A novel low-molecular-mass gelator with a redox active ferrocenyl group: Tuning gel formation by oxidation

Liu, Jing; Yan, Jun; Yuan, Xuanwei; Liu, Kaiqiang; Peng, Junxia; Fang, Yu

doi:10.1016/j.jcis.2007.10.005

Cited by 68 publications

(36 citation statements)

References 43 publications

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“…This leads to the formation of Fc-LS clusters in methanol. This behavior is experimentally established [14,15] and further confirmed by the MD simulation obtained in this study.…”

Section: Conformational Properties Of Fc-ls Gelators In Solutionssupporting

confidence: 87%

“…This suggests that adding Fc-LS molecules into a methanol solution hardly affects its phase transition. It has been experimentally demonstrated that Fc-LS molecules are insoluble in methanol [14,15]; therefore, Fc-LS and methanol form separated phases, and increasing the temperature hardly affect the formation of clusters of Fc-LS molecules. Thus, the increase of the temperature simply brings the solvent to its boiling point.…”

Section: Gel Behavior In the Fc-ls/methanol And Fc-ls/1-pentanol Systemsmentioning

confidence: 99%

“…Cholesterol derivatives are versatile building blocks of LMOGs [12,13]. For instance, Yan et al synthesized a series of LMOGs by combining cholesterol and ferrocene [14]; Liu et al tested the phase behavior of LMGOs of cholesteryl linked to ferrocenyl groups in different solvents [15]. The aim of these studies was to synthesize conductive gels exploiting the well-known redox activity of ferrocene.…”

Section: Introductionmentioning

confidence: 99%

“…1). According to experimental finding [14,15], the ferrocene-amino acid-cholesteryl fragment may promote gel formation with the appropriate solvent. The different phenomenon is observed in different solutions.…”

Section: Introductionmentioning

confidence: 99%

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Phase behavior and electron transfer properties of ferrocenyl cholesteryl N-formanidoformamide gelator: a computational study

Chuang

Tseng

et al. 2015

Colloid Polym Sci

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Molecular dynamics (MD) simulations were carried out to investigate the conformations of a ferrocenyl cholesteryl N-formanidoformamide (Fc-LS) gelator in methanol and 1-pentanol. Our results showed that Fc-LS molecules form a gel in 1-pentanol, but not in methanol. In the Fc-LS/ methanol system, Fc-LS molecules aggregated into clusters stabilized by intermolecular hydrogen bonds. In the Fc-LS/ 1-pentanol system, the Fc-LS molecules dispersed uniformly in the solvent; in addition, the solvent molecules gathered around the Fc-LS molecules. Calculation of diffusion coefficients showed that the Fc-LS/1-pentanol system behaves like a gel over a wide range of temperatures, while the Fc-LS/ methanol system behaves more like a liquid. Charge-transfer properties of the Fc-LS/methanol and Fc-LS/1-pentanol systems were also investigated by quantum mechanical (QM) calculations. The results indicated that the electron transfer integrals of the Fc-LS/1-pentanol system are larger than those of the Fc-LS/methanol system. This suggests that the former is a favorable system for electron transport. Finally, our study demonstrated that the combination of MD and QM represents an effective approach to investigate conductive-gel systems.

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“…This leads to the formation of Fc-LS clusters in methanol. This behavior is experimentally established [14,15] and further confirmed by the MD simulation obtained in this study.…”

Section: Conformational Properties Of Fc-ls Gelators In Solutionssupporting

confidence: 87%

Section: Gel Behavior In the Fc-ls/methanol And Fc-ls/1-pentanol Systemsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Phase behavior and electron transfer properties of ferrocenyl cholesteryl N-formanidoformamide gelator: a computational study

Chuang

Tseng

et al. 2015

Colloid Polym Sci

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“…There are many functional groups showing oxidization-reduction dependent properties, such as ferrocene, 81 tetrathiafulvalene, 82 conjugated groups, 83 transition metal ions, 84 disulfides. 85 The typical example is the ferrocene functionalized polymer, which has a redox responsive center located in the polymer's main chain 51a, 51e or side chain.…”

mentioning

confidence: 99%

Switchable adhesion and friction by stimulus responsive polymer brushes

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An Organometallic Super‐Gelator with Multiple‐Stimulus Responsive Properties

et al. 2008

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Stimulus-responsive gels have recently attracted widespread attention as new functional materials for potential applications in sensors, [1] actuators, [2] shape memories, [3] drug delivery devices, [4] and displays. [5] One of the promising properties that organogels based on low molecular mass organic gelators (LMOGs) can offer is their reversible sol-gel phase transition as a result of external stimuli. [6] As far as we know, redoxresponsive organogels from LMOGs, however, are limited. Shinkai and coworkers [7a] reported the first example of organogels of this kind, which contains a redox-active Cu I / Cu II center. Besides, they also synthesized a series of quater-, quinque-, and sexithiophene derivatives bearing two cholesteryl moieties at the a-position. It was found that a sol-gel phase transition can be implemented by addition of oxidizing and reducing reagents.[7b] Zhu and colleagues [7c] prepared an electro-active LMOG containing a tetrathiafulvalene (TTF) entity. The gel formation can be tuned by means of oxidation/ reduction of the TTF group chemically or electrochemically. Although these gel systems are redox responsive, their properties, such as mechanical strength, flexibility, and sensitivity to external stimulus, are far from those required for practical uses. Therefore, creating instant, reversible, redox-responsive, and mechanically flexible organogels still remains a challenge. As a remarkable organometallic compound, ferrocene (Fc) contains an oxidizable metal ion, Fe II , and is a nonpolar compound in the neutral state, and thereby it dissolves readily in hydrocarbon solvents. This property, however, can be easily reversed by simple oxidation of the central ion. Our interest in stimulus-responsive supramolecular gel systems led us to consider the compound as a neutral-cation redox pair that may be employed to tune the gelling ability of a gelator containing it. Actually, the same idea has been adopted by a number of groups for studies of switchable complexation and molecular aggregation in micelles and vesicles. [8] However, all compounds containing the apolar ferrocenyl or charged ferrocenium moiety reported so far do not result in gelation, as documented for a number of solvents. [8b,8c] Introduction of metal ions is a practical way of giving organogels some smart properties.[9] For example, Sijbesma and coworkers [9a] designed and prepared two chloroform gels with reported a palladium-based organometallic LMOG that is able to catalyze C-C bond formation even in the gel state. We report here four novel cholesterol-appended ferrocene derivatives ( Fig. 1a; see Supporting Information for preparation details), and present first evidence for the gelation ability of organometallic compounds of this kind, and particularly the unusual redox-, mechanical-, and ultrasonic-controllable sol-gel phase transition phenomena. These gelators contain one redox-active ferrocenyl moiety and one cholesteryl residue linked by different diamino units. This design was chosen on the basis of the analys...

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A novel low-molecular-mass gelator with a redox active ferrocenyl group: Tuning gel formation by oxidation

Cited by 68 publications

References 43 publications

Phase behavior and electron transfer properties of ferrocenyl cholesteryl N-formanidoformamide gelator: a computational study

Phase behavior and electron transfer properties of ferrocenyl cholesteryl N-formanidoformamide gelator: a computational study

Switchable adhesion and friction by stimulus responsive polymer brushes

An Organometallic Super‐Gelator with Multiple‐Stimulus Responsive Properties

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