Spiropyran-based reversible, light-modulated sensing with reduced photofatigue

Switchable materials have tremendous potential for application in sensor development that could be applied to many fields. We are focusing on emerging area of wireless sensor networks due to the potential impact of this concept in society. Spiropyran-based sensors are probably the most studied type of photoswitchable sensing devices. They suffer from many issues but photofatigue, insufficient selectivity and lack of sensitivity are probably the most important characteristics that hinder their wider application. Here, we are address these issues and demonstrate that covalent attachment of modified spiropyran into a polymeric film significantly reduces photodegradation. The observed signal loss after 12th cycle of switching between the spiropyran and merocyanine forms is only about 27% compared to the loss of 57% of the initial signal in an equivalent experiment based on non-immobilized spiropyran. This has enabled us to demonstrate at least five reversible cycles of detection of an ion of interest (in our case H+) with minimal signal loss. Furthermore, we demonstrate that the sensitivity can be increased by incorporation of additional binding groups in the parent spiropyran molecule. Using molecular modelling to calculate the relevant bond lengths as a measure of interaction between MC and H+, the calculated increase of H-bond strength is approximately an order of magnitude for a derivative containing a methoxy group incorporated in the o-position of the parent spiropyran in comparison to the equivalent unsubstituted phenol. This theoretical result was found to correspond very well with experimental observation. As a result, we have increased the sensitivity to H+ by approximately one order of magnitude

Spiropyran modified micro-fluidic chip channels as photonically controlled self-indicating system for metal ion accumulation and release

In this paper, we show how through integrating the beneficial characteristics of micro-fluidic devices and spiropyrans dyes, a simple and very innovative chip configured as an on-line photonically controlled self-indicating system for metal ion accumulation and release can be realised. The micro-fluidic device consists of five independent 94 μm depth, 150 μm width channels fabricated in polydimethylsiloxane. The spiropyran 1’-(3-carboxypropyl)-3,3’-dimethyl-6-nitrospiro-1-benzopyran-2,2’-indoline is immobilised by physical adsorption into a polydimethylsiloxane matrix and covalently on the ozone plasma activated polydimehylsiloxane micro-channel walls. When the colourless, inactive, spiropyran coating absorbs UV light it switches to the highly coloured merocyanine form, which also has an active binding site for certain metal ions. Therefore metal ion uptake can be triggered using UV light and subsequently reversed on demand by shining white light on the coloured complex, which regenerates the inactive spiropyran form, and releases the metal ion. When stock solutions of several metal ions (Ca2+, Zn2+, Hg2+, Cu2+, Co2+) are pumped independently through the five channels, different optical responses were observed for each metal, and the platform can therefore be regarded as a micro-structured device for online self-indicating metal ion complexation, accumulation and release

Push-pull zinc phthalocyanine bearing hexa-tertiary substituted carbazolyl donor groups for dye-sensitized solar cells

An asymmetrical, push-pull phthalocyanine bearing bulky tert-butylcarbazolyl moieties as electron donor and carboxylic acid as anchoring group was synthetized and tested as a photosensitizer in dye-sensitized solar cells (DSSC). The new photosensitizer was characterized by 1H and 13C NMR, UV-Vis and mass spectrometry. The bulky tert-butylcarbazolyl moieties avoid the aggregation of the phthalocyanine dye. DFT studies indicate that the HOMO is delocalized throughout the π-electron system of the substituted phthalocyanine and the LUMO is located on the core of the molecule with a sizable electron density distribution on carboxyl groups. The new dye has been used as a photosensitizer in transparent and opaque dye-sensitized solar cells, which exhibit poor efficiencies related to a low JscThis work was financially supported by the Kuwait Foundation for the Advancement of Science (Grant Number PN18-12-SC01) and the RSP unit general facilities of the Faculty of Science GFS (GS 01/01, GS 03/01, GS 01/03, GS 01/05, and GS 02/13) (S.M.). T.T. thanks MINECO (project CTQ2017-85393-P) and ERA-NET/European Commission/MINECO, (UNIQUE, SOLAR-ERA.NET Cofund 2 Nº 008/PCI2019-111889-2). R.D. acknowledges ANR for funding through ODYCE project. (Grant agreement No ANR-14-OHRI-0003-01). RD thanks European Research Council (ERC) for funding. This project has received funding from the European Union’s Horizon 2020 research and innovation program (grant agreement No 832606)—Project PISC

Probing the Local Conformation within pi-Conjugated One-dimensional Supramolecular Stacks using Frequency Modulation Atomic Force Microscopy

peer reviewedFrequency-modulation atomic force microscopy is used to investigate the local conformation within 1D stacks obtained by the self-assembly of p-conjugated molecules from solution. The structural parameters extracted from the experimental data can be interpreted in terms of local molecular conformation, by comparison with models obtained by molecular mechanics and dynamics simulations

Functional Panchromatic BODIPY Dyes with near-infrared absorption: design, synthesis, characterization, and use in Dye-Sensitized Solar Cells

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Characterization of Photochromic Dye Solar Cells Using Small-Signal Perturbation Techniques

