Bistability of Fc-PTM-Based Dyads: The Role of the Donor Strength
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- 作者：Judith Guasch ; Luca Grisanti ; Stefan Jung ; Dayana Morales ; Gabriele D鈥橝vino ; Manuel Souto ; Xavier Fontrodona ; Anna Painelli ; Franz Renz ; Imma Ratera ; Jaume Veciana
- 刊名：Chemistry of Materials
- 出版年：2013
- 出版时间：March 12, 2013
- 年：2013
- 卷：25
- 期：5
- 页码：808-814
- 全文大小：434K
- 年卷期：v.25,no.5(March 12, 2013)
- ISSN：1520-5002
文摘
Bistability of valence tautomeric donor鈥揳cceptor 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 M枚ssbauer 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.