Molecular Photochemistry and Photophysics group utilizes time-resolved laser spectroscopy from femtosecond to millisecond time scales on various molecular systems.
Overview
Core fields of research
Basic natural phenomena and mathematical thinking
Research areas
Nanoscience Center
Second quantum revolution
Chemical Nanoscience
Faculty
Faculty of Mathematics and Science
Department
Department of Chemistry
Research group description
Molecular Photochemistry and Photophysics Group is headed by Dr. Tatu Kumpulainen. We are a member of the LaserLab-NSC and the Department of Chemistry at the University of Jyväskylä.
Our research is focused on detailed investigations of excited-state proton-transfer (ESPT) reactions in different media. In particular, we are interested in the influence of the environment on acidity, proton transfer and proton diffusion in liquid solutions and heterogeneous media. Most of our research is carried out on “super” photoacids, compounds that are weak acids in their electronic ground-states but become extremely strong acids in their excited-state. In our work, we utilize several optical spectroscopic techniques and quantum chemical calculations to investigate both the ground and excited-state properties of photoacids and other solvatochromic dyes. Read more about our Research topics and check our latest Publications below for further details.
Solvation dynamics can have a direct influence on ultrafast photochemical reactions (e.g. proton transfer) and is therefore of key importance for our research. We utilize femtosecond broadband FLuorescence UP-conversion Spectroscopy (FLUPS) for detailed investigations on solvation dynamics in polar liquids and heterogeneous media. We are interested in how the chemical structure of solutes and dielectric properties of solvents influences the time scale of the solvent relaxation. In addition, we are developing novel methods for the analysis of the broadband fluorescence data.
Excited-state proton transfer (ESPT) in organic solvents forms the core of our research interests. We utilize a large range of optical spectroscopic methods for detailed investigations on the mechanism and dynamics of ESPT reactions. Our work relies on “super” photoacids, acids that have negative excited-state acidities and are able to deprotonate in several organic solvents. Our research questions are focused on the influence of solvation dynamics as well as macroscopic solvent parameters (e.g. dielectric constant, acidity, viscosity etc.) on the ground-state acidity and ESPT to solvent and organic bases.
Last research topic is focused on studying acidity, proton transfer and proton diffusion in biological media such as phospholipid liposomes and protein environment. The research on liposomes relies on specially designed photoacids that can the anchored on the membrane surface. Due to the thorough understanding of the influence of the environment on ESPT, the properties of the photoacids in these media are expected to provide direct information about the local biological environment. Therefore, the main research questions are related to the properties of the biological media rather than to the proton transfer itself.
Publications
Summer School Report: Jyväskylä Summer School Course on Ultrafast Spectroscopy K. M. Yallum* and T. Kumpulainen* Chimia 2023, 77, 797–798.
Atomistic View of the Energy Transfer in a Fluorophore-Functionalized Gold Nanocluster K. Pyo, M. F. Matus, E. Hulkko, P. Myllyperkiö, S. Malola, T. Kumpulainen*, H. Häkkinen* and M. Pettersson* J. Am. Chem. Soc. 2023, 145, 14697–14704.
Spectroscopic Investigation of Photophysics and Tautomerism of Amino- and Nitroporphycenes I. Mbakara, A. Gajewsks, A. Listkowski, M. Kijak, K Nawara, T. Kumpulainen, E. Vauthey and J. Waluk* Phys. Chem. Chem. Phys.2022, 24, 29655–29666.
Photoinduced Electron Transfer in a Porphyrin–Fullerene Dyad at a Liquid Interface J. Sissaoui, A. Efimov, T. Kumpulainen*, and E. Vauthey* J. Phys. Chem. B2022, 126, 4723–4730.