Photochromic dye-sensitized solar cells (DSSCs) are novel semi-transparent photovoltaic devices that self-adjust their optical properties to the irradiation conditions, a feature that makes them especially suitable for building integrated photovoltaics. These novel solar cells have already achieved efficiencies above 4%, and there are multiple pathways to improve the performance. In this work, we conduct a full characterization of DSSCs with the photochromic dye NPI, combining electrical impedance spectroscopy (EIS) and intensity-modulated photocurrent spectroscopy (IMPS). We argue that the inherent properties of the photochromic dye, which result in a modification of the functioning of the solar cell by the optical excitation that also acts as a probe, pose unique challenges to the interpretation of the results using conventional models. Absorption of light in the visible range significantly increases when the NPI dye is in the activated state; however, the recombination rate also increases, thus limiting the efficiency. We identify and quantify the mechanism of enhanced recombination when the photochromic dye is activated using a combination of EIS and IMPS. From the comparison to a state-of-the-art reference dye (RK1), we were able to detect a new feature in the IMPS spectrum that is associated with the optical activation of the photochromic dye, providing a useful tool for assessing the electronic behavior of the device under different conditions of light excitation. This study provides guidelines to adequate characterization protocols of photochromic solar cells and essential insights on the interfacial electronic processes.Universidad Pablo de Olavide / CEA Grenobl

Visible and near-infrared organic photosensitizers comprising isoindigo derivatives as chromophores: synthesis, optoelectronic properties and factors limiting their efficiency in dye solar cells

The development of ruthenium-free organic photosensitizers showing panchromatic absorption up to the near-infrared (NIR) region for application in dye-sensitized solar cells (DSSCs) is still scarce. Among the sensitizers with absorption beyond 700 nm and developed for DSSCs, only zinc-phthalocyanine and boron-dibenzopyrromethene-based dyes have been able to reach efficiencies as high as 6%. Here we report metal-free organic dyes based on isoindigo, thieno-isoindigo or benzo-thieno-isoindigo chromophores that absorb in the UV-visible and NIR spectral range up to 900 nm. These molecules, that exhibit purple, blue, or green hues, were used to sensitize TiO2 mesoporous electrodes in order to fabricate DSSCs with an iodide/triiodide-based electrolyte. Advanced photophysical characterizations, including charge extraction, transient photovoltage, and laser transient absorption spectroscopy experiments, combined with density functional theory modeling and computational investigations allow us to fully unravel the interfacial processes at the origin of the solar cell performances and to identify the limiting factors. A power conversion efficiency as high as 7% associated with a Jsc close to 19 mA cm−2 was obtained with one of the dyes, which is comparable to those of the best panchromatic organic dyes reported so far. We also demonstrate in this work that the Voc of the solar cells is linearly correlated to the dipolar moments of the oxidized dyes, the molecules possessing larger dipoles leading to the highest Voc value

Multidimensional nanoarchitectures for improved indoor light harvesting in dye-sensitized solar cells

Dye Sensitized Solar Cells (DSSCs) have recently gained renewed interest for their potential in indoor light harvesting and powering wireless devices. However, to fully exploit their potential, crucial aspects require further attention, in particular, the improvement of spectral compatibility and low-light harvesting mechanisms, as well as the development of efficient photoanodes through high-yield scalable methods. In this article, we propose the use of nanocomposite photoanodes integrating mesoporous TiO2 nanoparticles, ITO nanotubes (NT), and anatase TiO2 shells (ITO@TiO2 NT) prepared by step-by-step method relying on mild temperature conditions and avoiding toxic precursors. These photoanodes outperform previous attempts to implement low-dimensional ITO and ITO@TiO2 nanowires and nanotubes for outdoor light conversion, demonstrating a power conversion efficiency under low artificial light intensity of 24 % for at 0.014 mW cm−2, a 166 % increase compared to the conventional architectures. Advanced microstructural, optical, and electrochemical characterizations have revealed that the strong scattering effect of the light in the visible range coupled with enhanced charge collection at low-intensity illumination are the essential mechanisms responsible for such enhanced energy conversion. Remarkably, our devices retain up to 90 % of the normal incidence efficiency even under glancing illumination, while conventional reference devices retain only 30 %.We thank the projects PID2019-109603RA-I00, TED2021-130916B-I00, PID2019-110430 GB-C21, and PID2022-143120OB-I00 funded by MCIN/AEI/10.13039/501100011033 and by “ERDF (FEDER) A way of making Europe, Fondos NextgenerationEU and Plan de Recuperación, Transformación y Resiliencia”. LCB acknowledges the French embassy in Spain for the grant “123892U” within framework of the proposal scientific call 2022 “Becas doctorales y postdoctorales”. Thanks to C.M.D Felipe II, particularly María Inmaculada Carmona Rivera, for providing some tools for preparing counter-electrodes. The authors also thank CSIC for its financial support through the Interdisciplinary Thematic Platform (PTI) Transición Energética Sostenible (PTI-TRANSENER+). R.D. acknowledges the European Research Council (ERC) for funding. This work was funded under the European Union's Horizon 2020 research and innovation programme (grant agreement number 832606; project PISCO). The project leading to this article has received funding from the EU H2020 program under grant agreement 851929 (ERC Starting Grant 3DScavengers).Peer reviewe