According to Hund's rule, the lowest triplet state (T 1 ) is lower in energy than the lowest excited singlet state (S 1 ) in closed-shell molecules. The exchange integral lowers the energy of the triplet state and raises the energy of the singlet state of the same orbital character, leading to a positive singlet−triplet energy gap (Δ ST ). Exceptions are known for biradicals and charge-transfer excited states of large molecules in which the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) are spatially separated, resulting in a small exchange integral. In the present work, we discovered with ADC(2), CC2, EOM-CCSD, and CASPT2 calculations that heptazine (1,3,4,6,7,9,9bheptaazaphenalene or tri-s-triazine) exhibits an inverted S 1 /T 1 energy gap (Δ ST ≈ −0.25 eV). This appears to be the first example of a stable closedshell organic molecule exhibiting S 1 /T 1 inversion at its equilibrium geometry. The origins of this phenomenon are the nearly pure HOMO− LUMO excitation character of the S 1 and T 1 states and the lack of spatial overlap of HOMO and LUMO due to a unique structure of these orbitals of heptazine. The S 1 /T 1 inversion is found to be extremely robust, being affected neither by substitution of heptazine nor by oligomerization of heptazine units. Using time-resolved photoluminescence and transient absorption spectroscopy, we investigated the excited-state dynamics of 2,5,8-tris(4-methoxyphenyl)-1,3,4,6,7,9,9bheptaazaphenalene (TAHz), a chemically stable heptazine derivative, in the presence of external heavy atom sources as well as triplet-quenching oxygen. These spectroscopic data are consistent with TAHz singlet excited state decay in the absence of a low-energy triplet loss channel. The absence of intersystem crossing and an exceptionally low radiative rate result in unusually long S 1 lifetimes (of the order of hundreds of nanoseconds in nonaqueous solvents). These features of the heptazine chromophore have profound implications for organic optoelectronics as well as for water-splitting photocatalysis with heptazinebased polymers (e.g., graphitic carbon nitride) which have yet to be systematically explored and exploited.

All-inorganic cesium lead bromide (CsPbBr 3 ) perovskite quantum dots (QDs) have recently emerged as highly promising solution-processed materials for nextgeneration light-emitting applications. They combine the advantages of QD and perovskite materials, which makes them an attractive platform for achieving high optical gain with high stability. Here, we report an ultralow lasing threshold (0.39 μJ/cm 2 ) from a hybrid vertical cavity surface emitting laser (VCSEL) structure consisting of a CsPbBr 3 QD thin film and two highly reflective distributed Bragg reflectors (DBRs). Temperature dependence of the lasing threshold and longterm stability of the device were also characterized. Notably, the CsPbBr 3 QDs provide superior stability and enable stable device operation over 5 h/1.8 × 10 7 optical pulse excitations under ambient conditions. This work demonstrates the significant potential of CsPbBr 3 perovskite QD VCSELs for highly reliable lasers, capable of operating in the short-pulse (femtosecond) and quasi-continuous-wave (nanosecond) regimes.

Solar hydrogen generation from water represents a compelling component of a future sustainable energy portfolio. Recently, chemically robust heptazine-based polymers known as graphitic carbon nitrides (g-CN) have emerged as promising photocatalysts for hydrogen evolution using visible light while withstanding harsh chemical environments. However, since g-CN electron-transfer dynamics are poorly understood, rational design rules for improving activity remain unclear. Here, we use visible and near-infrared femtosecond transient absorption (TA) spectroscopy to reveal an electron-transfer cascade that correlates with a near-doubling in photocatalytic activity from 2050 to 3810 μmol h g when we infuse a suspension of bulk g-CN with 10% mass loading of chemically exfoliated carbon nitride. TA spectroscopy indicates that exfoliated carbon nitride quenches photogenerated electrons on g-CN at rates approaching the molecular diffusion limit. The TA signal for photogenerated electrons on g-CN decays with a time constant of 1/k' = 660 ps in the mixture versus 1/k = 4.1 ns in g-CN alone. Our TA measurements suggest that the charge generation efficiency in g-CN is greater than 65%. Exfoliated carbon nitride, which liberates only trace hydrogen levels when photoexcited directly, does not appear to independently sustain appreciable long-lived charge generation. Thus, the activity enhancement in the two-component infusion evidently results from a cooperative effect in which charge is generated on g-CN, followed by electron transfer to exfoliated carbon nitride containing photocatalytic chain terminations. This correlation between electron transfer and photocatalytic activity provides new insight into structural modifications for controlling charge separation dynamics and activity of carbon-based photocatalysts.

To gain mechanistic understanding of heptazine-based photochemistry, we synthesized and studied 2,5,8-tris­(4-methoxyphenyl)-1,3,4,6,7,9,9b-heptaazaphenalene (TAHz), a model molecular photocatalyst chemically related to carbon nitride. On the basis of time-resolved photoluminescence (TR-PL) spectroscopy, we kinetically reveal a new feature that emerges in aqueous dispersions of TAHz. Using global target analysis, we spectrally and kinetically resolve the new emission feature to be blue shifted from the steady-state luminescence, and observe a fast decay component exhibiting a kinetic isotope effect (KIE) of 2.9 in H2O versus D2O, not observed in the steady-state PL. From ab initio electronic-structure calculations, we attribute this new PL peak to the fluorescence of an upper excited state of mixed nπ*/ππ* character. In water, the KIE suggests the excited state is quenched by proton-coupled electron transfer, liberating hydroxyl radicals that we detect using terephthalic acid. Our findings are consistent with recent theoretical predictions that heptazine-based photocatalysts can participate in proton-coupled electron transfer with H2O.

To inform prospective design rules for controlling aza-arene photochemistry, we studied hydrogen-bonded complexes of 2,5,8-tris­(4-methoxyphenyl)-1,3,4,6,7,9,9b-heptaazaphenalene (TAHz), a molecular photocatalyst chemically related to graphitic carbon nitride, with a variety of phenol derivatives. We have focused on excited state proton-coupled electron transfer (ES-PCET) reactions of heptazines because the excited state properties governing this process remain conceptually opaque compared to proton reduction reactions for these materials. We used ground-state absorption, time-resolved photoluminescence, and ab initio quantum chemical calculations to analyze TAHz reactivity toward a series of six para-substituted phenol derivatives. We determined association constants (K A), excited-state quenching rate constants (k Q), kinetic isotope effects, and transition-state barriers (ΔE ⧧). From this data, we provide a generalizable picture of hydrogen bond formation and excited state reactivity of heptazine-based materials with hydrogen-atom donating solvents. These results provide important insights into strategies to tune charge transfer state energies and increase ES-PCET rates.