Conference Report: SCS Photochemistry Section Symposium, Online Conference, June 19, 2020 T. Kumpulainen* Chimia2020, 74 (7/8), 629–630. (pdf)
Broadband Fluorescence Reveals Mechanistic Differences in Excited-State Proton Transfer to Protic and Aprotic Solvents P. Verma, A. Rosspeintner, B. Dereka, E. Vauthey, and T. Kumpulainen* Chem. Sci.2020, 11, 7963–7971.
Propyl Acetate/Butyronitrile Mixture is Ideally Suited for Investigating the Effect of Dielectric Stabilization on (Photo)Chemical Reactions P. Verma, A. Rosspeintner, and T. Kumpulainen* RSC Adv.2020, 10, 23682-23689.
Press release In collaboration with Dr. Fabien Cougnon, we characterized the physico-chemical properties of a family of quinolinium-based molecular links and knots. Our results showed that the properties are progressively modified as the tightness of the knots increases.
Accelerating the Shuttling in Hydrogen-Bonded Rotaxanes: Active Role of the Axle and the End Station T. Kumpulainen,* M.R. Panman, B.H. Bakker, M. Hilbers, S. Woutersen,* and A.M. Brouwer* J. Am. Chem. Soc.2019, 141 (48), 19118–19129.
Press release We reported on the synthesis and mechanistic characterization of the world's fastest molecular shuttle. Furthermore, use of excited-state proton transfer from a photoacid as the driving mechanism of the molecular shuttle was demonstrated for the first time.
Tuning Symmetry Breaking Charge Separation in Perylene Bichromophores by Conformational Control A. Aster, G. Licari, F. Zinna, E. Brun, T. Kumpulainen, E. Tajkhorshid, J. Lacour, and E. Vauthey* Chem. Sci.2019, 10, 10629–10639.
Conference Report: SCS Photochemistry Section Meeting, Fribourg, June 14, 2019 T. Kumpulainen,* A. Fürstenberg* Chimia2019, 73 (10), 840.
Spectroscopic Study of a Cinchona Alkaloid-Catalyzed Henry Reaction T. Kumpulainen,* J. Qian, and A.M. Brouwer* ACS Omega2018, 3 (2), 1871–1880.
Influence of Solvent Relaxation on Ultrafast Excited-State Proton Transfer to Solvent T. Kumpulainen,* A. Rosspeintner, B. Dereka, and E. Vauthey* J. Phys. Chem. Lett. 2017, 8 (18), 4516–4521.
Ultrafast Elementary Photochemical Processes of Organic Molecules in Liquid Solution T. Kumpulainen, B. Lang, A. Rosspeintner, and E. Vauthey* Chem. Rev. 2017, 117 (16), 10826–10939.
Selective Co-Encapsulation Inside a M6L4 Cage S.H.A.M. Leenders, R. Becker, T. Kumpulainen, B. de Bruin, T. Sawada, T. Kato, M. Fujita, and J.N.H. Reek* Chem. – Eur. J. 2016, 22 (43), 15468-15474.
Complexes of a Naphthalimide Photoacid with Organic Bases, and Their Excited-State Dynamics in Polar Aprotic Organic Solvents T. Kumpulainen,* B.H. Bakker, and A.M. Brouwer* Phys. Chem. Chem. Phys. 2015, 17 (32), 20715-20724.
Synthesis and Spectroscopic Characterization of 1,8-Naphthalimide Derived “Super” Photoacids T. Kumpulainen, B.H. Bakker, M. Hilbers and A.M. Brouwer* J. Phys. Chem. B 2015, 119 (6), 2515-2524.
Effects of Carbon-Metal-Carbon Linkages on the Optical, Photophysical, and Electrochemical Properties of Phosphametallacycle-Linked Coplanar Porphyrin Dimers Y. Matano,* K. Matsumoto, H. Hayashi, Y. Nakao, T. Kumpulainen, V. Chukharev, N.,V. Tkachenko, H. Lemmetyinen,* S. Shimizu, N. Kobayashi,* D. Sakamaki, A. Ito, K. Tanaka, and H. Imahori J. Am. Chem. Soc.2012, 134 (3), 1825-1839.
