Acid-triggering of light-induced charge-separation in hybrid organic/inorganic molecular photoactive dyads for harnessing solar energy

Benazzi, Elisabetta; Karlsson, Joshua; M’Barek, Youssef Ben; Chábera, Pavel; Blanchard, Sébastien; Alvès, Sandra; Proust, Anna; Pullerits, Tõnu; Izzet, Guillaume; Gibson, Elizabeth A.

doi:10.1039/d0qi01368d

Cited by 13 publications

(12 citation statements)

References 39 publications

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“…Building on these studies, Izzet, Gibson and co‐workers developed BODIPY (boron dipyrromethene)‐functionalized Keggin‐anions as photoactive species for rapid charge‐separation and long charge‐separated state stabilization. The authors propose that the systems are well suited for incorporation in photoelectrochemical devices [22,23] . Related studies, pioneered by Harrimann, Ruhlmann, Lacote, Hasenknopf and others, have focused on the covalent linkage of organo‐functionalized POMs with metalated porphyrins, [24,25] and have used these systems for the development of hybrid organic‐inorganic polymer surface coatings, [26] as well as copolymer films for photocurrent generation [27] .…”

Section: Introductionmentioning

confidence: 99%

“…The authors propose that the systems are well suited for incorporation in photoelectrochemical devices. [ 22 , 23 ] Related studies, pioneered by Harrimann, Ruhlmann, Lacote, Hasenknopf and others, have focused on the covalent linkage of organo‐functionalized POMs with metalated porphyrins,[ 24 , 25 ] and have used these systems for the development of hybrid organic‐inorganic polymer surface coatings, [26] as well as copolymer films for photocurrent generation. [27] Following these seminal works, Streb and co‐workers have used Anderson‐molybdate POMs for the covalent anchoring of Ir‐photosensitizers.…”

Section: Introductionmentioning

confidence: 99%

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Covalent Linkage of BODIPY‐Photosensitizers to Anderson‐Type Polyoxometalates Using CLICK Chemistry

Çetindere

Clausing

Anjass

et al. 2021

Chemistry A European J

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The covalent attachment of molecular photosensitizers (PS) to polyoxometalates (POMs) opens new pathways to PS‐POM dyads for light‐driven charge‐transfer and charge‐storage. Here, we report a synthetic route for the covalent linkage of BODIPY‐dyes to Anderson‐type polyoxomolybdates by using CLICK chemistry (i. e. copper‐catalyzed azide‐alkyne cycloaddition, CuAAC). Photophysical properties of the dyad were investigated by combined experimental and theoretical methods and highlight the role of both sub‐components for the charge‐separation properties. The study demonstrates how CLICK chemistry can be used for the versatile linkage of organic functional units to molecular metal oxide clusters.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Covalent Linkage of BODIPY‐Photosensitizers to Anderson‐Type Polyoxometalates Using CLICK Chemistry

Çetindere

Clausing

Anjass

et al. 2021

Chemistry A European J

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“…In case of POM compounds, it is known that a single electron transfer occurs under neutral pH conditions, and two electrons are transferred under highly acidic pH conditions. Thus, acidic conditions can increase the driving force to trigger reduction reactions [46,47].…”

Section: Effect Of Initial Ph On the Reducing Power Of Mwcnts And Gacmentioning

confidence: 99%

Estimating the Reducing Power of Carbon Nanotubes and Granular Activated Carbon Using Various Compounds

Woo

Kim

Park

2021

Water

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Determining the degree of the reducing power of multi-walled carbon nanotubes (MWCNTs) and granular activated carbon (GAC) enables their effective application in various fields. In this study, we estimate the reducing power of carbon nanotubes (CNTs) and GAC by measuring the reduction degree of various compounds with different reduction potentials. MWCNTs and GAC materials can reduce Cr(VI), Fe(III) and PMo12O403−, where the reduction potentials range from +1.33 V to +0.65 V. However, no reduced forms of PW12O403− and SiW12O404− compounds were detected, indicating that the reducing power of MWCNTs and GAC is insufficient for reduction potentials in the range +0.218 V to +0.054 V. MWCNTs exhibit a short reduction time (5 min), whereas GAC exhibits a gradually increasing reduction degree of all the compounds assessed until the end of the reaction. This indicates a higher reduction degree than that of MWCNTs systems. Acidic initial pH values favor reduction, and the reduction degree increases as the pH becomes lower than 4.0. Moreover, large quantities of MWCNTs and GAC increase the concentrations of the reduced compounds.

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“…In view of these significant results, we decided to enlarge our strategy to BODIPY entities with the hope of recovering their outstanding physicochemical properties in the solid state in a simple and controlled way. To date, very scarce examples of BODIPY/POM dyads have been mentioned in the literature, and in most of the cases, the organic and inorganic fragments have been linked through covalent bonds. − We can mention the synthesis in 2015 of a molecular fluorescent photoswitch obtained by combining in a single molecule an Anderson-type POM, a spiropyran group, and a BODIPY moiety . Very recently, two supramolecular assemblies of a cationic iodobodipy and polyoxovanadates have been elaborated for photochemotherapy in a solution .…”

Section: Introductionmentioning

confidence: 99%

Tailoring the Solid-State Fluorescence of BODIPY by Supramolecular Assembly with Polyoxometalates

et al. 2021

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A cationic boron dipyrromethene (BODIPY) derivative (1 + ) has been successfully combined with two polyoxometalates (POMs), the Lindqvist-type [W6O19] 2and the β-[Mo8O26] 4units, into three new supramolecular fluorescent materials(1)2[W6O19]⋅2CH3CN, (1)2[W6O19] and (1)4[Mo8O26]⋅DMF⋅H2O. The resulting hybrid compounds have been fully characterized by a combination of single-crystal X-ray diffraction, IR and UV-Vis spectroscopies and photoluminescence analyses. This self-assembly approach prevents any π-π stacking interactions between the BODIPY units, responsible for aggregation-caused quenching (ACQ) effects, but also between the BODIPY and the POMs, avoiding intermolecular charge-transfer effects. Noticeably, the POM units do not only act as bulky spacers but their negative charge density drives the molecular arrangement of the 1 + luminophore, strongly modifying its fluorescence in the solid state. As a consequence, the 1 + cations are organized into dimers in (1)2[W6O19]⋅2CH3CN and (1)2[W6O19], which are weakly emissive at room temperature, and in a more compact layered assembly in (1)4[Mo8O26]⋅DMF⋅H2O which exhibits a redshifted and intense emission upon similar photoexcitation.

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Acid-triggering of light-induced charge-separation in hybrid organic/inorganic molecular photoactive dyads for harnessing solar energy

Abstract: H+ modulated charge-transfer in photoexcited covalently linked W and Mo Keggin-bodipy conjugates is demonstrated using transient absorption spectroscopy and photoluminescence. Adding acid switches on (W) or accelerates (Mo) charge separation.

Cited by 13 publications

References 39 publications

Covalent Linkage of BODIPY‐Photosensitizers to Anderson‐Type Polyoxometalates Using CLICK Chemistry

Covalent Linkage of BODIPY‐Photosensitizers to Anderson‐Type Polyoxometalates Using CLICK Chemistry

Estimating the Reducing Power of Carbon Nanotubes and Granular Activated Carbon Using Various Compounds

Tailoring the Solid-State Fluorescence of BODIPY by Supramolecular Assembly with Polyoxometalates

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