Energy exchange between Nd3+ and Er3+ centers within molecular complexes.

Developing controlled and reproducible molecular assemblies incorporating lanthanide centers is a crucial step for driving forward up- and down-conversion processes. This challenge calls for the development of strategies to facilitate the efficient in situ segregation of different Ln metal ions into distinct positions within the molecule. The unique family of pure [LnLn'Ln] heterometallic coordination compounds previously developed by us represents an ideal platform for studying the desired Ln-to-Ln' energy transfer (ET). In this context, we report here the new pure one-step synthetically produced [ErNdEr] (3) complex, which allows for the first time at the molecular level to study the mechanisms behind Nd-to-Er energy transfer. To further assess the photophysical properties of this complex, the analogous [LuNdLu] (1) and [ErLaEr] (2) complexes have also been prepared and photophysically studied. Efficient sensitization via the two ß-diketones employed as main ligands was probed for both Nd3+ and Er3+ ions, resulting in highly resolved emission spectra and sufficiently long excited state lifetimes, which allowed further assessment of the Ln-to-Ln' ET. This intermetallic transfer was first detected by comparing the emission spectra of iso-absorbant solutions and demonstrated by comparing the lifetime values with or without the lanthanide quencher (Er3+), as well as with a deep analysis of the excitation spectrum of the three complexes. Thus, a very unique phenomenon was discovered, consisting of a mutual Nd-to-Er and Er-to-Nd ET with no net increase of brightness by any metal; while Nd3+ transfers the energy received from the antenna to Er3+, the sensitization of the latter results in back-transfer to Nd3+ into a non-emissive, thus silent, state.

A new G-quadruplex-specific photosensitizer inducing genome instability in cancer cells by triggering oxidative DNA damage and impeding replication fork progression.

Photodynamic therapy (PDT) ideally relies on the administration, selective accumulation and photoactivation of a photosensitizer (PS) into diseased tissues. In this context, we report a new heavy-atom-free fluorescent G-quadruplex (G4) DNA-binding PS, named DBI. We reveal by fluorescence microscopy that DBI preferentially localizes in intraluminal vesicles (ILVs), precursors of exosomes, which are key components of cancer cell proliferation. Moreover, purified exosomal DNA was recognized by a G4-specific antibody, thus highlighting the presence of such G4-forming sequences in the vesicles. Despite the absence of fluorescence signal from DBI in nuclei, light-irradiated DBI-treated cells generated reactive oxygen species (ROS), triggering a 3-fold increase of nuclear G4 foci, slowing fork progression and elevated levels of both DNA base damage, 8-oxoguanine, and double-stranded DNA breaks. Consequently, DBI was found to exert significant phototoxic effects (at nanomolar scale) toward cancer cell lines and tumor organoids. Furthermore, in vivo testing reveals that photoactivation of DBI induces not only G4 formation and DNA damage but also apoptosis in zebrafish, specifically in the area where DBI had accumulated. Collectively, this approach shows significant promise for image-guided PDT.

Site-selected thionated benzothioxanthene chromophores as heavy-atom-free small-molecule photosensitizers for photodynamic therapy.

Photodynamic therapy is a clinically approved anticancer modality that employs a light-activated agent (photosensitizer) to generate cytotoxic reactive oxygen species (ROS). There is therefore a growing interest for developing innovative photosensitizing agents with enhanced phototherapeutic performances. Herein, we report on a rational design synthetic procedure that converts the ultrabright benzothioxanthene imide (BTI) dye into three heavy-atom-free thionated compounds featuring close-to-unit singlet oxygen quantum yields. In contrast to the BTI, these thionated analogs display an almost fully quenched fluorescence emission, in agreement with the formation of highly populated triplet states. Indeed, the sequential thionation on the BTI scaffold induces torsion of its skeleton reducing the singlet-triplet energy gaps and enhancing the spin-orbit coupling. These potential PSs show potent cancer-cell ablation under light irradiation while remaining non-toxic under dark condition owing to a photo-cytotoxic mechanism that we believe simultaneously involves singlet oxygen and superoxide species, which could be both characterized in vitro. Our study demonstrates that this simple site-selected thionated platform is an effective strategy to convert conventional carbonyl-containing fluorophores into phototherapeutic agents for anticancer PDT.

Excited State Properties of Lanthanide(III) Complexes with a Nonadentate Bispidine Ligand.

