Light-responsive reversible solvation and precipitation of gold nanoparticles

Raimondo, Corinna; Reinders, Federica; Soydaner, Umut; Mayor, Marcel; Samorı́, Paolo

doi:10.1039/b915491d

Cited by 61 publications

(57 citation statements)

References 41 publications

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“…1D). The isomerization state of the SAM has been shown capable to modulate the AuNP aggregation within the blend, thus the density and dispersion of the particles in the polymeric host (25). In the following, we name the set of devices prepared starting from the trans isomer "a-AZONPs" (in which "a" stands for aggregated), and those starting with the cis isomer "s-AZONPs" (with "s" meaning solvated).…”

Section: Resultsmentioning

confidence: 99%

“…Thus, to allow data comparison for different binary systems, we prepared devices using the highest amount of NPs that, once blended with the P3HT, showed a gate response. The C TH amounted to 18 wt% for s-AZONPs and only to 1 wt% for a-AZONPs because of its markedly high propensity to aggregate (25). For the case of OPE-NPs, 18 wt% was used to allow optimal comparison with the s-AZONPs devices.…”

Section: Figurementioning

confidence: 99%

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Optically switchable organic field-effect transistors based on photoresponsive gold nanoparticles blended with poly(3-hexylthiophene)

Raimondo

Crivillers

Reinders

et al. 2012

Proc. Natl. Acad. Sci. U.S.A.

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Interface tailoring represents a route for integrating complex functions in systems and materials. Although it is ubiquitous in biological systems-e.g., in membranes-synthetic attempts have not yet reached the same level of sophistication. Here, we report on the fabrication of an organic field-effect transistor featuring dualgate response. Alongside the electric control through the gate electrode, we incorporated photoresponsive nanostructures in the polymeric semiconductor via blending, thereby providing optical switching ability to the device. In particular, we mixed poly(3-hexylthiophene) with gold nanoparticles (AuNP) coated with a chemisorbed azobenzene-based self-assembled monolayer, acting as traps for the charges in the device. The light-induced isomerization between the trans and cis states of the azobenzene molecules coating the AuNP induces a variation of the tunneling barrier, which controls the efficiency of the charge trapping/detrapping process within the semiconducting film. Our approach offers unique solutions to digital commuting between optical and electric signals.O rganic field-effect transistors (OFETs) are basic building blocks for logic applications and for the development of electronic technologies based on soft matter (1-4). Currently, the greatest challenges in the field are the achievement of higher device performance and the development of devices featuring uncommon and multiple functionalities (5). In this regard, hybrid organic-inorganic materials are gaining much attention because, besides their easy processing, they can take advantage of the tunability of the chemical properties of the components, and thus of the material as a whole. Nanoparticles (NPs) of different materials (gold, silver, metal oxides, etc.) can be coated with selfassembled monolayers (SAMs) of a given molecular system, thereby providing them additional functions such as a specific surface energy or optoelectronic properties (6-8). These features can be optimized by achieving control over the packing of SAMs on the NPs (7). When NPs are integrated in a device, they can, for example, act as charge storage sites-i.e., trapping charges centers, allowing the system to act as a memory (9, 10).The incorporation of photochromic molecules into electronic devices to confer them a photoresponsive nature has been recently explored (11)(12)(13)(14). Among photochromic systems (15-18), azobenzene derivatives are known to undergo isomerization from trans to cis form, and vice versa, under illumination at a specific wavelength, as well as from cis to trans with temperature (15). In the last few years, we have extensively investigated the thiol-substituted azo-biphenyl (AZO, Fig. 1A) when chemisorbed on gold surfaces (19)(20)(21)(22). We demonstrated that such a SAM chemisorbed on the planar source and drain electrodes of an OFET can be used to modulate optically the charge injection at the metal-semiconductor interface because of the different tunneling barrier of the cis and trans SAMs (19). However, the observed light-modul...

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Section: Resultsmentioning

confidence: 99%

Section: Figurementioning

confidence: 99%

Optically switchable organic field-effect transistors based on photoresponsive gold nanoparticles blended with poly(3-hexylthiophene)

Raimondo

Crivillers

Reinders

et al. 2012

Proc. Natl. Acad. Sci. U.S.A.

