Expanding the series of alkali metal plumbolyl complexes to Na and K.

Herein we detail the straightforward and scalable synthesis of sodium and potassium complexes of the 2,5-bis(tert-butyldimethylsilyl)-3,4-diphenylplumbolyl dianion (PblTBS,Ph). Their solid-state structures were found to comprise either monomeric solvates or coordination polymers depending on the alkali metal ion and crystallization medium. These complexes were readily prepared with high yields and purity compared to known routes to the dilithium congener of PblTBS,Ph and are well-positioned to serve as convenient precursors for salt metathesis-type reactions leading to metal complexes of the understudied PblTBS,Ph ligand.

Toward Opto-Structural Correlation to Investigate Luminescence Thermometry in an Organometallic Eu(II) Complex.

Lanthanide-based luminescent materials have unique properties and are well-studied for many potential applications. In particular, the characteristic 5d → 4f emission of divalent lanthanide ions such as EuII allows for tunability of the emissive properties via modulation of the coordination environment. We report the synthesis and photoluminescence investigation of pentamethylcyclopentadienyleuropium(II) tetrahydroborate bis(tetrahydrofuran) dimer (1), the first example of an organometallic, discrete molecular EuII band-shift luminescence thermometer. Complex 1 exhibits an absolute sensitivity of 8.2 cm-1 K-1 at 320 K, the highest thus far observed for a lanthanide-based band-shift thermometer. Opto-structural correlation via variable-temperature single-crystal X-ray diffraction and fluorescence spectroscopy allows rationalization of the remarkable thermometric luminescence of complex 1 and reveals the significant potential of molecular EuII compounds in luminescence thermometry.

Introducing the Tellurophene-Appended BODIPY: PDT Agent with Mass Cytometry Tracking Capabilities.

The synthesis and characterization of the first BODIPY appended to the five-membered heterocylic tellurophene [Te] moiety is reported. By incorporating tellurophene at the meso position, the tellurophene-appended boron-dipyrromethene dye (BODIPY) acts as a multimodal agent, becoming a potent photosensitizer with a mass cytometry tag. To synthesize the compound, we developed a method to enable late-stage Suzuki-Miyaura coupling by preparing and isolating tellurophene-2-BPin in a one-step procedure from the parent tellurophene. Coupling to a meso-substituted BODIPY functionalized with a pendant aryl bromide provides the desired tellurophene-appended BODIPY. This compound demonstrated a singlet oxygen quantum yield of 0.26 ± 0.01 and produced a light dose-dependent cytotoxicity with nanomolar IC50 values against 2D cultured HeLa cells and high efficacy against 3D cultured HeLa tumor spheroids, proving to be a strong photosensitizer. The presence of the tellurophene moiety could be detected using mass cytometry, thus showcasing the ability of a tellurophene-appended BODIPY as a novel photodynamic-therapy-mass-cytometry theranostic agent.

Synthesis, properties and reactivity of BCl2 aza-BODIPY complexes and salts of the aza-dipyrrinato scaffold.

The synthesis and characterisation of the BCl2-chelated complexes of both archetypal aza-dipyrrin sub-types are presented. A stepwise halogen exchange, leading to a mixed-halide Cl-B-F intermediate, is implicated in the conversion of F-aza-BODIPYs to Cl-aza-BODIPYs upon treatment with BCl3. The utility of the Cl-aza-BODIPY scaffold to facilitate substitutions at boron is demonstrated under mild conditions through treatment with aryl Grignard reagents. Additionally, the lability of the B-Cl bond enables facile removal of the BCl2 group, i.e. deprotection of F-aza-BODIPYs, under aqueous conditions. Three aza-dipyrrin HX salts were also synthesised and characterised. The pKa of the protonated aza-dipyrrin was determined to be 4, thereby providing insight regarding the storage and stability of such species.

Bis[pyrrolyl Ru(ii)] triads: a new class of photosensitizers for metal-organic photodynamic therapy.

A new family of ten dinuclear Ru(ii) complexes based on the bis[pyrrolyl Ru(ii)] triad scaffold, where two Ru(bpy)2 centers are separated by a variety of organic linkers, was prepared to evaluate the influence of the organic chromophore on the spectroscopic and in vitro photodynamic therapy (PDT) properties of the compounds. The bis[pyrrolyl Ru(ii)] triads absorbed strongly throughout the visible region, with several members having molar extinction coefficients (ε) ≥ 104 at 600-620 nm and longer. Phosphorescence quantum yields (Φ p) were generally less than 0.1% and in some cases undetectable. The singlet oxygen quantum yields (Φ Δ) ranged from 5% to 77% and generally correlated with their photocytotoxicities toward human leukemia (HL-60) cells regardless of the wavelength of light used. Dark cytotoxicities varied ten-fold, with EC50 values in the range of 10-100 µM and phototherapeutic indices (PIs) as large as 5400 and 260 with broadband visible (28 J cm-2, 7.8 mW cm-2) and 625 nm red (100 J cm-2, 42 mW cm-2) light, respectively. The bis[pyrrolyl Ru(ii)] triad with a pyrenyl linker (5h) was especially potent, with an EC50 value of 1 nM and PI > 27 000 with visible light and subnanomolar activity with 625 nm light (100 J cm-2, 28 mW cm-2). The lead compound 5h was also tested in a tumor spheroid assay using the HL60 cell line and exhibited greater photocytotoxicity in this more resistant model (EC50 = 60 nM and PI > 1200 with 625 nm light) despite a lower dark cytotoxicity. The in vitro PDT effects of 5h extended to bacteria, where submicromolar EC50 values and PIs >300 against S. mutans and S. aureus were obtained with visible light. This activity was attenuated with 625 nm red light, but PIs were still near 50. The ligand-localized 3ππ* state contributed by the pyrenyl linker of 5h likely plays a key role in its phototoxic effects toward cancer cells and bacteria.

Classifying donor strengths of dipyrrinato/aza-dipyrrinato ligands.

A parameter is reported by which to use 13C NMR chemical shifts to measure and predict the donor capabilities of N^N dipyrrinato and aza-dipyrrinato ligands chelating in L^X fashion. The results enable the rationalisation of the properties of these ligands and their complexes, as well as enable rational design incorporating both steric and electronic considerations when tuning to effect desired applications. Complexes containing these ligands are prevalent due to their desirable photophysical properties such as high chemical stability, resistance to photodegradation, strong absorbance, and ease of chemical modifiability.

Synthesis and reactivity of aza-dipyrrin alkali metal salts.

We report the lithium, sodium and potassium salts of aza-dipyrrins and detail their use as anionic aza-dipyrrinato ligand sources in complexation. Of the three types of alkali salts studied, those of lithium are found to be most useful as synthetic precursors. For example, they selectively afford heteroleptic aza-dipyrrinato zinc complexes which can be further modified via ligand exchange.