Accessing a Diverse Set of Functional Red-Light Photoswitches by Selective Copper-Catalyzed Indigo N-Arylation
The ability to correlate the structure of a molecule to its properties is the key to a rational and accelerated design of new functional compounds and materials. Taking photoswitches as an example, the thermal stability of meta-stable state is a crucial property that dictates their application in molecular systems. Indigos have recently emerged as an attractive motif for designing photoswitchable molecules due to their red-light addressability, which can be advantageous in biomedical and material applications. The absence of comprehensive synthetic techniques and a thorough understanding of the impact of structural factors on the photochemical and thermal properties of this widely available dye hinders its broad application. Herein, we report an efficient copper-catalyzed indigo N-arylation that enables the installation of a wide variety of aryl moieties carrying useful functional groups. The exclusive selectivity for mono-arylation likely originates from a bimetallic cooperative mechanism through a binuclear copper-indigo intermediate. Functional N-aryl-N′-alkylindigos were prepared and shown to photoisomerize efficiently under red light. Moreover, this design allows for the modulation of thermal half-lives through N-aryl substituents, while the N′-alkyl groups enable the independent attach-ment of functional moieties without affecting the photochromic properties. Strong correlation between the structure of N-aryl moiety and the thermal stability of the photogenerated Z-isomers was achieved by multivariate linear regression models obtained through a straightforward data-science workflow. This work thus builds an avenue leading to versatile red-light photoswitches and a general method for structure-property correlation that is expected to be broadly applicable to the design of photoresponsive molecules..
| Medienart: |
|
|---|
Preprint| Erscheinungsjahr: |
2024 |
|---|---|
| Erschienen: |
2024 |
| Enthalten in: |
chemRxiv.org - (2024) vom: 13. März Zur Gesamtaufnahme - year:2024 |
|---|
| Sprache: |
Englisch |
|---|
| Beteiligte Personen: |
Jaiswal, Amit K. [VerfasserIn] |
|---|
| Links: |
Volltext [kostenfrei] |
|---|
| Themen: |
|---|
| doi: |
10.26434/chemrxiv-2024-62zmf |
|---|
| funding: |
|
|---|---|
| Förderinstitution / Projekttitel: |
|
| PPN (Katalog-ID): |
XCH042902762 |
|---|
| LEADER | 01000naa a22002652 4500 | ||
|---|---|---|---|
| 001 | XCH042902762 | ||
| 003 | DE-627 | ||
| 005 | 20240314144821.0 | ||
| 007 | cr uuu---uuuuu | ||
| 008 | 240314s2024 xx |||||o 00| ||eng c | ||
| 024 | 7 | |a 10.26434/chemrxiv-2024-62zmf |2 doi | |
| 035 | |a (DE-627)XCH042902762 | ||
| 035 | |a (chemrXiv)10.26434/chemrxiv-2024-62zmf | ||
| 040 | |a DE-627 |b ger |c DE-627 |e rakwb | ||
| 041 | |a eng | ||
| 100 | 1 | |a Jaiswal, Amit K. |e verfasserin |4 aut | |
| 245 | 1 | 0 | |a Accessing a Diverse Set of Functional Red-Light Photoswitches by Selective Copper-Catalyzed Indigo N-Arylation |
| 264 | 1 | |c 2024 | |
| 336 | |a Text |b txt |2 rdacontent | ||
| 337 | |a Computermedien |b c |2 rdamedia | ||
| 338 | |a Online-Ressource |b cr |2 rdacarrier | ||
| 520 | |a The ability to correlate the structure of a molecule to its properties is the key to a rational and accelerated design of new functional compounds and materials. Taking photoswitches as an example, the thermal stability of meta-stable state is a crucial property that dictates their application in molecular systems. Indigos have recently emerged as an attractive motif for designing photoswitchable molecules due to their red-light addressability, which can be advantageous in biomedical and material applications. The absence of comprehensive synthetic techniques and a thorough understanding of the impact of structural factors on the photochemical and thermal properties of this widely available dye hinders its broad application. Herein, we report an efficient copper-catalyzed indigo N-arylation that enables the installation of a wide variety of aryl moieties carrying useful functional groups. The exclusive selectivity for mono-arylation likely originates from a bimetallic cooperative mechanism through a binuclear copper-indigo intermediate. Functional N-aryl-N′-alkylindigos were prepared and shown to photoisomerize efficiently under red light. Moreover, this design allows for the modulation of thermal half-lives through N-aryl substituents, while the N′-alkyl groups enable the independent attach-ment of functional moieties without affecting the photochromic properties. Strong correlation between the structure of N-aryl moiety and the thermal stability of the photogenerated Z-isomers was achieved by multivariate linear regression models obtained through a straightforward data-science workflow. This work thus builds an avenue leading to versatile red-light photoswitches and a general method for structure-property correlation that is expected to be broadly applicable to the design of photoresponsive molecules. | ||
| 650 | 4 | |a Chemistry |7 (dpeaa)DE-84 | |
| 650 | 4 | |a 540 |7 (dpeaa)DE-84 | |
| 700 | 1 | |a Saha, Priya |4 aut | |
| 700 | 1 | |a Jiang, Julong |4 aut | |
| 700 | 1 | |a Suzuki, Kimichi |4 aut | |
| 700 | 1 | |a Jasny, Anna |4 aut | |
| 700 | 1 | |a Schmidt, Bernd M. |0 (orcid)0000-0003-3622-8106 |4 aut | |
| 700 | 1 | |a Maeda, Satoshi |4 aut | |
| 700 | 1 | |a Hecht, Stefan |4 aut | |
| 700 | 1 | |a Huang, Chung-Yang (Dennis) |0 (orcid)0000-0003-2618-9668 |4 aut | |
| 773 | 0 | 8 | |i Enthalten in |t chemRxiv.org |g (2024) vom: 13. März |
| 773 | 1 | 8 | |g year:2024 |g day:13 |g month:03 |
| 856 | 4 | 0 | |u http://dx.doi.org/10.26434/chemrxiv-2024-62zmf |z kostenfrei |3 Volltext |
| 912 | |a GBV_XCH | ||
| 951 | |a AR | ||
| 952 | |j 2024 |b 13 |c 03 | ||