In a Fourier transform‐ion cyclotron resonance mass spectrometer the gas phase reactivities of niobium clusters Nb⁺_n (n=1–28) with molecular hydrogen, water, methane, ethane, n‐propane, n‐heptane, cyclohexane, acetylene, ethylene, allene, benzene, propene, toluene, xylene, and acetonitrile were investigated under single collision conditions as well as the reactivities of oxidized niobium cluster cations with ethylene and benzene. The reactions of larger clusters with a variety of unsaturated hydrocarbons are believed to proceed via long lived ‘‘physisorbed’’ addition intermediate complexes, which subsequently rearrange to form ‘‘chemisorbed,’’ extensively dehydrogenated final products. The overall reaction seems to proceed with near collision rates, almost independent of cluster size. In some cases also the physisorbed primary products are stabilized and detected. Their yields depend sensitively on the specific nature of the reactant, and on the niobium cluster size n. Fully saturated hydrocarbons unable to form the long lived complexes are unreactive with respect to the larger (n≳7) Nb⁺_n clusters. Smaller clusters with n≤7 seem to react by a different, prompt reaction mechanism. The rate of this reaction steeply decreases, and the degree of product dehydrogenation increases with n.

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(2-pyridylmethyl)pyridine) shifted to higher energy from ca. 780 nm observed for known highly emissive chromium(III) complexes to 709 nm. The photoluminescence quantum yields climb to 20%, and very long excited state lifetimes in the millisecond range are achieved at room temperature in acidic D₂O solution. Partial ligand deuteration increases the quantum yield to 25%. The high excited state energy of [Cr(bpmp)₂]³⁺ and its facile reduction to [Cr(bpmp)₂]²⁺ result in a high excited state redox potential. The ligand’s methylene bridge acts as a Brønsted acid quenching the luminescence at high pH. Combined with a pH-insensitive chromium(III) emitter, ratiometric optical pH sensing is achieved with single wavelength excitation. The photophysical and ground state properties (quantum yield, lifetime, redox potential, and acid/base) of this spin-flip complex incorporating an earth-abundant metal surpass those of the classical precious metal [Ru(α-diimine)₃]²⁺ charge transfer complexes, which are commonly employed in optical sensing and photo(redox) catalysis, underlining the bright future of these molecular ruby analogues.