Shahu Adelajda, Petropoulos Vasilis, Saridakis Emmanuel, Petrakis Vyron S, Ioannidis Nikolaos, Mitrikas George, Schiza Andriana, Chochos Christos L, Kasimati Eleni-Marina, Soultati Anastasia, Nika Maria Christina, Thomaidis Nikolaos S, Fakis Mihalis, Maiuri Margherita, Cerullo Giulio, Pistolis George
Department of Chemistry, National and Kapodistrian University of Athens, Athens 15771, Greece.
Institute of Nanoscience & Nanotechnology, NCSR "Demokritos", Athens 15310, Greece.
J Am Chem Soc. 2024 Jun 12;146(23):15659-15665. doi: 10.1021/jacs.4c02019. Epub 2024 May 31.
Molecular aggregation is a powerful tool for tuning advanced materials' photophysical and electronic properties. Here we present a novel potential for the aqueous-solvated aggregated state of boron dipyrromethene (BODIPY) to facilitate phototransformations otherwise achievable only under harsh chemical conditions. We show that the photoinduced symmetry-breaking charge separation state can itself initiate catalyst-free redox chemistry, leading to selective α-C(sp)-H bond activation/C-C coupling on the BODIPY backbone. The photoproduction progress was tracked by monitoring the evolution of the strong Stokes-shifted near-infrared emission, resulting from selective self-assembly of the terminal heterodimeric photoproduct into well-ordered J-aggregates, as revealed by X-ray structural analysis. These findings provide a facile and green route to further explore the promising frontier of packing-triggered selective photoconversions via supramolecular engineering.
分子聚集是调节先进材料光物理和电子性质的有力工具。在此，我们展示了硼二吡咯亚甲基（BODIPY）水合聚集态的一种新潜力，即促进光转化，而这种光转化在其他情况下只有在苛刻的化学条件下才能实现。我们表明，光诱导的对称破缺电荷分离态本身可以引发无催化剂的氧化还原化学，导致BODIPY主链上的选择性α-C(sp)-H键活化/C-C偶联。通过监测强斯托克斯位移近红外发射的演变来跟踪光生产过程，这种发射是由末端异二聚体光产物选择性自组装成有序的J-聚集体产生的，X射线结构分析揭示了这一点。这些发现为通过超分子工程进一步探索堆积触发的选择性光转化这一充满前景的前沿领域提供了一条简便且绿色的途径。
