Copper indium sulfide quantum dots enabling quantitative visible light photoisomerisation of (E)-azobenzene chromophores.

Azobenzene derivatives have long been studied for their photochromic behaviour. One of the greatest challenges in this field is the quantitative (E) to (Z) photoconversion triggered by visible light irradiation. In this work, the synthesis and characterization of CuInS2 quantum dots (CIS-QDs) appended with azobenzene units are reported: quantitative (E) → (Z) isomerisation is obtained by visible light (e.g., λex = 533 nm). Interestingly, catalytic amounts of CIS-QDs allow the full photoconversion of ungrafted (E)-azobenzene derivatives into the corresponding (Z)-isomers using visible light. This peculiar behaviour is associated with the direct complexation of the (Z)-isomer on the QD surface.

Optical modulation of cell nucleus penetration and singlet oxygen release of a switchable platinum complex.

The activation of anticancer molecules with visible light constitutes an elegant strategy to target tumors and to improve the selectivity of treatments. In this context, we report here a visible-light activatable bis-platinum complex (DHP-Pt2) incorporating an organic photo-switchable ligand based on the dimethyldihydropyrene moiety. Illumination of this metal complex with red light (660 nm) under air readily produces the corresponding endoperoxide form (CPDO2-Pt2). These two metal complexes exhibit different DNA binding properties and, more importantly, we show that only the photogenerated CPDO2-Pt2 is able to penetrate into cancer cell nuclei, where it is then capable of releasing cytotoxic singlet oxygen. This study represents the first proof-of-concept showing that dimethyldihydropyrene derivatives can be used to transport and deliver singlet oxygen into cancer cell nuclei upon visible-light activation.

All Visible Light Photoswitch Based on the Dimethyldihydropyrene Unit Operating in Aqueous Solutions with High Quantum Yields.

Molecular systems and devices whose properties can be modulated using light as an external stimulus are the subject of numerous research studies in the fields of materials and life sciences. In this context, the use of photochromic compounds that reversibly switch upon light irradiation is particularly attractive. However, for many envisioned applications, and in particular for biological purposes, illumination with harmful UV light must be avoided and these photoactivable systems must operate in aqueous media. In this context, we have designed a benzo[e]-fused dimethyldihydropyrene compound bearing a methyl-pyridinium electroacceptor group that meets these requirements. This compound (closed state) is able to reversibly isomerize under aerobic conditions into its corresponding cyclophanediene form (open isomer) through the opening of its central carbon-carbon bond. Both the photo-opening and the reverse photoclosing processes are triggered by visible light illumination and proceed with high quantum yields (respectively 14.5% yield at λ = 680 nm and quantitative quantum yield at λ = 470 nm, in water). This system has been investigated by nuclear magnetic resonance and absorption spectroscopy, and the efficient photoswitching behavior was rationalized by spin-flip time-dependent density functional theory calculations. In addition, it is demonstrated that the isomerization from the open to the closed form can be electrocatalytically triggered.

Synthesis of a Negative Photochrome with High Switching Quantum Yields and Capable of Singlet-Oxygen Production and Storage.

A dimethyldihydropyrene (DHP) photochromic unit has been functionalized by donor (triphenylamine group) and acceptor (methylpyridinium) substituents. This compound was characterized by NMR, absorption and emission spectroscopies as well as cyclic voltammetry, and its properties were rationalized by theoretical calculations. The incorporation of both electron-donor and -withdrawing groups at the photochromic center allows i) an efficient photo-isomerization of the system when illuminated at low energy (quantum yield: Φc-o =13.3 % at λex =660 nm), ii) the reversible and quantitative formation of two endoperoxyde isomers when illuminated under aerobic conditions at room temperature, and iii) the storage and production of singlet oxygen. The photo-isomerization mechanism was also investigated by spin-flip TD-DFT (SF-TD-DFT) calculations.

Metal free oxidation of vinamidine derivatives: a simple synthesis of α-keto-ß-diimine ligands.

Oxidation of vinamidinium salts with meta-chloroperbenzoic acid is the key synthetic step towards new persistent 1,3-di(amino)oxyallyl radical cations. When applied to parent vinamidines, this protocol allows for a simple straightforward synthesis of α-keto-ß-diimine ligands, for which no convenient synthesis was previously available.