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The photophysical properties of a series of recently synthesized single benzene fluorophores were investigated using ensemble density functional theory calculations. The energetic stability of the ground and excited state species were counterposed against the aromaticity index derived from local vibrational modes. It was found that the large Stokes shift of the fluorophores (up to ca. 5800 cm −1) originates from the effect of electron donating and electron withdrawing substituents rather than π‐delocalization and related (anti‐)aromaticity. On the basis of nonadiabatic molecular dynamics simulations, the absence of fluorescence from one of the regioisomers was explained by the occurrence of easily accessible S 1/S 0 conical intersections below the vertical excitation energy level. It is demonstrated in the manuscript that the analysis of local mode force constants and the related aromaticity index represent a useful tool for the characterization of π‐delocalization effects in π‐conjugated compounds. [ABSTRACT FROM AUTHOR]

The dynamics of excited‐state charge transfer (CT) in second near‐infrared (NIR‐II) fluorophore proceeds with conformational change that govern fluorescence. Unveiling the relationship between CT dynamics and conformational change in excited state is of great fundamental significance in optimizing NIR‐II fluorescence but remains less explored. This study unveils the pivotal role of large conformational change in promoting the evolution of emissive CT state into nonemissive CT state in NIR‐II fluorophore (CA‐BBT). Spectroscopic and computational results reveal that large conformational rotation/twisting leads to a pronounced increase in the CT character in excited state. This heightened CT character in CA‐BBT enables a rapid evolution of emissive CT state into a nonemissive CT state within 1.4 ps, as observed by ultrafast spectroscopy. Subsequently, this nonemissive state dominates nonradiative decay, resulting in very low NIR‐II fluorescence. Preventing such detrimental evolution by constraining the conformational dynamics of CA‐BBT results in a 10‐fold enhancement of NIR‐II fluorescence, enabling high‐resolution dynamic visualization of vasculature within osteosarcoma. This study offers a profound understanding of the relationship between CT dynamics and conformational changes in NIR‐II fluorescence, presenting innovative perspectives to develop bright NIR‐II fluorophores. [ABSTRACT FROM AUTHOR]

Donor–π–acceptor fluorophores that consist of an electron‐donating amino group and an electron‐accepting triarylborane moiety generally exhibit substantial solvatochromism in their fluorescence while retaining high fluorescence quantum yields even in polar media. Herein, we report a new family of this compound class, which bears ortho‐P(=X)R2‐substituted phenyl groups (X=O or S) as a photodissociative module. The P=X moiety that intramolecularly coordinates to the boron atom undergoes dissociation in the excited state, giving rise to dual emission from the corresponding tetra‐ and tricoordinate boron species. The susceptibility of the systems to photodissociation depends on the coordination ability of the P=O and P=S moieties, whereby the latter facilitates dissociation. The intensity ratios of the dual emission bands are sensitive to environmental parameters, including temperature, solution polarity, and the viscosity of the medium. Moreover, precise tuning of the P(=X)R2 group and the electron‐donating amino moiety led to single‐molecule white emission in solution. [ABSTRACT FROM AUTHOR]

Donor–π–acceptor fluorophores that consist of an electron‐donating amino group and an electron‐accepting triarylborane moiety generally exhibit substantial solvatochromism in their fluorescence while retaining high fluorescence quantum yields even in polar media. Herein, we report a new family of this compound class, which bears ortho‐P(=X)R2‐substituted phenyl groups (X=O or S) as a photodissociative module. The P=X moiety that intramolecularly coordinates to the boron atom undergoes dissociation in the excited state, giving rise to dual emission from the corresponding tetra‐ and tricoordinate boron species. The susceptibility of the systems to photodissociation depends on the coordination ability of the P=O and P=S moieties, whereby the latter facilitates dissociation. The intensity ratios of the dual emission bands are sensitive to environmental parameters, including temperature, solution polarity, and the viscosity of the medium. Moreover, precise tuning of the P(=X)R2 group and the electron‐donating amino moiety led to single‐molecule white emission in solution. [ABSTRACT FROM AUTHOR]

[Display omitted] • The excited state behavior of a group of newly developed fluoropurine analogues of aza-heterocycles, triazole pyrimidinyl fluorophores, has been comprehensively studied. • The reaction energy profiles indicate that ESIPT is difficult to happen. The large Stokes shift of the fluorophores, therefore, is reconsidered. • Based on the FMOs results, the large Stokes shift is attributed to an ICT process occurring in the excited state, the rationality of which is further confirmed by the fluorescence spectra results. Fluoropurine analogues are a kind of unnatural bases, which are widely used in chemistry, biological science, pharmacy and other fields. At the same time, fluoropurine analogues of aza-heterocycles play an important role in medicinals research and development. In this work, the excited state behavior of a group of newly developed fluoropurine analogues of aza-heterocycles, triazole pyrimidinyl fluorophores, was comprehensively studied. The reaction energy profiles indicate that excited state intramolecular proton transfer (ESIPT) is difficult to happen, which is further proved by fluorescent spectra results. This work proposed a new and reasonable fluorescence mechanism based on the original experiment, and found that the large Stokes shift of the triazole pyrimidine fluorophore is due to the intramolecular charge transfer (ICT) process of the excited state. Our new discovery is of great significance for the application of this group of fluorescent compounds in other fields and the regulation of fluorescence properties. [ABSTRACT FROM AUTHOR]

Keywords: Boron; Donor-Acceptor Systems; Excited State; Fluorescence; Stimulus-Responsiveness EN Boron Donor-Acceptor Systems Excited State Fluorescence Stimulus-Responsiveness 1 1 1 06/20/23 20230626 NES 230626 B Dual-emissive b triarylborane-based donor- -acceptor fluorophores sensitive to environmental parameters, including temperature, solvent polarity, and viscosity of the medium, are reported by Shigehiro Yamaguchi and co-workers in their Research Article (e202303725). Boron, Donor-Acceptor Systems, Excited State, Fluorescence, Stimulus-Responsiveness Back Cover: Photodissociative Modules that Control Dual-Emission Properties in Donor- -Acceptor Organoborane Fluorophores (Angew. [Extracted from the article]