Factorizing the Nephelauxetic Effect in Heteroleptic Molecular Rubies.

The interest in chromium(III) complexes has been renewed over the past decade for the design of efficient earth-abundant phosphorescent red-to-near-infrared spin-flip emitters and photocatalysts with long excited state lifetimes. In this context, we report the energy tuning of spin-flip excited states based on heteroleptic bis(tridentate) polypyridine chromium(III) complexes , namely, , and with the tridentate ligands L and L [X/Y = NMe, ,'-dimethyl-,'-dipyridin-2-ylpyridine-2,6-diamine; X/Y = CH, 2,6-bis(2-pyridylmethyl)pyridine and X/Y = S, 2,6-bis(pyridine-2-ylthio)pyridine]. The heteroleptic complexes are obtained via a novel synthetic approach toward the required intermediate labile triflato complexes Cr(L)(OTf) () from the respective chlorido precursors CrCl(L) () using trimethylsilyl trifluoromethanesulfonate.

Bridge editing of spin-flip emitters gives insight into excited state energies and dynamics.

Six-coordinate chromium(iii) complexes with high spin-flip (SF) photoluminescence quantum yields and lifetimes (molecular rubies) have attracted huge interest in the past years due to their applicability in sensing, photocatalysis or circularly polarised emission. However, clearcut design rules for high quantum yields and lifetimes are still lacking due to the multidimensional problem of the non-radiative decay of the SF states. Based on an isostructural series of complexes differing in the ligand backbone, we disentangle decisive structural and electronic features for SF excited state energies and non-radiative decays promoted by spin-orbit coupling, Jahn-Teller distortions and (thermally activated) multiphonon relaxation.

Efficient Triplet-Triplet Annihilation Upconversion Sensitized by a Chromium(III) Complex via an Underexplored Energy Transfer Mechanism.

Sensitized triplet-triplet annihilation upconversion (sTTA-UC) mainly relies on precious metal complexes thanks to their high intersystem crossing (ISC) efficiencies, excited state energies, and lifetimes, while complexes of abundant first-row transition metals are only rarely utilized and with often moderate UC quantum yields. [Cr(bpmp) ] (bpmp=2,6-bis(2-pyridylmethyl)pyridine) containing earth-abundant chromium possesses an absorption band suitable for green light excitation, a doublet excited state energy matching the triplet energy of 9,10-diphenyl anthracene (DPA), a close to millisecond excited state lifetime, and high photostability. Combined ISC and doublet-triplet energy transfer from excited [Cr(bpmp) ] to DPA gives DPA with close-to-unity quantum yield.

Strongly Red-Emissive Molecular Ruby [Cr(bpmp)] Surpasses [Ru(bpy)].

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.

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

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 [CrN ] chromophore [Cr(tpe) ] with close to octahedral symmetry (tpe=1,1,1-tris(pyrid-2-yl)ethane). [Cr(tpe) ] 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.