skip to main content

Title: Delayed photoacidity produced through the triplet–triplet annihilation of a neutral pyranine derivative
A novel pyranine derivative, Et HPTA-OH, was synthesized via the substitution of the anionic sulfonate groups with neutral diethylsulfonamide groups. The photophysical and photochemical properties of Et HPTA-OH were studied using photoluminescence quenching and transient absorption spectroscopy. The singlet state of Et HPTA-OH was found to be highly photoacidic (p K a * = 8.74 in acetonitrile). A series of aniline and pyridine bases were used to investigate excited-state proton transfer (ESPT) from singlet Et HPTA-OH, and rate constants for singlet quenching via ESPT were determined ( k q = 5.18 × 10 9 to 1.05 × 10 10 M −1 s −1 ). Et HPTA-OH was also found to exhibit a long-lived triplet state which reacts through a triplet–triplet annihilation (TTA) process to reform singlet Et HPTA-OH on timescales of up to 80 μs. Detection of ESPT photoproducts on timescales comparable to that of TTA singlet regeneration provides strong evidence for photoacidic behavior stemming from the regenerated singlet Et HPTA-OH.  more » « less
Award ID(s):
Author(s) / Creator(s):
; ;
Date Published:
Journal Name:
Physical Chemistry Chemical Physics
Page Range / eLocation ID:
16353 to 16358
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. The efficiency of solar cells may be increased by utilizing photons with energies below the band gap of the absorber. This may be enabled by upconversion of low energy photons into high energy photons via triplet–triplet annihilation (TTA) in organic chromophores. The quantum yield of TTA is often low due to competing processes. The singlet pathway, where a high energy photon is emitted, is one of three possible outcomes of an encounter between two triplet excitons. The quintet pathway is often too high in energy to be accessible, leaving the triplet pathway as the main competing process. Using many-body perturbation theory in the GW approximation and the Bethe–Salpeter equation, we calculate the energy release in both the singlet and triplet pathways for 59 chromophores of different chemical families. We find that in most cases the triplet pathway is open and has a larger energy release than the singlet pathway. Thus, the energetics perspective explains why there are so few TTA emitters and why the quantum yield of TTA is typically low. That said, our results also indicate that the performance of emitters from known chemical families may be improved by chemical modifications, such as functionalization with side groups, and that new chemical families could be explored to discover more TTA emitters. 
    more » « less
  2. Abstract

    Density functional theory and extrapolated CCSD(T) computations of several “anti‐Bredt” alkenes were carried to explore possible 1,2‐diyl “alkene” candidates with a triplet ground state. Ten candidates containing twisted double bonds at the bridgehead positions of bicyclic structures (1‐6) or adamantene (7‐10) derivatives were studied. Based on a combination of ring strain, rigid scaffolding, and steric crowding, four species were identified to have surprisingly low singlet‐triplet energy gaps (lower than 4 kcal/mol). Atert‐butyl substituted bicyclic structure (4) was identified to have a near‐zero singlet‐triplet energy gap, but no triplet ground‐state alkene was found. Ring strain energy (RSE) calculations, π‐orbital axis vector (POAV) analyses, and multiple linear regression models were performed to elucidate the geometric and energetic effects of double bond twisting in1‐10. Based on our computational exploration, it appears unlikely that there is a ground‐state triplet olefin.

    more » « less
  3. Optical upconversion (UC) of low energy photons into high energy photons enables solar cells to harvest photons with energies below the band gap of the absorber, reducing the transmission loss. UC based on triplet–triplet annihilation (TTA) in organic chromophores can upconvert photons from sunlight, albeit with low conversion efficiency. We utilize three energy-based criteria to assess the UC potential of TTA emitters in terms of the quantum yield (QY) and the anti-Stokes shift. The energy loss in the singlet pathway of an emitter encounter complex, where a high energy photon is emitted, determines whether a chromophore may undergo TTA. The energy loss in the triplet pathway, which is the main competing process, impacts the TTA QY. The energy difference between the lowest singlet and triplet excitation states in TTA emitters sets an upper bound for the anti-Stokes shift of TTA-UC. Using the energetic criteria evaluated by time-dependent density functional theory (TDDFT) calculations, we find that benzo[ a ]tetracene, benzo[ a ]pyrene, and their derivatives are promising TTA emitters. The energetics assessment and computer simulations could be used to efficiently discover and design more candidate high-performance TTA emitters. 
    more » « less
  4. The development of efficient solid-state photon upconversion (UC) devices remains paramount for practical applications of the technology. In recent years, the incorporation of perovskite thin films as triplet sensitizers for triplet–triplet annihilation (TTA)-based UC has provided a promising solution. In the pursuit of finding an “ideal annihilator” to maximize the apparent anti-Stokes shift, we investigate naphtho[2,3-a]pyrene (NaPy) as an annihilator in both solution-based and perovskite-sensitized TTA-UC systems. Surprisingly, we observe different emission behaviors of NaPy in the solid state based on the excitation wavelength. Under direct excitation, a high-energy transition S1' dominates the emission spectrum, while UC results in increased emission from a lower lying state S1''. We propose that this is the result of aggregation-related lowering of the singlet excited state thus changing the fundamental energetic landscape underlying TTA. Aggregation decreases the singlet energy below the energy level of the triplet pair state 1(TT), yielding energetically favorable emission from the aggregated singlet state S1'' and weak emission from the higher lying singlet state S1' through thermally or entropically driven TTA-UC. 
    more » « less
  5. Abstract

    Not long ago, the occurrence of quantum mechanical tunneling (QMT) chemistry involving atoms heavier than hydrogen was considered unreasonable. Contributing to the shift of this paradigm, we present here the discovery of a new and distinct heavy‐atom QMT reaction. Triplet syn‐2‐formyl‐3‐fluorophenylnitrene, generated in argon matrices by UV‐irradiation of an azide precursor, was found to spontaneously cyclize to singlet 4‐fluoro‐2,1‐benzisoxazole. Monitoring the transformation by IR spectroscopy, temperature‐independent rate constants (k≈1.4×10−3 s−1; half‐life of ≈8 min) were measured from 10 to 20 K. Computational estimated rate constants are in fair agreement with experimental values, providing evidence for a mechanism involving heavy‐atom QMT through crossing triplet to singlet potential energy surfaces. Moreover, the heavy‐atom QMT takes place with considerable displacement of the oxygen atom, which establishes a new limit for the heavier atom involved in a QMT reaction in cryogenic matrices.

    more » « less