Independence and Inverted Dependence on Temperature of Rates of Photoinduced Electron Transfer in Double-Linked Phthalocyanine-Fullerene Dyads H. Lemmetyinen,*T. Kumpulainen, M. Niemi, A. Efimov, J. Ranta, K. Stranius, and N.V. Tkachenko Photochem. Photobiol. Sci.2010, 9 (7), 949-959.
Close Proximity Dibenzo[a,c]phenazine-Fullerene Dyad: Synthesis and Photoinduced Singlet Energy Transfer R.K. Dubey,*T. Kumpulainen, A. Efimov, N.V. Tkachenko, and H. Lemmetyinen Eur. J. Org. Chem. 2010, 18, 3428-3436.
Synthesis and Characterization of Monoisomeric 1,8,15,22-Substituted (A3B and A2B2) Phthalocyanines and Phthalocyanine-Fullerene Dyads J. Ranta,*T. Kumpulainen, H. Lemmetyinen, and A. Efimov J. Org. Chem.2010, 75 (15), 5178-5194.
Interlayer Energy Transfer Between Perylene Diimide and Phthalocyanine Monolayers H. Lehtivuori,*T. Kumpulainen, A. Efimov, H. Lemmetyinen, F. Würthner, and N.V. Tkachenko J. Photochem. Photobiol. A2010, 221 (1), 26-31.
Electronic Energy Harvesting Multi BODIPY-Zinc Porphyrin Dyads Accommodating Fullerene as Photosynthetic Composite of Antenna-Reaction Center E. Maligaspe, T. Kumpulainen, N.K. Subbaiyan, M.E. Zandler, H. Lemmetyinen, N.V. Tkachenko,* and F. D′Souza* Phys. Chem. Chem. Phys.2010, 12 (27), 7434-7444.
Ultrafast Singlet-Singlet Energy Transfer in Self-Assembled via Metal-Ligand Axial Coordination of Free-Base Porphyrin-Zinc Phthalocyanine and Free-Base Porphyrin-Zinc Naphthalocyanine Dyads E. Maligaspe, T. Kumpulainen, H. Lemmetyinen, N.V. Tkachenko,* N.K. Subbaiyan, M.E. Zandler, and F. D′Souza* J. Phys. Chem. A2010, 114 (1), 268-277.
Photodynamics of Charge Separation and Recombination in Solid Alternating Films of Phthalocyanine or Phthalocyanine–Fullerene Dyad and Perylene Dicarboximide H. Lehtivuori,*T. Kumpulainen, M. Hietala, A. Efimov, H. Lemmetyinen, A. Kira, H. Imahori, and N.V. Tkachenko J. Phys. Chem. C2009, 113 (5), 1984-1992.
Photoinduced Electron Transfer in Langmuir-Blodgett Monolayers of Double-Linked Phthalocyanine-Fullerene Dyads H. Lehtivuori,*T. Kumpulainen, A. Efimov, H. Lemmetyinen, A. Kira, H. Imahori, and N.V. Tkachenko J. Phys. Chem. C2008, 112 (26), 9896-9902.
Theses:
Proton-Transfer Reactions in "Super" Photoacids and Supramolecular Aseemblies T. Kumpulainen, PhD thesis, University of Amsterdam, The Netherlands, 2015. (link to thesis)
Doctoral students and postdoctoral researchers
We currently don't have any vacant positions. However, there are several funding possibilities, such as Marie Skłodowska-Curie Fellowships, Academy Research Fellow and various foundations, to support postdoctoral researchers. If you are interested in applying, we are willing to help.
Students
We are always looking for motivated students interested in optical spectroscopy and encourage students to enquire about possible internships and B.Sc./M.Sc. projects in our group. The group offers various opportunities to work with state-of-the-art optical spectroscopy methods. If you are interested in joining our group, please contact Dr. Tatu Kumpulainen directly with a brief description of why you would like to work with us.
