A dinuclear ruthenium(II) phototherapeutic that targets duplex and quadruplex DNA

With the aim of developing a sensitizer for photodynamic therapy, a previously reported luminescent dinuclear complex that functions as a DNA probe in live cells was modified to produce a new isostructural derivative containing RuII(TAP)2 fragments (TAP = 1,4,5,8- tetraazaphenanthrene). The structure of the new complex has been confirmed by a variety of techniques including single crystal X-ray analysis. Unlike its parent, the new complex displays RuL-based 3MLCT emission in both MeCN and water. Results from electrochemical studies and emission quenching experiments involving guanosine monophosphate are consistent with an excited state located on a TAP moiety. This hypothesis is further supported by detailed DFT calculations, which take into account solvent effects on excited state dynamics. Cell-free steady-state and time-resolved optical studies on the interaction of the new complex with duplex and quadruplex DNA show that the complex binds with high affinity to both structures and indicate that its photoexcited state is also quenched by DNA, a process that is accompanied by the generation of the guanine radical cation sites as photo-oxidization products. Like the parent complex, this new compound is taken up by live cells where it primarily localizes within the nucleus and displays low cytotoxicity in the absence of light. However, in complete contrast to [{RuII(phen)2}2(tpphz)]4+, the new complex is therapeutically activated by light to become highly phototoxic toward malignant human melanoma cell line showing that it is a promising lead for the treatment of this recalcitrant cancer.EPSRC grant EP/M015572/1 Unviersity of Sheffield/EPSRC Doctoral Fellowship Prize EPSRC Capital Equipment Award ERASMUS

A Near Infra-Red Luminescent Cr(III) N-Heterocyclic Carbene Complex

Photoluminescent coordination complexes of Cr(III) are of interest as near-infrared spin-flip emitters. Here, we explore the preparation, electrochemistry, and photophysical properties of the first two examples of homoleptic N-heterocyclic carbene complexes of Cr(III), featuring 2,6-bis(imidazolyl)pyridine (ImPyIm) and 2-imidazolylpyridine (ImPy) ligands. The complex [Cr(ImPy)3]3+ displays luminescence at 803 nm on the microsecond time scale (13.7 μs) from a spin-flip doublet excited state, which transient absorption spectroscopy reveals to be populated within several picoseconds following photoexcitation. Conversely, [Cr(ImPyIm)2]3+ is nonemissive and has a ca. 500 ps excited-state lifetime

A stronger acceptor decreases the rates of charge transfer:Ultrafast dynamics and on/off switching of charge separation in organometallic Donor-Bridge-Acceptor systems

To unravel the role of driving force and structural changes in directing the photoinduced pathways in donor–bridge–acceptor (DBA) systems, we compared the ultrafast dynamics in novel DBAs which share a phenothiazine (PTZ) electron donor and a Pt(II) trans-acetylide bridge (–C[triple bond, length as m-dash]C–Pt–C[triple bond, length as m-dash]C–), but bear different acceptors conjugated into the bridge (naphthalene-diimide, NDI; or naphthalene-monoimide, NAP). The excited state dynamics were elucidated by transient absorption, time-resolved infrared (TRIR, directly following electron density changes on the bridge/acceptor), and broadband fluorescence-upconversion (FLUP, directly following sub-picosecond intersystem crossing) spectroscopies, supported by TDDFT calculations. Direct conjugation of a strong acceptor into the bridge leads to switching of the lowest excited state from the intraligand 3IL state to the desired charge-separated 3CSS state. We observe two surprising effects of an increased strength of the acceptor in NDI vs. NAP: a ca. 70-fold slow-down of the 3CSS formation—(971 ps)−1 vs. (14 ps)−1, and a longer lifetime of the 3CSS (5.9 vs. 1 ns); these are attributed to differences in the driving force ΔGet, and to distance dependence. The 100-fold increase in the rate of intersystem crossing—to sub-500 fs—by the stronger acceptor highlights the role of delocalisation across the heavy-atom containing bridge in this process. The close proximity of several excited states allows one to control the yield of 3CSS from ∼100% to 0% by solvent polarity. The new DBAs offer a versatile platform for investigating the role of bridge vibrations as a tool to control excited state dynamics