Using diketopyrrolopyrroles to stabilize double excitation and control internal conversion

Casal, Mariana T. do; Toldo, Josene M.; Plasser, Felix; Barbatti, Mario

doi:10.1039/d2cp03533b

Cited by 8 publications

(12 citation statements)

References 74 publications

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“…A more extended set of derivatives is given in Table S4 †. As pointed out previously, 76 these molecules have an extended polyene backbone with additional functional groups. The lowest doubly excited singlet states (of A g symmetry) in these molecules lie at similar energies as the lowest singly excited B u singlet states.…”

Section: Resultsmentioning

confidence: 94%

“…8,74 Computationally, the energy gap and order of states are strongly method-dependent. 20,63,75,76 While MS-CASPT2 calculations correctly predict the state inversion, CC3 predicts that 1 1 B u remains above 2 1 A g , although both methods deliver a small energy gap between those states. 63 ADC(2)-x and ADC(3) always predict 2 1 A g state as the lowest excited state, while ADC(2)-s predicts that to be the 1 1 B u state for polyenes up to four double bonds.…”

Section: Resultsmentioning

confidence: 99%

“…8, and more data is presented in the ESI †. We start with a diketopyrrolopyrrole derivative 76 used in optoelectronics, 80,81 OLEDs 82 and as singlet-fission chromophores 83,84 and a derivative of its bis-thiophene building block (Fig. 8).…”

Section: Resultsmentioning

confidence: 99%

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Classification of doubly excited molecular electronic states

et al. 2023

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Section: Resultsmentioning

confidence: 94%

Section: Resultsmentioning

confidence: 99%

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Classification of doubly excited molecular electronic states

et al. 2023

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“…95 However, quantitative approaches enabling quantifying the degree of admixture between different excited states contributing to T 1 are necessary to unambiguously characterize the character of T 1 . The transition density matrix and decomposition analysis of the TD-DFT results, as implemented in THEODORE, have been successfully applied to characterize the excited states of both organic 96,97 and inorganic 98 molecular systems. We performed a decomposition analysis of the T 1 excited state for 1−30.…”

Section: Excited-state Character Of Tmentioning

confidence: 99%

Phosphorescent Properties of Heteroleptic Ir(III) Complexes: Uncovering Their Emissive Species

Kumar,

Pérez-Escribano,

van Raamsdonk

et al. 2023

J. Phys. Chem. A

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In this contribution, we assess the computational machinery to calculate the phosphorescence properties of a large pool of heteroleptic [Ir(C^N)2(N^N)]+ complexes (where N^N is an ancillary ligand and C^N is a cyclometalating ligand) including their phosphorescent rates and their emission spectra. Efficient computational protocols are next proposed. Specifically, different flavors of DFT functionals were benchmarked against DLPNO-CCSD(T) for the phosphorescence energies. The transition density matrix and decomposition analysis of the emitting triplet excited state enable us to categorize the studied complexes into different cases, from predominant triplet ligand-centered (3LC) character to predominant charge-transfer (3CT) character, either of metal-to-ligand charge transfer (3MLCT), ligand-to-ligand charge transfer (3LLCT), or a combination of the two. We have also calculated the vibronically resolved phosphorescent spectra and rates. Ir(III) complexes with predominant 3CT character are characterized by less vibronically resolved bands as compared to those with predominant 3LC character. Furthermore, some of the complexes are characterized by close-lying triplet excited states so that the calculation of their phosphorescence properties poses additional challenges. In these scenarios, it is necessary to perform geometry optimizations of higher-lying triplet excited states (i.e., Tn). We demonstrate that in the latter scenarios all of the close-lying triplet species must be considered to recover the shape of the experimental emission spectra. The global analysis of computed emission energies, shape of the computed emission spectra, computed rates, etc. enable us to unambiguously pinpoint for the first time the triplet states involved in the emission process and to provide a general classification of Ir(III) complexes with regard to their phosphorescence properties.

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“…95 However, quantitative approaches enabling to e.g., quantify the degree of admixture between different excited states contributing to T 1 are necessary to unambiguously characterize the character of T 1 . The transition density matrix and decomposition analysis of the TD-DFT results, as implemented in THEODORE, has been successfully applied to characterize the excited states of both organic 96,97 and inorganic 98 molecular systems. We performed the decomposition analysis of the T 1 excited state for 1-30.…”

Section: Excited State Character Of Tmentioning

confidence: 99%

The phosphorescent properties of heteroleptic Ir (III) complexes: uncovearing their emissive species

Kumar

Pérez-Escribano

Raamsdonk

et al. 2023

Preprint

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In this contribution we assess the computational machinery to calculate the phosphorescence properties of a large pool of heteroleptic [Ir(C^N)2(N^N)]+ complexes (where N^N is an ancillary ligand and C^N is a cyclometalating ligand) including their phosphorescent rates and their emission spectra. Efficient computational protocols are next proposed. Specifically, different flavors of DFT functionals were benchmarked against DLPNO-CCSD(T) for the phosphorescence energies. Transition density matrix and decomposition analysis of the emitting triplet excited state enables to categorize the studied complexes into different cases, from e.g., predominant triplet ligand-centered (3LC) character to predominant charge-transfer (3CT) character, either of metal-to-ligand charge transfer (3MLCT), ligand-to-ligand charge transfer (3LLCT) or a combination of the two. We have also calculated the vibronically resolved phosphorescent spectra and rates. Ir (III) complexes with predominant 3CT character are characterized by less vibronically-resolved bands as compared to those with predominant 3LC character. Furthermore, some of the complexes are characterized by close-lying triplet excited states, so that the calculation of their phosphorescence properties poses additional challenges. In these scenarios, it is necessary to perform geometry optimizations of higher-lying triplet excited states (i.e., Tn). We demonstrate that in the latter scenarios all the close-lying triplet species must be considered to recover the shape of the experimental emission spectra. The global analysis of computed emission energies, shape of the computed emission spectra, computed rates, etc. enable us to unambiguously pinpoint for the first time the triplet states involved in the emission process and to provide a general classification of Ir (III) complexes with regards to their phosphorescent properties.

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Using diketopyrrolopyrroles to stabilize double excitation and control internal conversion

Abstract: Diketopyrrolopyrrole (DPP) is a pivotal functional group to tune the physicochemical properties of novel organic photoelectronic materials. Among its multiple uses, DPP-thiophene derivatives forming a dimer through a vinyl linker...

Cited by 8 publications

References 74 publications

Classification of doubly excited molecular electronic states

Classification of doubly excited molecular electronic states

Phosphorescent Properties of Heteroleptic Ir(III) Complexes: Uncovering Their Emissive Species

The phosphorescent properties of heteroleptic Ir (III) complexes: uncovearing their emissive species

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