Transient FTIR spectroscopy after one- and two-colour excitation on a highly luminescent chromium(III) complex.

The development of photoactive transition metal complexes with Earth-abundant metals is a rapidly growing research field, where a deeper understanding of the underlying photophysical processes is of great importance. A multitude of potential applications in the fields of photosensitizing, optical sensing, photoluminescence and photoredox catalysis motivates demanding spectroscopic studies. We applied a series of high-level spectroscopic methods on the previously reported highly luminescent chromium(iii) complex [Cr(ddpd)2](BF4)3 (ddpd = N,N'-dimethyl-N,N'-dipyridine-2-ylpyridine-2,6-diamine) possessing two near-IR emissive doublet states with microsecond lifetimes. Luminescence measurements…

Titelbild: Luminescence and Light‐Driven Energy and Electron Transfer from an Exceptionally Long‐Lived Excited State of a Non‐Innocent Chromium(III) Complex (Angew. Chem. 50/2019)

A Vanadium(III) Complex with Blue and NIR-II Spin-Flip Luminescence in Solution.

Luminescence from Earth-abundant metal ions in solution at room temperature is a very challenging objective due to the intrinsically weak ligand field splitting of first-row transition metal ions, which leads to efficient nonradiative deactivation via metal-centered states. Only a handful of 3d

Strongly Red-Emissive Molecular Ruby [Cr(bpmp)2]3+ Surpasses [Ru(bpy)3]2+

Gaining chemical control over the thermodynamics and kinetics of photoexcited states is paramount to an efficient and sustainable utilization of photoactive transition metal complexes in a plethora of technologies. In contrast to energies of charge transfer states described by spatially separated orbitals, the energies of spin-flip states cannot straightforwardly be predicted as Pauli repulsion and the nephelauxetic effect play key roles. Guided by multireference quantum chemical calculations, we report a novel highly luminescent spin-flip emitter with a quantum chemically predicted blue-shifted luminescence. The spin-flip emission band of the chromium complex [Cr(bpmp)2]3+ (bpmp = 2,6-bis(…

Luminescence and Light‐Driven Energy and Electron Transfer from an Exceptionally Long‐Lived Excited State of a Non‐Innocent Chromium(III) Complex

Abstract Photoactive metal complexes employing Earth‐abundant metal ions are a key to sustainable photophysical and photochemical applications. We exploit the effects of an inversion center and ligand non‐innocence to tune the luminescence and photochemistry of the excited state of the [CrN6] chromophore [Cr(tpe)2]3+ with close to octahedral symmetry (tpe=1,1,1‐tris(pyrid‐2‐yl)ethane). [Cr(tpe)2]3+ exhibits the longest luminescence lifetime (τ=4500 μs) reported up to date for a molecular polypyridyl chromium(III) complex together with a very high luminescence quantum yield of Φ=8.2 % at room temperature in fluid solution. Furthermore, the tpe ligands in [Cr(tpe)2]3+ are redox non‐innocent, …

Ultrafast and long-time excited state kinetics of an NIR-emissive vanadium(iii) complex I: synthesis, spectroscopy and static quantum chemistry.

In spite of intense, recent research efforts, luminescent transition metal complexes with Earth-abundant metals are still very rare owing to the small ligand field splitting of 3d transition metal complexes and the resulting non-emissive low-energy metal-centered states. Low-energy excited states decay efficiently non-radiatively, so that near-infrared emissive transition metal complexes with 3d transition metals are even more challenging. We report that the heteroleptic pseudo-octahedral d2-vanadium(iii) complex VCl3(ddpd) (ddpd = N,N′-dimethyl-N,N′-dipyridine-2-yl-pyridine-2,6-diamine) shows near-infrared singlet → triplet spin–flip phosphorescence maxima at 1102, 1219 and 1256 nm with a …

CCDC 1876390: Experimental Crystal Structure Determination

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CCDC 1989536: Experimental Crystal Structure Determination

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CCDC 1958562: Experimental Crystal Structure Determination

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CCDC 2083757: Experimental Crystal Structure Determination

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CCDC 1989537: Experimental Crystal Structure Determination

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CCDC 1876389: Experimental Crystal Structure Determination

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