RT Journal Article T1 Counterintuitive Fluorescence Blue Shift in Symmetry Breaking Dicationic Bis(indolium) with Two-Photon Absorption Properties for NIR Living Cell Imaging A1 Benítez-Martín, Carlos A1 Marín-Beloqui, José Manuel A1 López Navarrete, Juan T. A1 Casado-Cordón, Juan A1 Nájera-Albendín, Francisco A1 Perez-Inestrosa, Ezequiel K1 Fluorescencia K1 Mitocondrias K1 Fotones - Absorción AB Two-photon absorption (2PA) has become a cornerstone for bioimaging,enabling deeper tissue penetration while minimizing photodamage. Recently,the correlation between 2PA and excited-state symmetry breaking (ES-SB) hasbeen probed. Typically, the first hallmark of ES-SB is a red shift in fluorescencewith increasing solvent polarity. Herein, water-soluble bis(indolium)dyes, synthesized in only one step are reported, that exhibit remarkable2PA performance, coupled to the ES-SB process, displaying a counterintuitivefluorescence blue shift in polar solvents. The relationship betweentheir chemical structure and the extent of the ES-SB and 2PA properties isinvestigated via steady-state optical spectroscopies and transient absorptionspectroscopy (TAS). The unusual blue shift is ascribed to their dicationic nature,leading to an uneven stabilization of the ground and ES-SB excited statesin polar environments due to inefficient excited state solvation and positivecharge confinement. These compounds also offer specific mitochondrialstaining of living HeLa cells, performing at the level of more complexcommercial mitochondria markers. Herein, a novel family of dicationic dyesare introduced with robust 2PA properties and practical use in bioimagingand provide connections between their dication quadrupolar nature, whichimparts larger water solubility, 2PA performance, and ES-SB, which improvingfluorescence properties and bioimaging microscopy detection and resolution. PB Wiley YR 2025 FD 2025 LK https://hdl.handle.net/10630/40043 UL https://hdl.handle.net/10630/40043 LA eng NO C. Benitez-Martin, J. M. Marin-Beloqui, J. T. L. Navarrete, J. Casado, F. Najera, and E. Perez-Inestrosa, “ Counterintuitive Fluorescence Blue Shift in Symmetry Breaking Dicationic Bis(indolium) with Two-Photon Absorption Properties for NIR Living Cell Imaging.” Adv. Mater. (2025): e10730. https://doi.org/10.1002/adma.202510730 NO Universidad de Málaga NO Junta de Andalucía NO Ministerio de Universidades DS RIUMA. Repositorio Institucional de la Universidad de Málaga RD 25 ene 2026