Article
Chemistry, Multidisciplinary
Fabien Ceugniet, Quentin Huaulme, Alexandra Sutter, Denis Jacquemin, Nicolas Leclerc, Gilles Ulrich
Summary: This article reports the synthesis and properties of heterosubstituted alpha beta-fused BODIPY fluorophores. The compounds were synthesized from 2,3,5,6-tetrahalo-BODIPY through sequential and selective Stille cross-coupling reactions, allowing the introduction of different substituents at specific positions on the BODIPY ring. The fully fused compounds showed a bathochromically shifted emission and a hyperchromic shift of the absorption maxima, with relatively high fluorescence quantum yields. Computational studies were conducted to gain a comprehensive understanding of the photophysical behavior of these dyes.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Johann Bosson, Geraldine M. Labrador, Celine Besnard, Denis Jacquemin, Jerome Lacour
Summary: By oxidizing tertiary alkyl amines to enamines and further reacting them to form donor-pi-acceptor coupling products, this synthetic approach extends conjugation, resulting in chromophores that absorb intensely in far-red or NIR domains. These chromophores also fluoresce in the NIR region, showing intense ECD properties with a |Delta epsilon| value up to 60 M^-1 cm^-1 around 790 nm.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Applied
Mateusz Urban, Krzysztof Durka, Artur Kasprzak, Tomasz Klis (Klis), Andrew P. Monkman, Michal Piszcz, Krzysztof Wozniak (Wozniak)
Summary: Three pyrene-containing boronated dyes were studied to evaluate the effect of pyrene moiety localization on photophysical properties. The solvents were found to significantly influence the emission maximum and quantum yield. One compound exhibited dual fluorescence, while the other two showed higher quantum yield in the solid state possibly due to aggregation-induced emission.
Article
Chemistry, Inorganic & Nuclear
Diana Mathew, Pattiyil Parameswaran
Summary: In this study, meso-aryl BODIPYs were designed as a structural motif for the transformation from aggregation-caused quenching (ACQ) to aggregation-induced emission (AIE). A series of meso-aryl BODIPY derivatives were synthesized and their photophysical properties were analyzed. The emission properties were found to be correlated with the flexibility of the aromatic ring. Decorating BODIPYs with polycyclic aromatic systems inhibited pi-pi stacking and allowed for the conversion of planar aryl luminophores from ACQ to AIEgens. The meso-pyrene BODIPY derivative also exhibited excellent mechanofluorochromic behavior.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Nanoscience & Nanotechnology
Rodrigo Plaza-Pedroche, M. Paz Fernandez-Liencres, Sonia B. Jimenez-Pulido, Nuria A. Illan-Cabeza, Sylvain Achelle, Amparo Navarro, Julian Rodriguez-Lopez
Summary: The photophysical properties of a series of original compounds were investigated, and the emission control through proton transfer and protonation was demonstrated, showing potential applications in chemical sensing and anti-counterfeiting.
ACS APPLIED MATERIALS & INTERFACES
(2022)
Article
Chemistry, Applied
Seda Cinar, Pinar Seyitdanlioglu, Canan Unaleroglu
Summary: Novel porphyrin-BODIPY dyads linked by alkyl chains of different lengths were synthesized and their intramolecular energy transfer properties were investigated. The results showed that alkyl chain shortening led to an increase in energy transfer. Calculations and experiments were performed to evaluate the optical and electronic behaviors of the dyads.
Article
Chemistry, Physical
Changjiao Shang, Yunjian Cao, Chaofan Sun, Huifang Zhao
Summary: This study systematically investigates the excited-state intramolecular proton transfer (ESIPT) process in the dual hydrogen-bonded system L, revealing that the proton transfer occurs along weakened intramolecular hydrogen bonds (IHBs). The study confirms the existence of two primary configurations in the ground state and shows that both IHBs of L are weakened upon photoexcitation. The proton transfer behavior is analyzed in different solvents, and it is found that only one specific hydrogen bond allows the proton transfer, with an increasing energy barrier in more polar solvents. The study also highlights the importance of appropriate structural torsion in the weakened IHB-induced ESIPT mechanism.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Lu Xing, Zhenguo Dou, Xiumian Cao, Panpan Ren, Wei Zhang, Shenghan Wang, Chenglin Sun, Zhiwei Men
Summary: Carotenoids are natural pigments that play important roles in photosynthesis and optoelectronics. The complexity of their energy level structure and electronic states has made it difficult to understand their photophysics and photochemistry. This study used time-dependent DFT to investigate the energy levels and electronic excitation process of beta-carotene, providing insights into its electronic energy level structure and possible dark states.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Spectroscopy
I. K. Petrushenko, K. B. Petrushenko
Summary: Theoretical computations were performed on the absorption spectra of (8-R-TMB)(2) dimers with different substituents at the 8 position (meso) of monomer units. The results showed that the lower transitions of the dimers were linked to the conjugated orbitals of the monomers. The intensities of these transitions were strongly influenced by the nature of the substituents, and could be controlled through chemical modifications. These findings have implications for the design of dimers with sensor functions.
SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY
(2022)
Article
Chemistry, Physical
Rudraditya Sarkar, Martial Boggio-Pasqua, Pierre-Francois Loos, Denis Jacquemin
Summary: This study compares the performances of various wave function methods and time-dependent density-functional theory under different conditions, highlighting the significant impact of gauge choice on oscillator strengths for ADC(2) and CC2. Moreover, it suggests that the accuracy and consistency obtained with the second-order wave function approaches ADC(2) and CC2 do not clearly outperform those of TD-DFT.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2021)
Article
Biochemistry & Molecular Biology
Marcin Gronowski, Robert Kolos
Summary: This article focuses on predicting the electronic spectra of highly unsaturated chain molecules and evaluates the performance of different functionals and basis sets in reproducing the spectroscopic parameters. The results show that the selected functionals and basis sets can adequately reproduce the experimental data, and optical excitation leads to a transition in the electronic structure of the molecules.
Article
Chemistry, Multidisciplinary
Lorena Mendive-Tapia, David Mendive-Tapia, Can Zhao, Doireann Gordon, Sam Benson, Michael J. Bromley, Wei Wang, Jun Wu, Adelina Kopp, Lutz Ackermann, Marc Vendrell
Summary: Fungal infections caused by Candida species are prevalent in hospitalized patients, but current detection methods are time-consuming. In this study, we developed new Phe-BODIPY amino acids and used them to produce fluorescent antimicrobial peptides for rapid labeling of Candida cells in urine. We also designed a simple and sensitive fluorescence-based assay for detecting Candida albicans in human urine samples.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Biochemistry & Molecular Biology
Evgenii Titov
Summary: The study examines the interactions and electron transition mechanisms of molecules containing azobenzene units in assemblies, finding significant charge transfer contributions under certain conditions. Different methods of partitioning transition density matrix between fragments were evaluated.
Article
Optics
Leandro D. Mena, Maria T. Baumgartner
Summary: The interest in organic molecules exhibiting Excited State Intramolecular Proton Transfer (ESIPT) has been increasing due to their unique properties for various applications. However, designing efficient ESIPT fluorophores can be challenging. In this study, we analyze the case of hydroxyphenyl-imidazo-isoindoles that were proposed to undergo ESIPT through a four-membered hydrogen-bonding cycle. We demonstrate that this process is unlikely to occur in the excited state and provide a simpler explanation for the experimental observations.
JOURNAL OF LUMINESCENCE
(2023)
Article
Chemistry, Physical
Wissam Helal, Ali Marashdeh, Qabas Alkhatib, Hana Qashmar, Mohammed Gharaibeh, Akef T. Afaneh
Summary: A series of BODIPY dyes for DSSC applications were designed to achieve a controlled red-shift in their absorption band maxima by changing the number and position of substituted methyl groups. The excited-state properties of these dyes were predicted and analyzed, showing a gradual red-shift in the lowest electronic excitation energy as the methyl groups were replaced by hydrogens. This substitution also led to increased charge transfer character, enhanced excited-state lifetimes and electron transport abilities, while slightly reducing the light harvesting efficiency and electron injection free energy.
INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Thibaut Baron, Valentin Maffeis, Christophe Bucher, Boris Le Guennic, Akos Banyasz, Denis Jacquemin, Gerard Berginc, Olivier Maury, Chantal Andraud
Summary: This study presents the synthesis, spectroscopic, and electrochemical properties of new bis- and tetra-substituted azaboron-dipyrromethene (aza-BODIPY) dyes with electron donating groups connected to the aza-BODIPY core through a thiophene unit. Experimental measurements and theoretical calculations show that the thiophene group functions as a secondary donor group, enhancing the intramolecular charge transfer process compared to previously reported aza-BODIPY dyes. Additionally, this heterocycle can tune the oxidative potential and stabilize the electro-generated species.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Fabrice Pointillart, Jessica Flores Gonzalez, Haiet Douib, Vincent Montigaud, Charles J. McMonagle, Boris Le Guennic, Olivier Cador, Dawid Pinkowicz, Michael R. Probert
Summary: The extreme sensitivity of trivalent lanthanide ions to crystal field variations leads to the emergence of single-molecule magnetic switching under various stimuli. Pressure can be used as an external stimulus to finely tune the magnetic modulation of single-molecule magnets, instead of traditional methods like light irradiation or chemical reactions. Experimental investigation of a well-known single-molecule magnet under high applied pressures demonstrated reversible piezo-chromic properties and pressure modulation of slow magnetic relaxation behavior, which were supported by ab initio calculations. The magnetic study of a diluted sample indicated that variations in the electronic structure mainly have an intermolecular origin with weak intramolecular contribution.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Applied
Marta Glodek, Elizaveta F. Petrusevich, Damian Plazuk, Denis Jacquemin, Borys Osmialowski
Summary: A series of difluoroborate fluorescent dyes with intramolecular charge transfer were synthesized and their properties were studied using both experimental and computational approaches. The size of the polyaromatic hydrocarbon side chains affects the photophysical properties of the dyes, especially their fluorescence quantum yield. Interestingly, corannulene, which is typically considered to lower the emission brightness, exhibited the highest fluorescence quantum yield in the series. Additionally, weak H/F or H/H intramolecular repulsions impacted the properties of BF2-carrying fluorophores.
Article
Electrochemistry
Jean-Francois Longevial, Iryna Knysh, Shaymaa Al Shehimy, Lhoussain Khrouz, Aramugam Pandurangan, Simon Pascal, Gabriel Canard, Christophe Bucher, Denis Jacquemin, Olivier Siri
Summary: Researchers have synthesized and characterized the soluble 6,13-dipivaloyl-5,14-dihydro-5,7,12,14-tetraazapentacene and its aromatic counterpart. Using complementary chemical, (spectro)-electrochemical, theoretical, and spectroscopic techniques, all the intermediates generated during the electrochemical processes of these compounds were fully characterized. The results demonstrate the ambipolar redox behavior of 6,13-dipivaloyl-5,14-dihydro-5,7,12,14-tetraazapentacene, leading to drastic color changes through proton-coupled electron transfer in a totally reversible fashion.
ELECTROCHIMICA ACTA
(2023)
Article
Chemistry, Physical
Samir Meskaldji, Lotfi Belkhiri, Remi Maurice, Karine Costuas, Boris Le Guennic, Abdou Boucekkine, Michel Ephritikhine
Summary: The magnetic properties of trinuclear Schiff base complexes M2AnLi have been theoretically investigated. The presence of covalent bonding within the Cu-O-U coordination favors superexchange coupling between the transition metal and the uranium magnetic centers, explaining the observed magnetic transition. The study of mixed ZnCuULi and Cu2ThLi complexes supports the aforementioned conclusions.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Multidisciplinary
Moritz Bernhardt, Maciej D. D. Korzynski, Zachariah J. J. Berkson, Fabrice Pointillart, Boris Le Guennic, Olivier Cador, Christophe Coperet
Summary: Generating or retaining slow magnetic relaxation in surface-immobilized single-molecule magnets (SMMs) from molecular precursors is a challenging task. However, a material with SMM characteristics has been successfully generated by chemisorption of (Cp-ttt)(2)DyCl on a silica surface containing tailored Lewis acidic Al-(III) sites. Detailed studies reveal slow magnetic relaxation up to 51 K, hysteresis up to 8 K, and an effective energy barrier (U (eff)) of 449 cm(-1), the highest reported for a supported SMM.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Moritz Bernhardt, Lukas Latsch, Boris Le Guennic, Christophe Coperet
Summary: This work models surface sites with ten neutral complexes and investigates their potential as single-molecule magnets. The results show that the spatial position of the anionic ligands significantly influences the magnetic properties, while the neutral ligands have a minor role.
