CaltechAUTHORS
  A Caltech Library Service

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

Nemykin, Victor N. and Makarova, Elena A. and Grosland, Jeffrey O. and Hadt, Ryan G. and Koposov, Alexey Y. (2007) Preparation, characterization, molecular and electronic structures, TDDFT, and TDDFT/PCM study of the solvatochromism in cyanovinylferrocenes. Inorganic Chemistry, 46 (23). pp. 9591-9601. ISSN 0020-1669. http://resolver.caltech.edu/CaltechAUTHORS:20180612-161523450

[img] Crystallographic Info File (CIF) - Supplemental Material
See Usage Policy.

20Kb
[img] Crystallographic Info File (CIF) - Supplemental Material
See Usage Policy.

19Kb
[img] Crystallographic Info File (CIF) - Supplemental Material
See Usage Policy.

19Kb
[img] Crystallographic Info File (CIF) - Supplemental Material
See Usage Policy.

19Kb
[img] PDF - Supplemental Material
See Usage Policy.

811Kb

Use this Persistent URL to link to this item: http://resolver.caltech.edu/CaltechAUTHORS:20180612-161523450

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.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/ic700558vDOIArticle
https://pubs.acs.org/doi/suppl/10.1021/ic700558vPublisherSupporting Information
ORCID:
AuthorORCID
Hadt, Ryan G.0000-0001-6026-1358
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.
Funders:
Funding AgencyGrant Number
Cottrell Scholar of Research CorporationCC6766
University of Minnesota Duluth20209
Minnesota Supercomputing InstituteUNSPECIFIED
Record Number:CaltechAUTHORS:20180612-161523450
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20180612-161523450
Official Citation:Preparation, Characterization, Molecular and Electronic Structures, TDDFT, and TDDFT/PCM Study of the Solvatochromism in Cyanovinylferrocenes Victor N. Nemykin, Elena A. Makarova, Jeffrey O. Grosland, Ryan G. Hadt, and Alexey Y. Koposov Inorganic Chemistry 2007 46 (23), 9591-9601 DOI: 10.1021/ic700558v
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:87042
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:13 Jun 2018 14:39
Last Modified:13 Jun 2018 14:39

Repository Staff Only: item control page