EuIII , TbIII , GdIII and YbIII complexes of the nonadentate bispidine derivative L2 (bispidine=3,7-diazabicyclo[3.3.1]nonane) were successfully synthesized and their emission properties studied. The X-ray crystallography reveals full encapsulation by the nonadentate ligand L2 that enforces to all LnIII cations a common highly symmetrical capped square antiprismatic (CSAPR) coordination geometry (pseudo C4v symmetry). The well-resolved identical emission spectra in solid state and in solution confirm equal structures in both media. As therefore expected, this results in long-lived excited states and high emission quantum yields ([EuIII L2 ]+ , H2 O, 298 K, τ=1.51 ms, ϕ=0.35; [TbIII L2 ]+ , H2 O, 298 K, τ=1.95 ms, ϕ=0.68). Together with the very high kinetic and thermodynamic stabilities, these complexes are a possible basis for interesting biological probes.

Accessing Lanthanide-to-Lanthanide Energy Transfer in a Family of Site-Resolved [LnIII LnIII '] Heterodimetallic Complexes.

The ligand H3 L (6-[3-oxo-3-(2-hydroxyphenyl)propionyl]pyridine-2-carboxylic acid), which exhibits two different coordination pockets, has been exploited to engender and study energy transfer (ET) in two dinuclear [LnIII LnIII '] analogues of interest, [EuYb] and [NdYb]. Their structural and physical properties have been compared with newly synthesised analogues featuring no possible ET ([EuLu], [NdLu], and [GdYb]) and with the corresponding homometallic [EuEu] and [NdNd] analogues, which have been previously reported. Photophysical data suggest that ET between EuIII and YbIII does not occur to a significant extent, whereas emission from YbIII originates from sensitisation of the ligand. In contrast, energy migration seems to be occurring between the two NdIII centres in [NdNd], as well as in [NdYb], in which YbIII luminescence is thus, in part, sensitised by ET from Nd. This study shows the versatility of this molecular platform to further the investigation of lanthanide-to-lanthanide ET phenomena in defined molecular systems.

Synthesis, characterization and use of benzothioxanthene imide based dimers.

The synthesis of benzothioxanthene imide based dimers is reported herein. Subtle chemical modifications were carried out and their impact on the optical and electrochemical properties was investigated for a better structure-property relationship analysis. The icing on the cake was that these new structures were used as light emitting materials for the fabrication and demonstration of the first BTXI-based OLEDs.

Aza-BODIPY Platform: Toward an Efficient Water-Soluble Bimodal Imaging Probe for MRI and Near-Infrared Fluorescence.

In this study, an original aza-BODIPY system comprising two Gd3+ complexes has been designed and synthesized for magnetic resonance imaging/optical imaging applications, by functionalization of the boron center. This strategy enabled the obtainment of a positively charged bimodal probe, which displays an increased water solubility, optimized photophysical properties in the near-infrared region, and very promising relaxometric properties. The absorption and emission wavelengths are 705 and 741 nm, respectively, with a quantum yield of around 10% in aqueous media. Moreover, the system does not produce singlet oxygen upon excitation, which would be toxic for tissues. The relaxivity obtained is high at intermediate fields (16.1 mM-1 s-1 at 20 MHz and 310 K) and competes with that of bigger or more rigid systems. A full relaxometric and 17O NMR study and fitting of the data using the Lipari-Szabo approach showed that this high relaxivity can be explained by the size of the system and the presence of some small aggregates. These optimized photophysical and relaxometric properties highlight the potential use of such systems for future bimodal imaging studies.

Synthesis and structural, redox and photophysical properties of tris-(2,5-di(2-pyridyl)pyrrolide) lanthanide complexes.

A first series of lanthanide complexes of tris(dipyridyl)pyrrolide ligands has been prepared. The [Ln(dppR1,R2)3] complexes (Ln = La(iii), Sm(iii), Eu(iii), Gd(iii) and Yb(iii); and dppR1,R2 = 2,5-di(2-pyridyl-3-(R1)-4-(R2)) pyrrolide) have been isolated and their structures and photophysical and redox properties characterised, both in the solid-state and in solution. In the complexes, the three dpp- ligands form a distorted tricapped trigonal prismatic coordination geometry about the lanthanide ions, with the antiparallel isomer observed in the solid state for non-symmetric (dppCO2Me,Me)-. However, 1H NMR spectroscopy of the diamagnetic and paramagnetic [Ln(dppR1,R2)3] complexes in d6-benzene solution reveal evidence for a statistical distribution of all possible isomers. Time-resolved luminescence studies suggest that the dpp- ligand (with triplet excited state T1 energy at 18 622 cm-1) sensitises red emission from [Eu(dppCO2Me,Me)3] and near-infrared emission from [Yb(dppCO2Me,Me)3] through the antenna effect. Cyclic voltammetry reveals three consecutive, reversible, one-electron oxidation processes for each [Ln(dppR1,R2)3] complex, corresponding to oxidations of each dpp- ligand between 0.3-0.8 V vs. E1/2 (Fc+/0), and for [Eu(dppCO2Me,Me)3] the EuIII/II couple was -2.099 V vs. E1/2 (Fc+/0).

