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

Abstract

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.

Diiodo-BODIPY Sensitizing of the [Mo3S13]2– Cluster for Noble-Metal-Free Visible-Light-Driven Hydrogen Evolution within a Polyampholytic Matrix

“…49,50 Lately, polyoxometalates have been reported for covalent conjugation to BODIPY PSs to create organic−inorganic hybrid materials toward unimolecular photocatalysts. 51,52 This work aims at developing photocatalytic hydrogen evolution systems that circumvent noble metal nuclei in both the visible-light-active and the catalytically active components. In our previous work, the thiomolybdate cluster [Mo 3 S 13 ] 2− was identified as an ideal candidate that provided high photocatalytic activity with [Ru(bpy) 3 ] 2+ PSs.…”

A photo-switchable molecular capsule: sequential photoinduced processes

“…Significant steps to address this deficiency have been made by the groups of Izzet, Gibson, Proust, Streb and Dietzek amongst others. [20][21][22][23] On the contrary the photochemical dynamics of diarylethenes (DAEs) are well-documented 24,25 , however, the absence of hybrid DAE-POM materials in the literature has to date precluded their study, except for our prior report and a recent solid-state investigation by Dessapt et.al.…”

“…Signicant steps to address this deciency have been made by the groups of Izzet, Gibson, Proust, Streb and Dietzek amongst others. [20][21][22][23] In contrast the photochemical dynamics of diarylethenes (DAEs) are welldocumented, 24,25 however, the absence of hybrid DAE-POM materials in the literature has to date precluded their study, except for our prior report and a recent solid-state investigation by Dessapt et al Prior studies conducted on photochromic spiropyran POM hybrids and the report that [PMo 9 O 31 (py) 3 ] 3− -{PMo 9 } can be utilised as a precursor for the preparation of organically functionalised lacunary phosphomolybdates served as inspiration for this work. [26][27][28] Intrigued by the opportunity that the combination of DAEs and POMs in a molecular assembly would present to investigate this balance of photochemical processes, we designed and prepared the photochromic molecular capsule [(PMo 9 O 31 ) 2 (-DAE) 3 ] 6− -(1) reported herein (Fig.…”

Latest progress in covalently modified polyoxometalates-based molecular assemblies and advanced materials

“…The use of noble-metal-free PS such as boron dipyrromethene (BODIPY) and their derivatives made great progress in light-driven charge-separation and applications, due to the versatile photophysical properties, high chemical stability, easy and versatile chemical modification. Streb and co-workers proposed a synthetic route for the covalent linkage of BODIPY-dyes to Anderson-type MnMo6 by using CLICK chemistry, and the dyad retained the unique photophysical properties of BODIPY [67] .…”