HELVETICA CHIMICA ACTA
(2023)
Article
Chemistry, Physical
J. Villalobos-Castro, Iryna Knysh, Denis Jacquemin, Ivan Duchemin, Xavier Blase
Summary: We propose a method for calculating excited-state analytic gradients in the Bethe-Salpeter equation formalism. The method uses an adapted Lagrangian Z-vector approach to achieve a cost independent of the number of perturbations. We evaluate the accuracy of common approximations in the Bethe-Salpeter community and compare the results with time-dependent density-functional theory (TD-DFT) data.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Manon H. E. Bousquet, Thomas V. V. Papineau, Koen Veys, Daniel Escudero, Denis Jacquemin
Summary: Defining a theoretical model for accurately predicting the fluorescence quantum yields of organic dyes is important in designing improved fluorophores systematically. This study analyzed the impact of different computational parameters on the determination of reliable radiative rates (k (r)) using time-dependent density functional theory calculations. The results showed that the chosen vibronic model, especially the potential energy surface model, had a significant impact on the computed k (r) and the difference observed between different exchange-correlation functionals. However, all evaluated functionals yielded reasonable trends for the treated compounds, fitting the experimental values.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Physical
Liwei Guo, Zilong Li, Marie Cordier, Remi Marchal, Boris Le Guennic, Cedric Fischmeister
Summary: Research has found that new ruthenium and iridium complexes can efficiently dehydrogenate formic acid without any additives, providing a new approach to reducing the cost of energy transition.
Article
Chemistry, Physical
Thibaut Baron, Waad Naim, Mate Kurucz, Ilias Nikolinakos, Baptiste Andrin, Yann Pellegrin, Denis Jacquemin, Stefan Haacke, Frederic Sauvage, Fabrice Odobel
Summary: Fully transparent and colorless dye-sensitized solar cells have attracted much attention, and in this study, a new type of thienyl-PPcy dye was prepared by redshifting the absorption band of diketopyrrolopyrrole chromophores through molecular engineering. The new dyes showed a significant bathochromic shift compared to previous PPcys, leading to a better average visible transmittance of 67%. However, the lower performance of these dyes was attributed to stronger aggregation tendency, slower electron injection rate, and lower driving force, resulting in higher quenching degree by energy transfer towards aggregates.
JOURNAL OF MATERIALS CHEMISTRY A
(2023)
Article
Materials Science, Multidisciplinary
Fabien Ceugniet, Amina Labiod, Denis Jacquemin, Benoit Heinrich, Fanny Richard, Patrick Leveque, Gilles Ulrich, Nicolas Leclerc
Summary: Thanks to the rise of efficient push-pull non-fullerene acceptors (NFAs), the power conversion efficiency of bulk-heterojunction organic solar cells has reached over 18% for binary active layers. In this study, a new series of NFAs called BTTs were designed and synthesized, utilizing the uncommon BODIPY unit as the central electron accepting unit. These BTT molecules exhibited low optical bandgaps, high extinction coefficients, and suitable energy levels for efficient electron-donor molecules. Despite the unfavorable orientation, the most efficient derivative achieved a PCE of around 6%, one of the best results for a BODIPY-based NFA.
JOURNAL OF MATERIALS CHEMISTRY C
(2023)
Review
Chemistry, Physical
Martyna Durko-Maciag, Gilles Ulrich, Denis Jacquemin, Jaroslaw Mysliwiec, Julien Massue
Summary: This review provides an overview of recent advances in dual solution-solid emitters and lasing applications based on organic dyes with the excited-state intramolecular proton transfer (ESIPT) process, which will be of interest to material and physical chemists and researchers in ab initio calculations. ESIPT is highly sensitive to the environment, allowing for the engineering of stimuli-responsive fluorescent dyes. With the diverse structural capabilities of ESIPT fluorophores, there have been numerous applications in optoelectronics, biology, and luminescent displays. This review focuses on two emerging applications: emitters fluorescing in both solution and the solid state, and those capable of light amplification.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Isabella C. D. Merritt, Denis Jacquemin, Morgane Vacher
Summary: This study benchmarks the impact of different approximations to the nonadiabatic coupling term on the trajectory surface hopping (TSH) dynamics of isomerization and ring-opening reactions. It is found that the popular local diabatization scheme and a scheme based on biorthonormal wave function overlap in the OpenMOLCAS code can reproduce the dynamics obtained using explicitly calculated nonadiabatic coupling vectors at a reduced cost. However, the other two schemes tested can give different and even incorrect results.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Physical
Iryna Knysh, Kelvine Letellier, Ivan Duchemin, Xavier Blase, Denis Jacquemin
Summary: The study investigates the mixing between charge transfer (CT) and local excited (LE) characters upon twisting of N-phenylpyrrole (N-PP) geometry using theoretical calculations of six low-lying singlet excited states (ES). Results show that the Bethe-Salpeter equation (BSE) formalism is more reliable than Time-Dependent Density Functional Theory (TD-DFT) for close-lying ES with mixed CT/LE nature. BSE/GW provides a more accurate evolution of the excited state potential energy surfaces (PES) with negligible exchange-correlation functional starting point dependency.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
