Quest for novel fluorogenic xanthene dyes: Synthesis, spectral properties and stability of 3-imino-3H-xanthen-6-amine (pyronin) and its silicon analog

Romieu, Anthony; Dejouy, Garance; Valverde, Ibai E.

doi:10.1016/j.tetlet.2018.11.031

“…[6] It has been widely known that the intramolecular charge transfer (ICT) could be modulated via adjusting the "push-pull" effect in acompound consisting of an electron-donating group (EDG) and/or an electron-withdrawing group (EWG). [7] In such compounds, ICT is further enhanced upon photoexcitation. In particular, in al andmark study,G rabowski and co-workers proposed that quasi-rigid donor-acceptor (D-A) compounds could undergo approximately 908 8 intramolecular twisting in the excited state,greatly reinforcing charge transfer and resulting in ac harge-separated state (D + -A À ).…”

mentioning

confidence: 99%

A Photoexcitation‐Induced Twisted Intramolecular Charge Shuttle

Chi

¹

,

Qiao

²

,

Lee

³

et al. 2019

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Charge transfer and separation are important processes governing numerous chemicalreactions.Fundamental understanding of these processes and the underlying mechanisms is critical for photochemistry.H erein, we report the discovery of anew charge-transfer and separation process, namely the twisted intramolecular charge shuttle (TICS). In TICS systems,t he donor and acceptor moieties dynamically switch roles in the excited state because of an approximately 908 8 intramolecular rotation. TICS systems thus exhibit charge shuttling.T ICSs exist in several chemical families of fluorophores (sucha sc oumarin, BODIPY,a nd oxygen/carbon/ silicon-rhodamine), and could be utilized to construct functional fluorescent probes (i.e., viscosity-or biomoleculesensing probes). The discovery of the TICS process expands the current perspectives of charge-transfer processes and will inspire future applications.Photo-induced charge transfer and separation is af undamental process, [1] responsible for photosynthesis, [2] and has applications in solar cells, [3] photocatalysis, [4] and fluorescence probes. [5] Greater understanding of charge-transfer and separation processes is thus important to aid in improving photochemistry.H owever,o wing to fast photon-absorption rates and short excited state lifetime,u nderstanding charge transfer and separation at amolecular level remains asignificant challenge.This challenge could be overcome if the model systems under study emit fluorescence (or other forms of luminescence). [1b] Thec hanges in fluorescence output (for example, intensity,l ifetime,a nd wavelength) provide critical information on the thermodynamics and kinetics of the chargetransfer and separation processes in the excited state,a long with ap lethora of other important photo-physical and -chemical information. Accordingly,s tudies have been con-ducted to investigate charge-transfer and separation mechanisms in fluorescent compounds. [6] It has been widely known that the intramolecular charge transfer (ICT) could be modulated via adjusting the "push-pull" effect in acompound consisting of an electron-donating group (EDG) and/or an electron-withdrawing group (EWG). [7] In such compounds, ICT is further enhanced upon photoexcitation. In particular, in al andmark study,G rabowski and co-workers proposed that quasi-rigid donor-acceptor (D-A) compounds could undergo approximately 908 8 intramolecular twisting in the excited state,greatly reinforcing charge transfer and resulting in ac harge-separated state (D + -A À ). [8] They named this mechanism twisted intramolecular charge transfer (TICT; Figure 1a). Rationalization of the TICT mechanism [9] has greatly facilitated the development of many functional materials and devices,s uch as bright and photostable fluorophores, [10] dark quenchers, [11] viscosity sensors, [12] and polarity sensors. [6b] Notably,c harge-transfer and separation processes in both the ICT and TICT states are unidirectional, i.e., from the donor (D) to the acceptor (A) upon photoexcitation.In this study,w er...

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“…Another valuable feature of pyronin scaffold is the facile modulation of its absorption and fluorescence maxima through the formal replacement of intracyclic oxygen atom by a group 14 element (i.e., CMe2 [45][46][47], SiMe2 [26,44,48,49], or GeMe2 [25,50]). This heteroatomsubstitution approach is now viewed as the easiest way to obtain xanthene analogs with spectral features in the red and/or far-red regions while keeping a small compact size, hydrophilic character and less propensity for aggregation-caused quenching (ACQ) [51] in aq.…”

Section: Introductionmentioning

confidence: 99%

Synthetic routes to novel fluorogenic pyronins and silicon analogs with far-red spectral properties and enhanced aqueous stability

Dejouy

¹

,

Renault

²

,

Valverde

³

et al. 2020

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Fluorogenic detection of reactive (bio)analytes is often achieved with "smart" probes, whose activation mechanism causes the release of aniline-based fluorophores. Indeed, the protection-deprotection of their primary amino is the simplest way to induce dramatic and valuable changes in spectral features of the fluorogenic reporter. In this context, and due to their small size and intrinsic hydrophilicity, we focused on pyronin dyes and related heteroatom analogs (i.e., formal derivatives of 3-imino-3H-xanthen-6-amine and its silicon analog) for their use as optically tunable aniline-based fluorophores. To overcome some severe limitations associated with the use of such fluorogenic scaffolds (i.e., poor aqueous stability and spectral features only in the green-yellow spectral range), the synthesis of novel unsymmetrical derivatives of (Si)-pyronins bearing a single bulky tertiary aniline (i.e., N-methylindoline and julolidine) was explored and presented in this Article. This structural alteration has been found to be beneficial to dramatically lower electrophilicity of the meso-position and to reach attractive fluorescence properties within the far-red spectral region. File list (2) download file view on ChemRxiv Publication-GD4-ChemRxiv-Preprint-31032020.pdf (837.64 KiB) download file view on ChemRxiv Publication-GD04-ChemRxiv-SI-31032020.pdf (6.54 MiB)

