[en] The absorption spectrum of a representative BisBODIPY molecule is investigated using high-level quantum chemical methodology; the results are compared with experimental data. The S1 and S2 excited states are examined in detail to illuminate and to understand the electronic coupling between them. With the help of model systems in which the distance between the BODIPY monomers is increased or in which the dihedral angle between the subunits is changed, the electronic coupling is quantified, and its influence on energetics and oscillator strengths is highlighted. For the explanation of the experimental spectrum, orbital interaction effects are found to be important. Because of the large experimental Stokes shift of BisBODIPY, the nature of the emissive state is investigated and found to remain C2 symmetric as the ground state, and no localization of the excitation on one BODIPY subunit occurs. The excitonic coupling is in BisBODIPY still larger than the geometry relaxation energy, which explains the absence of a pseudo-Jahn−Teller effect.
Disciplines :
Chemistry
Author, co-author :
Knippenberg, Stefan ; Université de Liège > Département de chimie (sciences) > Laboratoire de chimie physique théorique
Bohnwagner, M. V.; Ruprecht-Karls University Heidelberg, Germany > Interdisciplinary Center for Scientific Computing
Harbach, P. H. P.; Ruprecht-Karls University Heidelberg, Germany > Interdisciplinary Center for Scientific Computing
Dreuw, A.; Ruprecht-Karls University Heidelberg, Germany > Interdisciplinary Center for Scientific Computing
Language :
English
Title :
Strong Electronic Coupling Dominates the Absorption and Fluorescence Spectra of Covalently Bound BisBODIPYs
Publication date :
2015
Journal title :
Journal of Physical Chemistry. A
ISSN :
1089-5639
eISSN :
1520-5215
Publisher :
American Chemical Society, Washington, United States - District of Columbia
Ulrich, G.; Ziessel, R.; Harriman, A. The Chemistry of Fluorescent Bodipy Dyes: Versatility Unsurpassed Angew. Chem., Int. Ed. 2008, 47, 1184-1201
Treibs, A.; Kreuzer, F.-H. Difluorboryl-Komplexe von Di- und Tripyrrylmethenen Justus Liebigs Ann. Chem. 1968, 718, 208-223
Monsma, F. J.; Barton, A. C.; Kang, H. C.; Brassard, D. L.; Haughland, R. P.; Sibley, D. R. Characterization of Novel Fluorescent Ligands with High-Affinity for D1 and D2 Dopaminergic Receptors J. Neurochem. 1989, 52, 1641-1644
Boens, N.; Leen, V.; Dehaen, W. Fluorescent Indicators Based on BODIPY Chem. Soc. Rev. 2012, 41, 1130-1172
Kamkaew, A.; Lim, S. H.; Lee, H. B.; Kiew, L. V.; Chung, L. Y.; Burgess, K. BODIPY Dyes in Photodynamic Therapy Chem. Soc. Rev. 2013, 42, 77-88
Rohand, T.; Qin, W.; Boens, N.; Dehaen, W. Palladium-Catalyzed Coupling Reactions for the Functionalization of BODIPY Dyes with Fluorescence Spanning the Visible Spectrum Eur. J. Org. Chem. 2006, 4658-4663
Bröring, M.; Krüger, R.; Link, S.; Kleeberg, C.; Köhler, S.; Xie, X.; Ventura, B.; Flamigni, L. Bis(BF(2))-2,2'-bidipyrrins (BisBODIPYs): Highly Fluorescent BODIPY Dimers with Large Stokes Shifts Chem.-Eur. J. 2008, 14, 2976-2983
Ventura, B.; Marconi, G.; Bröring, M.; Krüger, R.; Flamigni, L. Bis(BF2)-2,2'-bidipyrrins, a Class of BODIPY Dyes with New Spectroscopic and Photophysical Properties New J. Chem. 2009, 33, 428-438
Bröring, M.; Yuan, Y.; Krüger, R.; Kleeberg, C.; Xie, X. Solution and Solid State Structure of a BisBODIPY Fluorophor Z. Anorg. Allg. Chem. 2010, 636, 518-523
Valeur, B. Molecular Fluorescence Principles and Applications; Wiley-VCH: Weinheim, Germany, 2001.
