journal article

Journal Article

Accounts of Chemical Research. 2024, 57(15), p. 2219-2232

Modulating the Photophysical Properties of Twisted Donor-Acceptor-Donor π-Conjugated Molecules: Effect of Heteroatoms, Molecular Conformation, and Molecular Topology

Takeda, Youhei

American Chemical Society

English

2024-07-24

https://doi.org/10.1021/acs.accounts.4c00353

Takeda Y. Modulating the Photophysical Properties of Twisted Donor-Acceptor-Donor π-Conjugated Molecules: Effect of Heteroatoms, Molecular Conformation, and Molecular Topology. Accounts of Chemical Research 57, 2219 (2024); https://doi.org/10.1021/acs.accounts.4c00353.

Conspectus: Modulating the photophysical properties of organic emitters through molecular design is a fundamental endeavor in materials science. A critical aspect of this process is the control of the excited-state energy, which is essential for the development of triplet exciton-harvesting organic emitters, such as those with thermally activated delayed fluorescence and room-temperature phosphorescence. These emitters are pivotal for developing highly efficient organic light-emitting diodes and bioimaging probes. A particularly promising class of these emitters consists of twisted donor-acceptor organic π-conjugated scaffolds. These structures facilitate a spatial separation of the frontier molecular orbitals, which is crucial for achieving a narrow singlet-triplet energy gap. This narrow gap is necessary to overcome the endothermic reverse intersystem crossing process, enhancing the efficiency of thermally activated delayed fluorescence. To precisely modulate the photophysical properties of these emitting materials, it is essential to understand the electronic structures of new donor-acceptor scaffolds, especially those influenced by heteroatoms, as well as their conformations and topologies. This understanding not only improves the efficiency of these emitters but also expands their potential applications in advance technologies. In 2014, the Takeda group made a significant breakthrough by discovering a novel method for synthesizing U-shaped diazaacenes (dibenzo[a,j]phenazine) through an oxidative skeletal rearrangement of 1,1′-binaphthalene-2,2′-diamines. This class of compounds is typically challenging to synthesize using conventional organic reactions. The resulting unique geometric and electronic structure of U-shaped diazaacenes opened new possibilities for photophysical applications. Leveraging the U-shaped structure, photoluminescent properties, and high electron affinity, we developed twisted donor-acceptor-donor compounds. These compounds exhibit efficient thermally activated delayed fluorescence, stimuli-responsive luminochromism, heavy atom-free room-temperature phosphorescence, and anion-responsive red shifts. These innovative emitters have demonstrated significant potential in various practical applications, including organic light-emitting diode devices and advanced sensing systems. In this Account, I summarize our achievements in modulating the photofunctions of dibenzo[a,j]phenazine-cored twisted donor-acceptor-donor compounds by controlling excited-state singlet-triplet energy gaps through conformational regulation. Our comprehensive studies revealed the significant impact of heteroatoms, molecular conformations, and topologies on the photophysics of these compounds. These findings highlight the importance of molecular engineering in tailoring the photophysical properties of organic donor-acceptor π-conjugated materials for specific applications. Our research has demonstrated that incorporating heteroatoms into the molecular framework effectively tunes the electronic properties and, consequently, the photophysical behavior of the compounds. Understanding the influence of heteroatoms, conformational dynamics, and molecular topology on excited-state behavior will open new avenues for next-generation optoelectronic devices and biological technologies. These advancements include ultra-low-power displays, photonic communication, and super-resolution biomedical imaging. Ultimately, our work highlights the potential of strategic molecular design in driving innovation across various fields, paving the way for the development of cutting-edge technologies that leverage the unique properties of organic emitters.

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97847

Modulating the Photophysical Properties of Twisted Donor-Acceptor-Donor π-Conjugated Molecules: Effect of Heteroatoms, Molecular Conformation, and Molecular Topology

Takeda, Youhei

American Chemical Society

English

2024-07-24

Accounts of Chemical Research

57

15

2219

2232

https://doi.org/10.1021/acs.accounts.4c00353

https://hdl.handle.net/11094/97847