Charge-transfer complexes interactions evidenced by chemical force microscopy

Gil, Richard; Fiaud, Jean‐Claude; Poulin, Jean-Claude; Schulz, Emmanuelle

doi:10.1039/b304829b

Cited by 19 publications

(26 citation statements)

References 12 publications

(11 reference statements)

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“…[146,147] For this purpose, trinitrofluorenone was immobilized on an AFM tip while anthracene was grafted on quartz surfaces. The pull-off force of the multiple intermolecular complexes was determined to be ≈6.6 nN in dodecane (a good solvent for the formation of the complex), while the use of a competitive solvent like 1-methylnaphthalene decreased the force to 1.7 nN, [147] demonstrating how the immediate environment influences the response of such complexes to mechanical stimuli. More recently, the use of charge-transfer complexes was explored for the preparation of microcapsulebased damage reporting polymer materials by Lavrenova et al [148] In this case, a colorless hexamethylbenzene donor and a chloranil acceptor were separately dissolved in toluene and Figure 8.…”

Section: Mechanoresponsive Materials With Charge-transfer Complexesmentioning

confidence: 99%

“…For example, the formation and dissociation of the chargetransfer complex between trinitrofluorene and anthracene were probed in SMFS experiments. [146,147] For this purpose, trinitrofluorenone was immobilized on an AFM tip while anthracene was grafted on quartz surfaces. The pull-off force of the multiple intermolecular complexes was determined to be ≈6.6 nN in dodecane (a good solvent for the formation of the complex), while the use of a competitive solvent like 1-methylnaphthalene decreased the force to 1.7 nN, [147] demonstrating how the immediate environment influences the response of such complexes to mechanical stimuli.…”

Section: Mechanoresponsive Materials With Charge-transfer Complexesmentioning

confidence: 99%

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From Molecules to Polymers—Harnessing Inter‐ and Intramolecular Interactions to Create Mechanochromic Materials

Traeger

Kiebala

Weder

et al. 2020

Macromol. Rapid Commun.

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tion occurs to avoid catastrophic materials failure and to possibly redirect degradation processes into useful responses. Consequently, research efforts directed toward the investigation and development of mechanoresponsive materials has drawn ever increasing attention. [2,3,5-8] Polymers that translate mechanical stresses into a defined response are thought to be useful for many different applications, including as tamper-proof packaging materials, [9] as degradable plastics, [10,11] or for structural health monitoring. [12] One possibility to render polymers mechanoresponsive is the integration of so-called mechanophores. The latter generally feature a weak covalent bond that undergoes either homo-or heterolytic cleavage upon experiencing a force that exceeds a certain threshold. [1,5,7,13,14] These motifs are covalently incorporated into a polymer and serve as predefined weak links that preferentially break or transform in response to an applied mechanical force. [1,6,14-16] Widely investigated mechanophores include spiropyrans, 1,2-dioxetanes, and Diels-Alder adducts. [16-18] The rate constants, threshold forces, and transition state bond-lengths and energies of many mechanophores have been well-characterized via techniques such as single-molecule force spectroscopy (SMFS), [19-22] force-modified potential energy surface modeling, [23] and in situ activation using sonication. [2,22,24] The insights gained in such studies have driven advancements in the field of mechanoresponsive materials and the mechanical activation has, for example, been harnessed to promote thermodynamically unfavorable reactions, [19] affect the intra-or intermolecular transfer of protons, [20,25,26] release small molecules, [27] initiate the depolymerization of the surrounding material, [10,28] or elicit changes in the material's color or fluorescence. [16,17,29] The fact that the active bond or functional group of a mechanophore is typically cleaved irreversibly can limit its utility. Some mechanophores can be returned to their original state through an additional stimulus such as light or heat, but unless the mechanophore undergoes a nonscissile cleavage (e.g., a ring-opening reaction, such as in spiropyrans), the reversal is generally hampered by kinetic factors that leave the mechanophore in its cleaved state. [30] An irreversible response can be desirable for some

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Section: Mechanoresponsive Materials With Charge-transfer Complexesmentioning

confidence: 99%

Section: Mechanoresponsive Materials With Charge-transfer Complexesmentioning

confidence: 99%

From Molecules to Polymers—Harnessing Inter‐ and Intramolecular Interactions to Create Mechanochromic Materials

Traeger

Kiebala

Weder

et al. 2020

Macromol. Rapid Commun.

