Direct Observation of Different One- and Two-Photon Fluorescent States in a Pyrrolo[3,2-b]pyrrole Fluorophore.

Two-photon fluorophores are frequently employed to obtain superior spatial resolution in optical microscopy applications. To guide the rational design of these molecules, a detailed understanding of their excited-state deactivation pathways after two-photon excitation is beneficial, especially to assess the often-assumed presumption that the one- and two-photon excited-state dynamics are similar after excitation. Here, we showcase the breakdown of this assumption for one- and two-photon excitation of a centrosymmetric pyrrolo[3,2-b]pyrrole chromophore by combining time-resolved fluorescence and broadband femtosecond transient absorption spectroscopy. Compared to one-photon excitation, where radiative decay dominates the photodynamics, two-photon excitation leads to dynamics arising from increased non-radiative decay pathways. These different photodynamics are manifest to different quantum yields, thus highlighting the types of time-resolved studies described here to be valuable guideposts in the design of two-photon fluorophores for imaging applications.

[1]  C. Ruckebusch,et al.  Excited-State Symmetry Breaking in a Quadrupolar Molecule Visualized in Time and Space. , 2017, The journal of physical chemistry letters.

[2]  D. Gryko,et al.  The Tetraarylpyrrolo[3,2-b]pyrroles-From Serendipitous Discovery to Promising Heterocyclic Optoelectronic Materials. , 2017, Accounts of chemical research.

[3]  Eric Vauthey,et al.  Solute-Solvent Interactions and Excited-State Symmetry Breaking: Beyond the Dipole-Dipole and the Hydrogen-Bond Interactions. , 2017, The journal of physical chemistry letters.

[4]  Gabriel F. Dorlhiac,et al.  PyLDM - An open source package for lifetime density analysis of time-resolved spectroscopic data , 2017, PLoS Comput. Biol..

[5]  E. Vauthey,et al.  A simple model of solvent-induced symmetry-breaking charge transfer in excited quadrupolar molecules. , 2017, The Journal of chemical physics.

[6]  Christopher G. Elles,et al.  Two-photon absorption spectroscopy of trans-stilbene, cis-stilbene, and phenanthrene: Theory and experiment. , 2017, The Journal of chemical physics.

[7]  E. Vauthey,et al.  Symmetry-Breaking Charge Transfer and Hydrogen Bonding: Toward Asymmetrical Photochemistry. , 2016, Angewandte Chemie.

[8]  A. Rebane,et al.  Pyrrolo[3,2-b]pyrroles-From Unprecedented Solvatofluorochromism to Two-Photon Absorption. , 2015, Chemistry.

[9]  Bosung Kim,et al.  Near-IR Two-Photon Fluorescent Sensor for K(+) Imaging in Live Cells. , 2015, ACS applied materials & interfaces.

[10]  Dai Fukumura,et al.  Micelle-Encapsulated Quantum Dot-Porphyrin Assemblies as in Vivo Two-Photon Oxygen Sensors. , 2015, Journal of the American Chemical Society.

[11]  S. Kovalenko,et al.  Broadband transient absorption spectroscopy with 1- and 2-photon excitations: Relaxation paths and cross sections of a triphenylamine dye in solution. , 2015, The Journal of chemical physics.

[12]  D. Gryko,et al.  1,4-Dihydropyrrolo[3,2-b]pyrrole and its π-expanded analogues. , 2014, Chemistry, an Asian journal.

[13]  D. Gryko,et al.  Tetraaryl-, pentaaryl-, and hexaaryl-1,4-dihydropyrrolo[3,2-b]pyrroles: synthesis and optical properties. , 2014, The Journal of organic chemistry.

[14]  A. Stolow,et al.  Two-Photon Excited State Dynamics of Dark Valence, Rydberg, and Superexcited States in 1,3-Butadiene. , 2014, The journal of physical chemistry letters.

[15]  M. Bawendi,et al.  Two-photon oxygen sensing with quantum dot-porphyrin conjugates. , 2013, Inorganic chemistry.

[16]  T. Stokłosa,et al.  Synthesis and Optical Properties of Tetraaryl‐1,4‐dihydropyrrolo[3,2‐b]pyrroles , 2013 .

[17]  Chih-Wei Chang,et al.  Validation of response function construction and probing heterogeneous protein hydration by intrinsic tryptophan. , 2012, The journal of physical chemistry. B.

[18]  M. Chergui,et al.  A femtosecond fluorescence study of vibrational relaxation and cooling dynamics of UV dyes. , 2012, Physical chemistry chemical physics : PCCP.

[19]  Pavel Ginzburg,et al.  Applications of two-photon processes in semiconductor photonic devices: invited review , 2011 .

[20]  Aleksander Rebane,et al.  Simultaneous multiple-excitation multiphoton microscopy yields increased imaging sensitivity and specificity , 2011, BMC biotechnology.

[21]  B. Bagchi,et al.  Solvation dynamics in dipolar liquids. , 2010, Chemical Society reviews.

[22]  B. Cho,et al.  Two-photon absorption properties of hexa-substituted benzene derivatives. Comparison between dipolar and octupolar molecules. , 2009, Chemical communications.

[23]  Hazel A. Collins,et al.  Two-photon absorption and the design of two-photon dyes. , 2009, Angewandte Chemie.

[24]  Michael J. Therien,et al.  Physical chemistry: How to improve your image , 2009, Nature.

[25]  Aleksander Rebane,et al.  Blood-vessel closure using photosensitizers engineered for two-photon excitation , 2008 .

[26]  Stanley B. Brown,et al.  Photodynamic Therapy: Two photons are better than one , 2008 .

[27]  Edwin P. Walker,et al.  Two-photon technology: A new dimension , 2008 .

[28]  P. Prasad,et al.  Multiphoton absorbing materials: molecular designs, characterizations, and applications. , 2008, Chemical reviews.

[29]  Claudine Katan,et al.  Charge instability in quadrupolar chromophores: symmetry breaking and solvatochromism. , 2006, Journal of the American Chemical Society.

[30]  W. Denk,et al.  Deep tissue two-photon microscopy , 2005, Nature Methods.

[31]  Richard K P Benninger,et al.  Two‐Photon Excitation Microscopy for the Study of Living Cells and Tissues , 2003, Current protocols in cell biology.

[32]  Michael D. Cahalan,et al.  Two-photon tissue imaging: seeing the immune system in a fresh light , 2002, Nature Reviews Immunology.

[33]  W. Rettig,et al.  Photoinduced Intramolecular Charge Transfer in a Series of Differently Twisted Donor−Acceptor Biphenyls As Revealed by Fluorescence , 1999 .

[34]  Seth R. Marder,et al.  Two-photon polymerization initiators for three-dimensional optical data storage and microfabrication , 1999, Nature.

[35]  M. Maroncelli,et al.  Dipole Solvation in Nondipolar Solvents: Experimental Studies of Reorganization Energies and Solvation Dynamics† , 1996 .

[36]  W. Denk,et al.  Two-photon laser scanning fluorescence microscopy. , 1990, Science.

[37]  M. Maroncelli,et al.  Picosecond solvation dynamics of coumarin 153: The importance of molecular aspects of solvation , 1987 .

[38]  D. Gryko,et al.  Diindolo[2,3-b:2',3'-f]pyrrolo[3,2-b]pyrroles as electron-rich, ladder-type fluorophores: synthesis and optical properties. , 2015, Chemistry, an Asian journal.

[39]  J. Bhawalkar,et al.  Two-photon photodynamic therapy. , 1997, Journal of clinical laser medicine & surgery.