Perylene-Monoimides: Singlet Fission Down-Conversion Competes with Up-Conversion by Geminate Triplet-Triplet Recombination

Papadopoulos I, Gutiérrez-Moreno D, McCosker PM, Casillas R, Keller PA, Sastre-Santos Á, Clark T, Fernández-Lázaro F, Guldi DM (2020)

Publication Type: Journal article

Publication year: 2020

Journal

Book Volume: 124

Pages Range: 5727-5736

Journal Issue: 28

DOI: 10.1021/acs.jpca.0c04091

Abstract

Triplet-excited-state energies of perylene-monoimides (PMIs) lie in the range 1.12 eV ± 2 meV when compared to singlet-excited-state energies of about 2.39 eV ± 2 meV; therefore, the corresponding naphthalene-linked PMI-Dimer was investigated as a novel singlet-fission (SF) material. Ultrafast transient absorption measurements demonstrated the (S1S0)-to-1(T1T1) transformation and the involvement of a mediating step in the overall 1(T1T1) formation. The intermediate is a charge-transfer state that links the initial (S1S0) with the final 1(T1T1), and imposes charge-transfer character on both, which are thus denoted (S1S0)CT and 1(T1T1)CT. At room temperature, the decorrelation and stability of 1(T1T1)CT is affected by the geminate triplet-triplet recombination (G-TTR) of the two triplets. Independent confirmation for G-TTR to afford up-converted (S1S0)UC in fsTA and nsTA measurements with PMI-Dimer, came from probing PMI-Monomer (T1)s in triplet-triplet annihilation up-conversion (TTA-UC). The G-TTR channel, active in the PMI-Dimer at room temperature, is suppressed by working at either low temperatures (∼140 K) or in polar solvents (benzonitrile): Both scenarios assist in stabilizing (T1T1)CT. As a consequence, the triplet quantum yields are 4.2% and 14.9% at room temperature and 140 K, respectively, in 2-methyltetrahydrofuran.

Authors with CRIS profile

Involved external institutions

Miguel Hernández University of Elche (UMH) / Universidad Miguel Hernández de Elche Spain (ES) University of Wollongong (UOW) Australia (AU)

How to cite

APA:

Papadopoulos, I., Gutiérrez-Moreno, D., McCosker, P.M., Casillas, R., Keller, P.A., Sastre-Santos, Á.,... Guldi, D.M. (2020). Perylene-Monoimides: Singlet Fission Down-Conversion Competes with Up-Conversion by Geminate Triplet-Triplet Recombination. Journal of Physical Chemistry A, 124(28), 5727-5736. https://dx.doi.org/10.1021/acs.jpca.0c04091

MLA:

Papadopoulos, Ilias, et al. "Perylene-Monoimides: Singlet Fission Down-Conversion Competes with Up-Conversion by Geminate Triplet-Triplet Recombination." Journal of Physical Chemistry A 124.28 (2020): 5727-5736.

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