Intramolecular through-space conjugation of chiral C2-spirooxindole

IF 4.1 3区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Photochemistry and Photobiology A-chemistry Pub Date : 2025-01-29 DOI:10.1016/j.jphotochem.2025.116316

Kosuke Nakashima , Aoi Imamura , Yasuyuki Matsushima , Shin-ichi Hirashima , Dancho Yordanov , Tsuyoshi Miura , Anton Georgiev

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Abstract

Chiral and non-conjugated C2-spirooxindole substituted at the C3 position by a phenyl ring has been studied for its unusual photoluminescence behaviour. The spectral results showed positive solvatochromism in absorption and visible emission with large Stokes shifts up to 5000 cm⁻¹ and good quantum yield. The C3-phenyl ring was found to play a central role in the unusual visible emission, allowing rotation through a single bond. Ground-state and excited-state DFT calculations revealed that the twisted phenyl plays a crucial role in the orbital interaction through space. Experiments with binary mixtures of MeCN/H₂O (v/v %), which are usually associated with aggregate formation and restriction of molecular rotation, clearly showed a gradual decrease in emission with increasing water fraction. Therefore, the excited state rotation of the phenyl ring is the key factor for the observed visible emission, and the quenched emission in the binary mixture of MeCN/H₂O is a result of the restricted rotation, which is incapable of effective through-space conjugation.

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来源期刊

Journal of Photochemistry and Photobiology A-chemistry 化学-物理化学

CiteScore

7.90

自引率

7.00%

发文量

580

审稿时长

48 days

期刊介绍： JPPA publishes the results of fundamental studies on all aspects of chemical phenomena induced by interactions between light and molecules/matter of all kinds. All systems capable of being described at the molecular or integrated multimolecular level are appropriate for the journal. This includes all molecular chemical species as well as biomolecular, supramolecular, polymer and other macromolecular systems, as well as solid state photochemistry. In addition, the journal publishes studies of semiconductor and other photoactive organic and inorganic materials, photocatalysis (organic, inorganic, supramolecular and superconductor). The scope includes condensed and gas phase photochemistry, as well as synchrotron radiation chemistry. A broad range of processes and techniques in photochemistry are covered such as light induced energy, electron and proton transfer; nonlinear photochemical behavior; mechanistic investigation of photochemical reactions and identification of the products of photochemical reactions; quantum yield determinations and measurements of rate constants for primary and secondary photochemical processes; steady-state and time-resolved emission, ultrafast spectroscopic methods, single molecule spectroscopy, time resolved X-ray diffraction, luminescence microscopy, and scattering spectroscopy applied to photochemistry. Papers in emerging and applied areas such as luminescent sensors, electroluminescence, solar energy conversion, atmospheric photochemistry, environmental remediation, and related photocatalytic chemistry are also welcome.