Colloidal quasi-one-dimensional dual semiconductor core/shell nanorod couple heterostructures with blue fluorescence.

Herein we report a nanorod couple heterostructure made of dual semiconductors, in which two parallelly aligned ZnSe nanorods are connected by the growth of ZnS on both end and side facets, producing hetero-ZnS (short arms)-ZnSe (long arms)/ZnS shell nanorod couples. As evidenced by electronic structure studies, both experimental and theoretical, such core/shell nanorod couple heterostructures can act as a platform to precisely tailor the quantum confinement of charge carriers between the constituting components within a single nano-object, generating blue fluorescence after the overgrowth of an alloyed ZnCdS layer on the heterostructures. We foresee the mechanistic insights gained and electronic structures revealed in this work would shed light on the rational design of more complex heterostructures with novel functionalities.

Photophysical investigation of near infrared emitting lanthanoid complexes incorporating tris(2-naphthoyl)methane as a new antenna ligand.

A conjugated ß-triketone, tris(2-naphthoyl)methane (tnmH), has been synthesized and successfully utilized as an antenna moiety for sensitization of the trivalent lanthanoids Eu3+, Sm3+, Yb3+ and Nd3+, in an isomorphous series of mononuclear complexes formulated as [Ln(tnm)3(DMSO)2] (Ln3+ = Nd3+, Sm3+, Eu3+, Gd3+ and Yb3+). The photophysical properties of the materials were characterized as comprehensively as possible, with overall quantum yields, intrinsic quantum yields based on calculated radiative decays, and sensitization efficiencies reported. This investigation improves understanding of the sensitization processes occurring in the near-infrared (NIR) region, where quantitative data are currently scarce. In fact, the [Yb(tnm)3(DMSO)2] and its deuterated analogue, [Yb(tnm)3(d6-DMSO)2], present high values of overall quantum yield of 4% and 6%, respectively, which makes them useful and readily accessible references for future investigation of NIR-emitting systems.

Lanthanoid complexes supported by retro-Claisen condensation products of ß-triketonates.

ß-Triketonates have been recently used as chelating ligands for lanthanoid ions, presenting unique structures varying from polynuclear assemblies to polymers. In an effort to overcome low solubility of the complexes of tribenzoylmethane, four ß-triketones with higher lipophilicity were synthesised. Complexation reactions were performed for each of these molecules using different alkaline bases in alcoholic media. X-ray diffraction studies suggested that the ligands were undergoing decomposition under the reaction conditions. This is proposed to be caused by in situ retro-Claisen condensation reactions, consistent with two examples that have been reported previously. The lability of the lanthanoid cations in the presence of a varying set of potential ligands gave rise to structures where one, two, or three of the molecules involved in the retro-Claisen condensation reaction were linked to the lanthanoid centres. These results, along with measurements of ligand decomposition in the presence of base alone, suggest the solvent used will modulate the impact of the retro-Claisen condensation in these complexes.

Energy transfer between Eu3+ and Nd3+ in near-infrared emitting ß-triketonate coordination polymers.

Isomorphous ß-triketonate-based lanthanoid polymers containing tris(4-methylbenzoyl)methanide (mtbm) and Rb+ with formula {[Ln(Rb)(mtbm)4]2}n (Ln = Eu3+ and Nd3+) have been synthesised and structurally characterised. The photophysical properties for the Nd3+ complex presented relatively long lifetimes and high quantum yields in comparison with analogous ß-diketonate complexes. Mixed lanthanoid complexes were also formed and their luminescence properties studied, with effective sensitisation of the 4F3/2 of Nd3+via the 5D0 of Eu3+, which is to the best of our knowledge the first example of Eu3+ to Nd3+ sensitisation in a structurally defined coordination complex or polymer.

Probing the effect of ß-triketonates in visible and NIR emitting lanthanoid complexes.

An isomorphous series of lanthanoid complexes containing tribenzoylmethanide (tbm) and 1,10-phenanthroline (phen) ligands has been synthesised and structurally characterised. These complexes, formulated as [Ln(phen)(tbm)3] (Ln = Eu3+, Er3+ and Yb3+), were compared with analogous dibenzoylmethanide (dbm) [Ln(phen)(dbm)3] complexes to investigate the effect of changing ß-diketonate to ß-triketonate ligands on the photophysical properties of the complex. The photophysical properties for the Eu3+ complexes were similar for both systems, whereas a modest enhancement was observed for Yb3+ and Er3+ moving from the dbm to the tbm complexes. A detailed study of the NIR photophysical properties was achieved by adapting the integrating sphere method for the calculation of overall quantum yields in the solid state.