Published November 12, 2007 | Supplemental Material
Journal Article Open

Preparation, characterization, molecular and electronic structures, TDDFT, and TDDFT/PCM study of the solvatochromism in cyanovinylferrocenes

Abstract

Cis and trans isomers of ferrocene-based donor-acceptor assemblies, Fc-C(I)=CH(I), Fc-C(I)=CH(CN), and Fc-C(CN)=CH(CN) (Fc is ferrocene), along with the Fc-C(CN)=C(CN)_2 complex have been prepared and characterized by ^1H, ^(13)C, gHMQC, and gHMBC NMR spectra, IR, UV-vis, and MCD spectroscopy methods, as well as elemental analyses. The oxidation potentials, investigated by cyclic voltammetry, of all donor-acceptor assemblies are in agreement with the electron-acceptor strength of the substituents attached to the ferrocene core. X-ray crystallography studies of cis and trans isomers of Fc-C(I)=CH(CN) and Fc-C(CN)=CH(CN) reveal a significant rotational flexibility of the cyanovinyl group, which was explained on the basis of semiempirical PM3 calculations. Electronic structures and solvatochromic properties of all complexes were investigated by UV-vis spectroscopy, density functional theory (DFT), time-dependent DFT (TDDFT), and polarized continuum model (PCM) TDDFT approaches. The calculated vertical excitation energies and magnitudes of solvatochromic effect are consistent with the experimental data and clearly suggest the dominance of metal-to-ligand charge-transfer bands in the visible region of the UV-vis spectra for all complexes.

Additional Information

© 2007 American Chemical Society. Received March 23, 2007. Generous support from the Research Corporation (Cottrell College Science Award CC6766), University of Minnesota Grant-in-Aid (Grant No. 20209) and Minnesota Supercomputing Institute to V.N. and University of Minnesota Duluth Undergraduate Research Opportunity Grants to J.G. and R.H. are greatly appreciated.

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Created:
August 19, 2023
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October 18, 2023