Selective Modification for Red‐Shifted Excitability: A Small Change in Structure, a Huge Change in Photochemistry

Becker, Yvonne; Roth, Sina; Scheurer, Maximilian; Jakob, A.; Gacek, Daniel A.; Walla, Peter Jomo; Dreuw, Andreas; Wachtveitl, Josef; Heckel, Alexander

doi:10.1002/chem.202003672

Cited by 17 publications

(18 citation statements)

References 50 publications

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“…[8,9] Taking the coumarin photocage as an example, popular methods were the extension of the π-system, or the addition of donor and acceptor substituents (see Figure 1a). [10][11][12][13] Also with other photolabile protecting groups, for example BODIPY, [14,15] fluorenol, [16,17] or nitrobenzyl [18,19] a considerable red-shift was achieved with similar approaches. Nevertheless, the improvement of the second parameter, the uncaging efficiency, has not Structures and photophysical properties of DEACM 1 and ATTO 390.…”

Section: Introductionmentioning

confidence: 99%

Inactivation of Competitive Decay Channels Leads to Enhanced Coumarin Photochemistry

Klimek

Asido

Hermanns

et al. 2022

Chemistry A European J

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In the development of photolabile protecting groups, it is of high interest to selectively modify photochemical properties with structural changes as simple as possible. In this work, knowledge of fluorophore optimization was adopted and used to design new coumarin‐ based photocages. Photolysis efficiency was selectively modulated by inactivating competitive decay channels, such as twisted intramolecular charge transfer (TICT) or hydrogen‐bonding, and the photolytic release of the neurotransmitter serotonin was demonstrated. Structural modifications inspired by the fluorophore ATTO 390 led to a significant increase in the uncaging cross section that can be further improved by the simple addition of a double bond. Ultrafast transient absorption spectroscopy gave insights into the underlying solvent‐dependent photophysical dynamics. The chromophores presented here are excellently suited as new photocages in the visible wavelength range due to their simple synthesis and their superior photochemical properties.

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Section: Introductionmentioning

confidence: 99%

Inactivation of Competitive Decay Channels Leads to Enhanced Coumarin Photochemistry

Klimek

Asido

Hermanns

et al. 2022

Chemistry A European J

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“…The product was purified by silica gel column chromatography (hexane/EtOAc = 95:5) to give desired compound 2 (51.1 mg, 80%) as a red solid. (5). In a round-bottom flask, compound 7 50 (114.4 mg, 0.17 mmol), compound 8c (125.9 mg, 0.21 mmol), Pd(PPh 3 ) 4 (22.1 mg, 0.019 mmol), and K 3 PO 4 (120.2 mg, 0.57 mmol) were mixed in 1,4-dioxane/H 2 O (2:1, 1.5 mL).…”

Section: ■ Conclusionmentioning

confidence: 99%

Tris(4′-Nitrobiphenyl)amine─An Octupolar Chromophore with High Two-Photon Absorption Cross-Section and Its Application for Uncaging of Calcium Ions in the Near-Infrared Region

Nguyen

Lin

et al. 2022

J. Org. Chem.

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Compounds with high two-photon absorption (2PA) performance in the near-infrared region have attracted great attention because of their application in the material and biological science. In this study, we have developed a simple and novel octupolar chromophore, tris(4′-nitrobiphenyl)amine 1, with three nitro peripheral groups attached to a triphenylamine core via biphenyl linkers. A mono-branched analogue 2 has also been prepared to investigate the effects of octupolar and dipolar systems on photophysical and 2PA behaviors. Compound 1, despite having a much simpler structure than the previous three-branched scaffolds, exhibits comparable σ 2 values, reaching 1330 GM at 730 nm and 900 GM at 820 nm in toluene. Combined with an outstanding σ 2 /MW ratio (2.2 GM g −1 mol) and a high fluorescence quantum yield (0.51), 1 displays potential as a promising twophoton (2P) probe for bioimaging. Subsequently, the ethylene glycol tetraacetic acid-substituted derivatives featuring octupolar (3 and 5) or dipolar (4 and 6) character have been synthesized and their one-photon (1P) and 2P photochemical reactions have been examined. Finally, 1P-and 2P-triggered uncaging of Ca 2+ from these calcium chelators has been confirmed.

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“…Deeper insight into these processes can be gained with computational methods, spectroscopically, with systematic synthetic work – or ideally with all of these approaches working together. The change of one parameter for example the solubility can have an impact on the excited state reactivity and therefore change the entire photochemistry [6–9] . Hence, the design of new photoactivatable compounds needs to be based on elementary, but relevant concepts, as for example nitro‐push–pull‐systems or Zimmerman's meta ‐effect (Figure 1a,b) [10–12] .…”

Section: Introductionmentioning

confidence: 99%

“…The change of one parameter for example the solubility can have an impact on the excited state reactivity and therefore change the entire photochemistry. [ 6 , 7 , 8 , 9 ] Hence, the design of new photoactivatable compounds needs to be based on elementary, but relevant concepts, as for example nitro‐push–pull‐systems or Zimmerman's meta ‐effect (Figure 1 a,b). [ 10 , 11 , 12 ] In the last decades, numerous new photocleavable protecting groups (PPGs, photocages) evolved from these existing concepts in photochemistry.…”

Section: Introductionmentioning

confidence: 99%

Rethinking Uncaging: A New Antiaromatic Photocage Driven by a Gain of Resonance Energy

Hermanns

Scheurer

Kersten

et al. 2021

Chemistry A European J

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Photoactivatable compounds for example photoswitches or photolabile protecting groups (PPGs, photocages) for spatiotemporal light control, play a crucial role in different areas of research. For each application, parameters such as the absorption spectrum, solubility in the respective media and/or photochemical quantum yields for several competing processes need to be optimized. The design of new photochemical tools therefore remains an important task. In this study, we exploited the concept of excited‐state‐aromaticity, first described by N. Colin Baird in 1971, to investigate a new class of photocages, based on cyclic, ground‐state‐antiaromatic systems. Several thio‐ and nitrogen‐functionalized compounds were synthesized, photochemically characterized and further optimized, supported by quantum chemical calculations. After choosing the optimal scaffold, which shows an excellent uncaging quantum yield of 28 %, we achieved a bathochromic shift of over 100 nm, resulting in a robust, well accessible, visible light absorbing, compact new photocage with a clean photoreaction and a high quantum product (ϵ⋅Φ) of 893 M−1 cm−1 at 405 nm.

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Selective Modification for Red‐Shifted Excitability: A Small Change in Structure, a Huge Change in Photochemistry

Cited by 17 publications

References 50 publications

Inactivation of Competitive Decay Channels Leads to Enhanced Coumarin Photochemistry

Inactivation of Competitive Decay Channels Leads to Enhanced Coumarin Photochemistry

Tris(4′-Nitrobiphenyl)amine─An Octupolar Chromophore with High Two-Photon Absorption Cross-Section and Its Application for Uncaging of Calcium Ions in the Near-Infrared Region

Rethinking Uncaging: A New Antiaromatic Photocage Driven by a Gain of Resonance Energy

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