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“…Beside slight decomposition the formation of boroxine was also observed, but fortunately such boroxine are as reactive as boronic acids in Suzuki cross coupling reactions. [298] Normally, azo functions are not sufficiently stable to t-BuLi but it seemed that n-BuLi followed by subsequent quenching with aqueous hydrochloride solution did not destroy the azo functional group. [299] However, according to the analytical data All this investigations show clearly the need of a completely new synthetic strategy.…”

Section: Cyclization Via Suzuki Reactionmentioning

confidence: 99%

Shape‐Switchable Azo‐Macrocycles

et al. 2009

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The synthesis of four shape‐switchable macrocycles comprising different peripheral substituents is described. The macrocycles 1–4 consist of m‐terphenyl semicircles interlinked by two azo joints. These macrocycles were assembled from nitro‐functionalized m‐terphenyl moieties through reductive dimerization. The semicircles were assembled through Suzuki cross‐coupling reactions. The molecular weights of the macrocycles were determined by vapour pressure osmometry, because mass spectrometry failed in the cases of 2 and 3. The E → Z photoisomerization reactions were analysed by UV/Vis spectroscopy complemented by 1H NMR studies. A very slow thermal back‐reaction indicated considerable stabilization of the Z isomer. The reduced efficiency of the thermal back‐reaction probably arises from the reduced degree of freedom due to the mechanical interlinking of the two azo groups. The photostationary state consisted of all‐Z (85 %) and all‐E isomers (15 %). The E → Z transformation induced by irradiation displayed simple exponential kinetics, which indicates pairwise switching of the two azo groups in a macrocycle, at least on the timescale under investigation. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

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“…However, among all the polymers that can be grafted on gold nanoparticles, the most interesting polymer systems in regard of optical properties of gold nanoparticles are the stimuli-responsive polymers. Stimuli-responsive polymers undergo reversible but signifi cant changes in their properties, in response to environmental variations such as temperature [53, 140 -143] , pH [143 -145] or light [146,147] , and thus, also infl uence (among others) the optical properties of gold nanoparticles, through changes in either local refractive index or inter-particle distance. The responsive behavior of such systems strongly depends on the chemical constitution of the polymeric coating.…”

Section: Polymer Brushesmentioning

confidence: 99%

Coating matters: the influence of coating materials on the optical properties of gold nanoparticles

Chanana¹,

Liz‐Marzán²

2012

Nanophotonics

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An essential element in the synthesis of nanomaterials based on gold nanoparticles comprises the control over parameters such as size, shape and composition, due to their strong infl uence on the properties of the particles. However, it is the coating material which often plays the primary role in tuning the size, morphology, and even plasmon resonance wavelength or mode multiplicity, as well as colloidal stability and functional versatility, ultimately determining the physical, chemical, optical, electronic and catalytic properties of the nanoparticles. Therefore, it is utterly important to select the adequate wet chemistry synthetic approach with the most suitable coating material for the preparation of gold nanoparticles with the desired requirements. Within this context, this review is focused on describing various types of organic and inorganic coating materials for gold nanoparticles that may notably affect their optical properties by either directly infl uencing the synthesis procedure or by changing their chemical and physical properties upon post-synthetic modifi cations, such that they exhibit novel and useful optical properties.

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Light-responsive reversible solvation and precipitation of gold nanoparticles

Abstract: Photo-irradiation with visible and UV light can be used to reversibly trigger the precipitation and solvation, in organic media, of Au nanoparticles coated with a rigid-rod type azobenzene.

Cited by 61 publications

References 41 publications

Optically switchable organic field-effect transistors based on photoresponsive gold nanoparticles blended with poly(3-hexylthiophene)

Optically switchable organic field-effect transistors based on photoresponsive gold nanoparticles blended with poly(3-hexylthiophene)

Shape‐Switchable Azo‐Macrocycles

Coating matters: the influence of coating materials on the optical properties of gold nanoparticles

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