View full text Add to dashboard Cite

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“…Charge-transfer complexes (CTCs) arising from the interaction of aromatic p-donor and p-acceptor molecules have been studied extensively 15 and recently charge-transfer complex interactions have been evidenced by chemical force microscopy. 16 CTCs have been used in supramolecular chemistry, 17 for chiral recognition, 18 and for selective organic transformation. 19 An adsorption process is being explored in our laboratory for ultra-deep desulfurization of distillate fuels based on selective removal of electron rich refractory sulfur compounds like 4,6dimethyl dibenzothiophene 1 (Fig.…”

Section: Introductionmentioning

confidence: 99%

Ultra-deep desulfurization of transportation fuels via charge-transfer complexes under ambient conditions

et al. 2005

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“…20,23,[28][29][30][31][32][33][34][35]37,38 We have evaluated the single force for specific hydrogen bonding between the phenylurea and carboxyl groups by a statistical method using autocorrelation analysis of the values of the adhesion force. In this analysis, an autocorrelation function is computed for the histogram data of the observed pull-off forces.…”

Section: Single Force Of Hydrogen Bonding On Mixed Mha/ht Sams (Cooh/mentioning

confidence: 99%

“…[8][9][10][11][12][13][14][15][16][17][18][19]36 Furthermore, the individual force for a variety of intermolecular forces at a single-molecule level can also be evaluated by statistical analyses of the forces obtained by repetitive adhesion force measurements. [20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35]37,38 In our previous studies, we measured specific intermolecular forces attributable to the characteristic molecular functionalities of the functional molecules, such as crown ether 36,37 and spirobenzopyran 38 derivatives, attached covalently on the probe tips. These functionalized AFM probe tips, which possess a powerful capability of detecting supramolecular interactions, can be potentially utilized for developing a novel analytical tool for surface analysis based on force sensing by AFM.…”

Section: Introductionmentioning

confidence: 99%

Effect of Intramonolayer Hydrogen Bonding of Carboxyl Groups in Self-assembled Monolayers on a Single Force with Phenylurea on an AFM Probe Tip

2006

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IntroductionDuring the recent decade, atomic force microscopy (AFM) has attracted much attention as a promising analytical tool for precisely measuring intermolecular forces.1-5 AFM can be used to detect the force between its probe tip and substrate surfaces, even at the pN level. It is thus of great importance that there is almost no limitation of the environment and conditions where the AFM force measurements are carried out. Thus, if the AFM probe tip and the substrate are modified chemically with selfassembled monolayers (SAMs) 6,7 terminating with target functional groups, the intermolecular force in their molecular pairs can be evaluated by force-curve measurements in appropriate solvents by AFM. [8][9][10][11][12][13][14][15][16][17][18][19]36 Furthermore, the individual force for a variety of intermolecular forces at a single-molecule level can also be evaluated by statistical analyses of the forces obtained by repetitive adhesion force measurements. [20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35]37,38 In our previous studies, we measured specific intermolecular forces attributable to the characteristic molecular functionalities of the functional molecules, such as crown ether 36,37 and spirobenzopyran 38 derivatives, attached covalently on the probe tips. These functionalized AFM probe tips, which possess a powerful capability of detecting supramolecular interactions, can be potentially utilized for developing a novel analytical tool for surface analysis based on force sensing by AFM.In such AFM force measurements, SAMs are often used for conveniently established covalent bonding of the target molecules onto the surfaces of the tip and substrate. Then, the intramonolayer interaction between the components in the SAMs can be expected to affect the force observed by the AFM technique. In other words, the AFM technique could detect such effects as the intramonolayer interaction on the interaction between the tip and the substrate. Intramonolayer hydrogen bonding is crucial in the SAMs of thiols or silanes bearing a terminal functional group, which can form hydrogen bondings between themselves. For example, terminal carboxyl groups in the SAMs of ω-carboxyalkanethiol can easily form hydrogen bonding within the monolayers. 39-42The COOH-terminated SAMs, such as thiol and silane, have been analyzed by FT-IR spectroscopy. 44 Especially, in the case of COOH-terminated SAMs, the effect of the intramonolayer hydrogen bonding between the neighboring carboxyl groups in the SAMs had been considered with respect to their surface property, such as wettability 45 and surface acidity (pKa) of the carboxyl groups. [41][42][43] In the present paper, we report an AFM force spectroscopic study concerning the effect of intramonolayer hydrogen bonding in COOH-terminated SAMs of 6-mercaptohexanoic acid (MHA) on the adhesion force observed between a SAM of MHA and a phenylurea derivative attached to the substrate and probe tip, respectively.Urea derivatives have a powerful ability to form hydrogen bondings, sin...

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Charge-transfer complexes interactions evidenced by chemical force microscopy

Abstract: Charge-transfer complexes have been detected by chemical force microscopy (CFM) between a tip and a substrate respectively functionalized with trinitrofluorenone and 9-anthracenemethanol siloxane derivatives.

Cited by 19 publications

References 12 publications

From Molecules to Polymers—Harnessing Inter‐ and Intramolecular Interactions to Create Mechanochromic Materials

From Molecules to Polymers—Harnessing Inter‐ and Intramolecular Interactions to Create Mechanochromic Materials

Ultra-deep desulfurization of transportation fuels via charge-transfer complexes under ambient conditions

Effect of Intramonolayer Hydrogen Bonding of Carboxyl Groups in Self-assembled Monolayers on a Single Force with Phenylurea on an AFM Probe Tip

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