Harriman, A.; Mallon, L. J.; Elliot, K. J.; Haefele, A.; Ulrich, G.; Ziessel, R. Length Dependence for Intramolecular Energy Transfer in Three- and Four-Color Donor-Spacer-Acceptor Arrays J. Am. Chem. Soc. 2009, 131, 13375-13386
Jin, J. L.; Wu, S. X.; Geng, Y.; Yang, S. Y.; Yang, G. C.; Yang, G. C.; Wu, J.; Muhammad, S.; Liao, Y.; Su, Z. M. Theoretical Study on Photophysical Properties of Novel Bis(BF2)-2,2'-bidipyrrins Dyes: Effect of Variation in Monomer Structure Int. J. Quantum Chem. 2012, 112, 440-452
May, V.; Kühn, O. Charge and Energy Transfer Dynamics in Molecular Systems, 2nd ed.; Wiley: Weinheim, Germany, 2004.
Scholes, G. D. Long-Range Resonance Energy Transfer in Molecular Systems Annu. Rev. Phys. Chem. 2003, 54, 57-87
Stone, A. J. The theory of intermolecular forces; Clarendon Press: Oxford, U.K., 1996.
Bröring, M.; Brégier, F.; Krüger, R.; Kleeberg, C. Functional Porphyrinoids from a Biomimetically Decorated Bipyrrole Eur. J. Inorg. Chem. 2008, 5505-5512
Becke, A. D. A New Mixing of Hartree-Fock and Local Density-Functional Theories J. Chem. Phys. 1993, 98, 1372-1377
Lee, C.; Yang, W.; Parr, R. G. Development of the Colle-Salvetti Correlation-Energy Formula into a Functional of the Electron-Density Phys. Rev. B 1988, 37, 785-789
Hariharan, P. C.; Pople, J. A. The Influence of Polarization Functions on Molecular Orbital Hydrogenation Energies Theoret. Chim. Acta 1973, 28, 213-222
Huzinaga, S. Basis-Sets for Mulecular Calculations Comput. Phys. Rep. 1985, 2, 281-339
Grimme, S. Semiempirical GGA-Type Density Functional Constructed with a Long-Range Dispersion Correction J. Comput. Chem. 2006, 27, 1787-1799
Becke, A. D. Density-Functional Thermochemistry. 3. The Role of Exact Exchange J. Chem. Phys. 1993, 98, 5648-5652
Christiansen, O.; Koch, H.; Jørgensen, P. Response Functions in the CC3 Iterative Triple Excitation Model J. Chem. Phys. 1995, 103, 7429-7441
Haettig, C.; Weigend, F. CC2 Excitation Energy Calculations on Large Molecules Using the Resolution of the Identity Approximation J. Chem. Phys. 2000, 113, 5154-5161
Haettig, C.; Hald, K. Implementation of RI-CC2 Triplet Excitation Energies with an Application to Trans-Azobenzene Phys. Chem. Chem. Phys. 2002, 4, 2111-2118
Casida, M. E. In Recent Advances in Density Functional Methods, Part I; Chong, D. P., Ed.; World Scientific: Singapore, 1995; pp 155-192.
