Sensitized triplet-triplet annihilation (sTTA) is the most promising mechanism for pooling the energy of two visible photons, but its applications in solution were so far limited to organic solvents, with a current maximum of the excited-singlet state energy of 3.6 eV. By combining tailor-made iridium complexes with naphthalenes, we demonstrate blue-light driven upconversion in water with unprecedented singlet-state energies approaching 4 eV. The annihilators have outstanding excited-state reactivities enabling challenging photoreductions driven by sTTA. Specifically, we found that an arylbromide bond activation can be achieved with blue photons, and we obtained full conversion for the very energy-demanding decomposition of a persistent ammonium compound as typical water pollutant, not only with a cw laser but also with an LED light source. These results provide the first proof-of-concept for the usage of low-power light sources for challenging reactions employing blue-to-UV upconversion in water, and pave the way for the further development of sustainable light-harvesting applications.
Biphenyl at its best: a (triisopropylsilyl)ethynyl group in para position converts biphenyl into a UV annihilator that is successfully employed for blue-to-UV upconversion with unprecedented output photon energies.
Several energy-demanding photoreactions require harsh UV light from inefficient light sources. The conversion of low-energy visible light to high-energy singlet states via triplet-triplet annihilation upconversion (TTA-UC) could offer a solution for driving such reactions under mild conditions. We present the first annihilator with an emission maximum in the UVB region that, combined with an organic sensitizer, is suitable for blue-to-UVB upconversion. The annihilator singlet was successfully employed as an energy donor in subsequent FRET activations of aliphatic carbonyls. This hitherto unreported UC-FRET reaction sequence was directly monitored using laser spectroscopy and applied to mechanistic irradiation experiments demonstrating the feasibility of Norrish chemistry. Our results provide clear evidence for a novel blue light-driven substrate or solvent activation strategy, which is important in the context of developing more sustainable lightto-chemical energy conversion systems.
Photoactive complexes with earth-abundant metals have
attracted
increasing interest in the recent years fueled by the promise of sustainable
photochemistry. However, sophisticated ligands with complicated syntheses
are oftentimes required to enable photoactivity with nonprecious metals.
Here, we combine a cheap metal with simple ligands to easily access
a photoactive complex. Specifically, we synthesize the molybdenum(0)
carbonyl complex Mo(CO)3(tpe) featuring the tripodal ligand
1,1,1-tris(pyrid-2-yl)ethane (tpe) in two steps with a high overall
yield. The complex shows intense deep-red phosphorescence with excited
state lifetimes of several hundred nanoseconds. Time-resolved infrared
spectroscopy and laser flash photolysis reveal a triplet metal-to-ligand
charge-transfer (3MLCT) state as the lowest excited state.
Temperature-dependent luminescence complemented by density functional
theory (DFT) calculations suggest thermal deactivation of the 3MLCT state via higher lying metal-centered states in analogy
to the well-known photophysics of [Ru(bpy)3]2+. Importantly, we found that the title compound is very photostable
due to the lack of labilized Mo–CO bonds (as caused by trans-coordinated CO) in the facial configuration of the
ligands. Finally, we show the versatility of the molybdenum(0) complex
in two applications: (1) green-to-blue photon upconversion via a triplet–triplet
annihilation mechanism and (2) photoredox catalysis for a green-light-driven
dehalogenation reaction. Overall, our results establish tripodal carbonyl
complexes as a promising design strategy to access stable photoactive
complexes of nonprecious metals avoiding tedious multistep syntheses.
Two novel bidentate C^C* spiro cyclometalated platinum(II) complexes comprising a spiro-conjugated bifluorene ligand and different β-diketonate auxiliary ligands are synthesized and characterized. Their preparation employs a robust and elaborate synthetic protocol commencing with an N-heterocyclic carbene precursor. Structural characterization by means of NMR techniques and solid-state structures validate the proposed and herein presented molecular scaffolds. Photophysical studies, including laser flash photolysis methods, reveal an almost exclusively ligand-centered triplet state, governed by the C^C* spiro −NHC ligand. The high triplet energies and the long triplet lifetimes in the order of 30 μs in solution make the complexes good candidates for light-emitting diode-driven photocatalysis, as initial energy transfer experiments reveal. In-depth time-dependent density functional theory investigations are in excellent accordance with our spectroscopic findings. The title compounds are highly emissive in the bluish-green color region with quantum yields of up to 87% in solid-state measurements.
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