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“…In TICS systems,t he donor and acceptor moieties dynamically switch roles in the excited state because of an approximately 908 8 intramolecular rotation. [7] In such compounds, ICT is further enhanced upon photoexcitation. The discovery of the TICS process expands the current perspectives of charge-transfer processes and will inspire future applications.…”

mentioning

confidence: 99%

“…[7] In such compounds, ICT is further enhanced upon photoexcitation. [1b] Thec hanges in fluorescence output (for example, intensity,l ifetime,a nd wavelength) provide critical information on the thermodynamics and kinetics of the chargetransfer and separation processes in the excited state,a long with ap lethora of other important photo-physical and -chemical information.…”

mentioning

confidence: 99%

“…[1b] Thec hanges in fluorescence output (for example, intensity,l ifetime,a nd wavelength) provide critical information on the thermodynamics and kinetics of the chargetransfer and separation processes in the excited state,a long with ap lethora of other important photo-physical and -chemical information. [7] In such compounds, ICT is further enhanced upon photoexcitation. [6] It has been widely known that the intramolecular charge transfer (ICT) could be modulated via adjusting the "push-pull" effect in acompound consisting of an electron-donating group (EDG) and/or an electron-withdrawing group (EWG).…”

mentioning

confidence: 99%

See 1 more Smart Citation

A Photoexcitation‐Induced Twisted Intramolecular Charge Shuttle

Chi

¹

,

Qiao

²

,

Lee

³

et al. 2019

View full text Add to dashboard Cite

Charge transfer and separation are important processes governing numerous chemicalreactions.Fundamental understanding of these processes and the underlying mechanisms is critical for photochemistry.H erein, we report the discovery of anew charge-transfer and separation process, namely the twisted intramolecular charge shuttle (TICS). In TICS systems,t he donor and acceptor moieties dynamically switch roles in the excited state because of an approximately 908 8 intramolecular rotation. TICS systems thus exhibit charge shuttling.T ICSs exist in several chemical families of fluorophores (sucha sc oumarin, BODIPY,a nd oxygen/carbon/ silicon-rhodamine), and could be utilized to construct functional fluorescent probes (i.e., viscosity-or biomoleculesensing probes). The discovery of the TICS process expands the current perspectives of charge-transfer processes and will inspire future applications.Photo-induced charge transfer and separation is af undamental process, [1] responsible for photosynthesis, [2] and has applications in solar cells, [3] photocatalysis, [4] and fluorescence probes. [5] Greater understanding of charge-transfer and separation processes is thus important to aid in improving photochemistry.H owever,o wing to fast photon-absorption rates and short excited state lifetime,u nderstanding charge transfer and separation at amolecular level remains asignificant challenge.This challenge could be overcome if the model systems under study emit fluorescence (or other forms of luminescence). [1b] Thec hanges in fluorescence output (for example, intensity,l ifetime,a nd wavelength) provide critical information on the thermodynamics and kinetics of the chargetransfer and separation processes in the excited state,a long with ap lethora of other important photo-physical and -chemical information. Accordingly,s tudies have been con-ducted to investigate charge-transfer and separation mechanisms in fluorescent compounds. [6] It has been widely known that the intramolecular charge transfer (ICT) could be modulated via adjusting the "push-pull" effect in acompound consisting of an electron-donating group (EDG) and/or an electron-withdrawing group (EWG). [7] In such compounds, ICT is further enhanced upon photoexcitation. In particular, in al andmark study,G rabowski and co-workers proposed that quasi-rigid donor-acceptor (D-A) compounds could undergo approximately 908 8 intramolecular twisting in the excited state,greatly reinforcing charge transfer and resulting in ac harge-separated state (D + -A À ). [8] They named this mechanism twisted intramolecular charge transfer (TICT; Figure 1a). Rationalization of the TICT mechanism [9] has greatly facilitated the development of many functional materials and devices,s uch as bright and photostable fluorophores, [10] dark quenchers, [11] viscosity sensors, [12] and polarity sensors. [6b] Notably,c harge-transfer and separation processes in both the ICT and TICT states are unidirectional, i.e., from the donor (D) to the acceptor (A) upon photoexcitation.In this study,w er...

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Quest for novel fluorogenic xanthene dyes: Synthesis, spectral properties and stability of 3-imino-3H-xanthen-6-amine (pyronin) and its silicon analog

Abstract: also been explored to rapidly access to near-infrared (NIR) fluorogenic dyes for more challenging biosensing/bioimaging applications, especially in vivo 14-17 (Fig. 1).

Cited by 11 publications

References 74 publications

A Photoexcitation‐Induced Twisted Intramolecular Charge Shuttle

A Photoexcitation‐Induced Twisted Intramolecular Charge Shuttle

Synthetic routes to novel fluorogenic pyronins and silicon analogs with far-red spectral properties and enhanced aqueous stability

A Photoexcitation‐Induced Twisted Intramolecular Charge Shuttle

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