Details
| Original language | English |
|---|---|
| Pages (from-to) | 808-814 |
| Number of pages | 7 |
| Journal | Chemistry of materials |
| Volume | 25 |
| Issue number | 5 |
| Early online date | 28 Feb 2013 |
| Publication status | Published - 12 Mar 2013 |
Abstract
Bistability of valence tautomeric donor-acceptor dyads formed by covalently linking a ferrocene-based electron-donor and the perchlorotriphenylmethyl radical, as the electron-acceptor, is tuned via a chemical modification of the ferrocene group. Specifically, the methylation of the ferrocene unit increases the strength of the donor group stabilizing the zwitterionic state in polar solvents and leading to an intriguing coexistence of neutral and zwitterionic species in solvents of intermediate polarity. Bistability in the crystalline phase is demonstrated by temperature dependent Mössbauer spectra. This complex and interesting behavior is quantitatively rationalized in the framework of a bottom-up modeling strategy. Optical spectra in solution are first analyzed to extract and parametrize an effective two-state molecular model, which is then adopted to rationalize the observed bistability in the solid state as due to cooperative electrostatic interchromophore interactions.
Keywords
- Bistability, Intramolecular electron-transfer, Mössbauer spectroscopy, Optical spectroscopy, Solvatochromism, Valence tautomers
ASJC Scopus subject areas
- Chemistry(all)
- General Chemistry
- Chemical Engineering(all)
- General Chemical Engineering
- Materials Science(all)
- Materials Chemistry
Cite this
- Standard
- Harvard
- Apa
- Vancouver
- BibTeX
- RIS
In: Chemistry of materials, Vol. 25, No. 5, 12.03.2013, p. 808-814.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - Bistability of Fc-PTM-Based Dyads
T2 - The Role of the Donor Strength
AU - Guasch, Judith
AU - Grisanti, Luca
AU - Jung, Stefan
AU - Morales, Dayana
AU - D'Avino, Gabriele
AU - Souto, Manuel
AU - Fontrodona, Xavier
AU - Painelli, Anna
AU - Renz, Franz
AU - Ratera, Imma
AU - Veciana, Jaume
PY - 2013/3/12
Y1 - 2013/3/12
N2 - Bistability of valence tautomeric donor-acceptor dyads formed by covalently linking a ferrocene-based electron-donor and the perchlorotriphenylmethyl radical, as the electron-acceptor, is tuned via a chemical modification of the ferrocene group. Specifically, the methylation of the ferrocene unit increases the strength of the donor group stabilizing the zwitterionic state in polar solvents and leading to an intriguing coexistence of neutral and zwitterionic species in solvents of intermediate polarity. Bistability in the crystalline phase is demonstrated by temperature dependent Mössbauer spectra. This complex and interesting behavior is quantitatively rationalized in the framework of a bottom-up modeling strategy. Optical spectra in solution are first analyzed to extract and parametrize an effective two-state molecular model, which is then adopted to rationalize the observed bistability in the solid state as due to cooperative electrostatic interchromophore interactions.
AB - Bistability of valence tautomeric donor-acceptor dyads formed by covalently linking a ferrocene-based electron-donor and the perchlorotriphenylmethyl radical, as the electron-acceptor, is tuned via a chemical modification of the ferrocene group. Specifically, the methylation of the ferrocene unit increases the strength of the donor group stabilizing the zwitterionic state in polar solvents and leading to an intriguing coexistence of neutral and zwitterionic species in solvents of intermediate polarity. Bistability in the crystalline phase is demonstrated by temperature dependent Mössbauer spectra. This complex and interesting behavior is quantitatively rationalized in the framework of a bottom-up modeling strategy. Optical spectra in solution are first analyzed to extract and parametrize an effective two-state molecular model, which is then adopted to rationalize the observed bistability in the solid state as due to cooperative electrostatic interchromophore interactions.
KW - Bistability
KW - Intramolecular electron-transfer
KW - Mössbauer spectroscopy
KW - Optical spectroscopy
KW - Solvatochromism
KW - Valence tautomers
UR - http://www.scopus.com/inward/record.url?scp=84874998919&partnerID=8YFLogxK
U2 - 10.1021/cm400147p
DO - 10.1021/cm400147p
M3 - Article
AN - SCOPUS:84874998919
VL - 25
SP - 808
EP - 814
JO - Chemistry of materials
JF - Chemistry of materials
SN - 0897-4756
IS - 5
ER -