Dreuw, A.; Head-Gordon, M. Single-Reference Ab Initio Methods for the Calculation of Excited States of Large Molecules Chem. Rev. 2005, 105, 4009-4037
Hirata, S.; Head-Gordon, M. Time-Dependent Density Functional Theory within the Tamm-Dancoff Approximation Chem. Phys. Lett. 1999, 314, 291-299
Furche, F. On the Density Matrix Based Approach to Time-Dependent Density Functional Response Theory J. Chem. Phys. 2001, 114, 5982-5992
Trofimov, A. B.; Schirmer, J. An Efficient Polarization Propagator Approach to Valence Electron-Excitation Spectra J. Phys. B 1995, 28, 2299-2324
Wormit, M.; Rehn, D. R.; Harbach, P. H. P.; Wenzel, J.; Krauter, C. M.; Epifanovskyc, E.; Dreuw, A. Investigating Excited Electronic States Using the Algebraic Diagrammatic Construction (ADC) Approach of the Polarisation Propagator Mol. Phys. 2014, 112, 774-784
Chai, J.-D.; Head-Gordon, M. Systematic Optimization of Long-Range Corrected Hybrid Density Functionals J. Chem. Phys. 2008, 128, 084106
Vydrov, O. A.; Scuseria, G. E. Assessment of a Long-Range Corrected Hybrid Functional J. Chem. Phys. 2006, 125, 234109
Weigend, F.; Ahlrichs, R. Balanced Basis Sets of Split Valence, Triple Zeta Valence and Quadruple Zeta Valence Quality for H to Rn: Design and Assessment of Accuracy Phys. Chem. Chem. Phys. 2005, 7, 3297-3305
Ahlrichs, R. TURBOMOLE, version 5.10; University of Karlsruhe: Karlsruhe, Germany, 2008.
Shao, Y.; Molnar, L. F.; Jung, Y.; Kussmann, J.; Ochsenfeld, C.; Brown, S. T.; Gilbert, A. T. B.; Slipchenko, L. V.; Levchenko, S. V.; O'Neill, D. P. Advances in Methods and Algorithms in a Modern Quantum Chemistry Program Package Phys. Chem. Chem. Phys. 2006, 8, 3172-3191
Harbach, P. H. P.; Dreuw, A. In Modeling of Molecular Properties; Comba, P., Ed.; Wiley-VCH: Weinheim, Germany, 2011; p 29.
Starcke, J. H.; Wormit, M.; Schirmer, J.; Dreuw, A. How Much Double Excitation Character Do the Lowest Excited States of Linear Polyenes Have? Chem. Phys. 2006, 329, 39-49
Starcke, J. H.; Wormit, M.; Dreuw, A. Unrestricted Algebraic Diagrammatic Construction Scheme of Second Order for the Calculation of Excited States of Medium-Sized and Large Molecules J. Chem. Phys. 2009, 130, 024104
Knippenberg, S.; Starcke, J. H.; Wormit, M.; Dreuw, A. The Low-Lying Excited States of Neutral Polyacenes and Their Radical Cations: a Quantum Chemical Study Employing the Algebraic Diagrammatic Construction Scheme of Second Order Mol. Phys. 2010, 108, 2801-2813
Peach, M. J.; Benfield, P.; Helgaker, T.; Tozer, D. J. Excitation Energies in Density Functional Theory: An Evaluation and a Diagnostic Test J. Chem. Phys. 2008, 128, 044118
Hieringer, W.; Görling, A. Failure of Time-Dependent Density Functional Methods for Excitations in Spatially Separated Systems Chem. Phys. Lett. 2006, 419, 557-562
Dreuw, A.; Head-Gordon, M. Comment on: 'Failure of Time-Dependent Density Functional Methods for Excitations in Spatially Separated Systems' by Wolfgang Hieringer and Andreas Gorling Chem. Phys. Lett. 2006, 426, 231-233
Harbach, P. H. P.; Dreuw, A. A Fresh Look at Excitonically Coupled Chromophores from a Jahn-Teller Perspective Chem. Phys. 2010, 377, 78-85
Garcia-Fernandez, P.; Andjelkovi, L.; Zlatar, M.; Gruden-Pavlovi, M.; Dreuw, A. A Simple Monomer-Based Model-Hamiltonian Approach to Combine Excitonic Coupling and Jahn-Teller Theory J. Chem. Phys. 2013, 139, 174101