Why and how could an aliphatic bridge allow for a long-range photoinduced charge separation in Tröger’s bases derivatives

Lanza, Priscila A.; Dusso, Diego; Mena, Leandro Daniel; Parise, Alejandro R.; Moyano, Elizabeth L.; Chesta, Carlos A.; Vera, D. Mariano A.

doi:10.1016/j.jphotochem.2023.114699

Cited by 3 publications

(2 citation statements)

References 41 publications

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“…If μ = 0, the long-range-corrected (LC) DFT calculation corresponds to the pure (non-LC) DFT calculation, and conversely μ = ∞ corresponds to the standard HF calculation . The parameter μ in CAM-B3LYP is 0.33 and, to lower the HF contribution, this parameter is adjusted to 0.27 for TD-DFT computations here and elsewhere for direct comparison with experimental emission data. ,− …”

Section: Experimental Methodsmentioning

confidence: 99%

Exciplex, Not Heavy-Atom Effect, Controls the Triplet Dynamics of a Series of Sulfur-Containing Thermally Activated Delayed Fluorescence Molecules

Öner,

Kuila,

Stavrou

et al. 2024

Chem. Mater.

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The efficiency of thermally activated delayed fluorescence (TADF) in organic materials relies on rapid intersystem crossing rates and fast conversion of triplet (T) excitons into a singlet (S) state. Heavy atoms such as sulfur or selenium are now frequently incorporated into TADF molecular structures to enhance these properties by increased spin−orbit coupling [spin orbit coupling (SOC)] between the T and S states. Here a series of donor−acceptor (D−A) molecules based on 12Hbenzo [4,5]thieno[2,3-a]carbazole and dicyanopyridine is compared with their nonsulfur control molecules designed to probe such SOC effects. We reveal that unexpected intermolecular interactions of the D−A molecules with carbazolecontaining host materials instead serve as the dominant pathway for triplet decay kinetics in these materials. In-depth photophysical and computational studies combined with organic light emitting diode measurements demonstrate that the anticipated heavy-atom effect from sulfur is overshadowed by exciplex formation. Indeed, even the unsubstituted acceptor fragments exhibit pronounced TADF exciplex emission in appropriate carbazole hosts. The intermolecular charge transfer and TADF in these systems are further confirmed by detailed time-dependent density functional theory studies. This work demonstrates that anticipated heavy-atom effects in TADF emitters do not always control or even impact the photophysical and electroluminescence properties.

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Section: Experimental Methodsmentioning

confidence: 99%

Exciplex, Not Heavy-Atom Effect, Controls the Triplet Dynamics of a Series of Sulfur-Containing Thermally Activated Delayed Fluorescence Molecules

Öner,

Kuila,

Stavrou

et al. 2024

Chem. Mater.

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show abstract

“…[15] On the other hand, it was also possible to setup an asymmetric derivative as a proof of principle pull-push dye, once again, as if it were a donor/π-linked/acceptor system. [16,42] Due to the large number and variability of applications found for these compounds and analogues, many efforts have been made to improve and optimize their synthesis. For this, different solvents were tested, [17] the sources of methylene and the nature of the acids used also were varied [18][19][20][21] and different amino-aromatic compounds (anilines, naphthylamine, aminopirazoles, among others) were used to obtain different families of TBs.…”

Section: Introductionmentioning

confidence: 99%

Mechanism of Synthesis of Tröger and Spiro‐Tröger Base Derivatives Starting from Naphthyl‐ and Anthracenylamines: A Computational Study

et al. 2023

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Tröger's bases (TB) have enormous applicability in different areas of science and technology. The mechanisms of reaction of different aminoaromatics with formaldehyde in acid media are described in depth using DFT calculations and model synthesis from our group. When different naphthylamines and anthracenylamine were used, a mixture of products was obtained, highlighting the corresponding TB, acridine and a novel isomer of TB, called SpiroTB, depending on the amino precursor and reaction conditions. Using methyl‐6‐amino‐naphthalene‐2‐carboxylate, ten possible synthesis pathways for TB, SpiroTB and acridine were explored thoroughly on their free energy surfaces. The most likely pathways were also evaluated for 2‐aminonaphthalene, 2‐aminoanthracene and 2‐methoxy‐6‐amino‐naphthalene. It was found that the first formaldehyde enters on a carbon ortho to the amino and the distribution of products is driven by the relative energies of the transition states required to form the methylene bridge between two aromatic carbons and/or between an ortho carbon and the nitrogen of the second aminoaromatic. The absence of spiroTB starting from 4‐bromoaniline was also explained.

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AIE-active dyes based on Tröger's base: Synthesis and mechanochromic luminescence

Yu,

Guo,

et al. 2024

Dyes and Pigments

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Why and how could an aliphatic bridge allow for a long-range photoinduced charge separation in Tröger’s bases derivatives

Cited by 3 publications

References 41 publications

Exciplex, Not Heavy-Atom Effect, Controls the Triplet Dynamics of a Series of Sulfur-Containing Thermally Activated Delayed Fluorescence Molecules

Exciplex, Not Heavy-Atom Effect, Controls the Triplet Dynamics of a Series of Sulfur-Containing Thermally Activated Delayed Fluorescence Molecules

Mechanism of Synthesis of Tröger and Spiro‐Tröger Base Derivatives Starting from Naphthyl‐ and Anthracenylamines: A Computational Study

AIE-active dyes based on Tröger's base: Synthesis and mechanochromic luminescence

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