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Organisationseinheit der BAM
Bright, long-lived emission from first-row transition-metal complexes is very challenging to achieve. Herein, we present a new strategy relying on the rational tuning of energy levels. With the aid of the large N-Cr-N bite angle of the tridentate ligand ddpd (N,N′-dimethyl-N,N′-dipyridine-2-ylpyridine-2,6-diamine) and its strong σ-donating capabilities, a very large ligand-field splitting could be introduced in the chromium(III) complex [Cr(ddpd)2]3+, that shifts the deactivating and photoreactive 4T2 state well above the emitting 2E state. Prevention of back-intersystem crossing from the 2E to the 4T2 state enables exceptionally high near-infrared phosphorescence quantum yields and lifetimes for this 3d metal complex. The complex [Cr(ddpd)2](BF4)3 is highly water-soluble and very stable towards thermal and photo-induced substitution reactions and can be used for fluorescence intensity- and lifetime-based oxygen sensing in the NIR.
The syntheses, structures, and photophysical properties of two new zinc(II) complexes bearing the tridentate N,N′-dimethyl-N,N′-dipyridin-2-ylpyridine-2,6-diamine (ddpd) ligand are presented. Structural investigations through single-crystal X-ray diffractometry, NMR spectroscopy, and density functional theory calculations revealed a diverse coordination behavior that depends on the counterion. Spectroscopic (UV/Vis and emission spectroscopy) and theoretical techniques (DFT and time-dependent DFT calculations) were employed to explore the photophysical properties of the complexes.
Two nanosensors for simultaneous optical measurements of the bioanalytically and biologically relevant analytes temperature (“T”), oxygen (“O”), and pH (“P”) have been designed. These “TOP” nanosensors are based on 100 nmsized silica-coated polystyrene nanoparticles (PS-NPs) doped with a near-infrared emissive oxygen- and temperature-sensitive chromium(III) complex ([Cr(ddpd)2][BPh4]3, CrBPh4) and an inert reference dye (Nile Red, NR or 5,10,15,20tetrakis(pentafluorophenyl) porphyrin, TFPP) and are covalently labeled with pHsensitive fluorescein isothiocyanate (FITC). These emitters can be excited at the same wavelength and reveal spectrally distinguishable emission bands, allowing for ratiometric intensity-based and time-resolved studies in the visible and near-infrared wavelength region. Studies in PBS buffer solutions and in a model body liquid demonstrate the applicability of these nanosensors for the sensitive luminescence readout of TOP simultaneously at the same spatialposition.
The synthesis, structure, reactivity,and photophysical properties of anovel acidic,luminescentchromium(III) complex [Cr(H2tpda)2]3+ (23+ +)bearing the tridentate H2tpda (2,6-bis(2-pyridylamino)pyridine) ligand are presented. Excitation of 23+ + at 442 nm results in strong, long-lived NIR luminescence at 782 nm in water and in acetonitrile. X-ray diffraction analysis and IR spectroscopy revealhydrogen-bonding interactions of the counter ions to the NH groups of 23+ + in the solidstate. Deprotonation of the NH groups of 23+ + by using anon-nucleophilic Schwesinger base in CH3CN switches off the luminescence. Re-protonation by using HClO4 restores the emission. In water,the pKa value of 23+ + amountsto8 .8, yet deprotonation is not reversible in the presence of hydroxide ions. Dioxygen quenches the emission of 23+ +,but to aweaker extent than expected. This is possibly due to the strong ion-pairing properties of 23+ + even in solution, reducing the energy transfer efficiency to O2.Deuteration of the NH groups of 23+ + approximately doubles the quantum yield and lifetime in water,demonstrating the importance of multiphoton relaxation in these NIR emitters.