Article
Chemistry, Multidisciplinary
Jared Bryce Weaver, Jacek Kozuch, Jacob M. Kirsh, Steven G. Boxer
Summary: This study reports a new vibrational Stark effect that can be used to measure electric fields and reveal the electric field characteristics of nitriles through their frequency and integrated intensity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Physical
Yvonne Rippers, Barbara Procacci, Neil T. Hunt, Marius Horch
Summary: This study presents a computational approach for simulating and analyzing static 2D-IR spectra of [NiFe] hydrogenases and similar organometallic systems. By accurately reproducing experimental spectra, it reveals the crucial role of the [NiFe] core in shaping the enzymatic potential energy surface and provides molecular information not accessible by experiments.
Article
Chemistry, Physical
Jiale Zhao, Qing Shi, Dengmeng Song, Bo Li, Hong Ren, Di Zhang, Xuzhuo Sun, Jun Li, Ning Wang
Summary: The dithiolato [NiN2S2] complexes were used to synthesize bimetallic models of the active site of [NiFe]-Hydrogenases. Three [NiN2S2] complexes were reacted with [NiCl2(PNP)] to investigate the influences of [NiN2S2] ligands on the structure and property of model complexes. The study found that complex 1, as a model of [NiFe]-H(2)ases, could catalyze H-2 evolution with a high rate constant in the presence of acetic acid.
Article
Polymer Science
Mathew C. Celina, Erik Linde, Estevan Martinez
Summary: Carbonyl formation is a key indicator for oxidative processes and degradation of plastics, with infrared spectroscopy being a commonly used method for identification and quantification. However, there are significant error margins in carbonyl quantification, with various factors influencing the accuracy of measurements.
POLYMER DEGRADATION AND STABILITY
(2021)
Article
Chemistry, Physical
Apakorn Phasuk, Ricardo B. B. Metz
Summary: The interaction between aluminum cations and acetone in the gas phase was studied using photodissociation vibrational spectroscopy. The spectra of Al+(acetone)(N-2) and Al+(acetone)( n ) (n = 2-5) ions were measured and compared to DFT calculated vibrational spectra to determine the structures of the complexes. The experiments showed red shift of the C=O stretch and blue shift of the CCC stretch, which decreased as the size of the clusters increased. The calculations predicted that the most stable isomer for n ≥ 3 was pinacolate, where oxidation of Al+ enabled reductive C-C coupling between two acetone ligands. Experimentally, pinacolate formation was observed for n = 5, as evidenced by a new peak at 1185 cm(-1) characteristic of the pinacolate C-O stretch.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Inorganic & Nuclear
Martin Ertl, Uwe Monkowius, Kerstin T. Oppelt
Summary: This study investigates the reactivity of a series of Re tricarbonyl complexes with 8-(diphenylphosphanyl)quinoline or 8-(diphenylarsanyl)quinoline as bidendate ligands, comparing them with other complexes. Electrochemical and spectroelectrochemical methods were employed, along with time-resolved spectroscopy, to study the peculiar reactivity of these complexes, including reduction reactions and reactions involving protons.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Benedict J. Elvers, Vera Krewald, Carola Schulzke, Christian Fischer
Summary: The reduction of a molybdenum monodithiolene complex in the presence of dichloromethane leads to the transfer of CH2 to sulfur and respective sulfonium species. Detailed studies reveal that the unexpected formation and composition of the resultant complexes are electronic-energetic in nature.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Inorganic & Nuclear
Francesca Realini, Catherine Elleouet, Francois Y. Petillon, Philippe Schollhammer
Summary: Novel carbonyl dithiolato diiron complexes related to the active site of [FeFe]-hydrogenases have been synthesized and characterized. Their fluxionality in solution and bridge motion were studied using NMR experiments. Preliminary results on protonation and electrochemical properties were reported.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Biochemistry & Molecular Biology
Tomaz Trobec, Kristina Sepcic, Monika Cecilija Zuzek, Jerneja Kladnik, Nina Podjed, Catarina Cardoso Pascoa, Iztok Turel, Robert Frangez
Summary: The study demonstrates the significance of different structural elements of organoruthenium complexes for their inhibitory activities against ChEs and GSTs. Some compounds show potential as drugs for further testing.
Article
Chemistry, Multidisciplinary
Shuanglin He, Fang Huang, Qianqian Wu, Ping Zhang, Ying Xiong, Jie Yang, Rong Zhang, Fang Wang, Lin Chen, T. Leo Liu, Fei Li
Summary: A rare mononuclear manganese complex was reported as a mimic of [FeFe]-hydrogenase, successfully mimicking the functions of its active site by utilizing two consecutive MS-CPET processes to achieve low overpotential in electrochemical hydrogen production.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Biochemistry & Molecular Biology
Jinsong Xuan, Lingling He, Wen Wen, Yingang Feng
Summary: Biohydrogen production through microbes offers a renewable and abundant hydrogen supply by utilizing raw materials like sunlight, water, and organic waste, thus addressing the issues of energy supply and environmental protection simultaneously.
Article
Chemistry, Inorganic & Nuclear
Tatiana Guseva, Philipp Gerschel, Daniel Siegmund, Ulf-Peter Apfel
Summary: This work investigates ligand exchange reactions between a [FeFe] hydrogenase model and phosphines. By varying the properties of the phosphines, the reaction conditions, and the amount of phosphines, the formation of complexes with multiple phosphines or altered binding modes was studied. The ligand exchanges resulted in specific main products at room temperature, but reflux conditions induced decomposition and altered binding modes in some cases. Additionally, the electrochemical investigation of the novel phosphine substituted models revealed a shift in cathodic behavior compared to the starting material.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Biochemistry & Molecular Biology
Attila Kovacs, Werner Klotzbuecher
Summary: Recent studies using mass spectrometry and IR photodissociation have provided evidence for the existence of octa-coordinated ionic lanthanide-carbonyl complexes under extreme gaseous conditions. Previous literature on cryogenic studies of neutral Ln(CO)(x) species suggested a maximum coordination number of hexa-coordinated Ln(CO)(6) molecules. This study aims to clarify the controversy through matrix isolation spectroscopy and DFT calculations, confirming the preference for octa-coordinated Ln(CO)(8) complexes in cryogenic neat CO matrices.
Article
Chemistry, Multidisciplinary
Pooja Varak, Avisikta Sinha, Mangalampalli Ravikanth
Summary: Fluorene-based tripyrrane was used as a precursor to synthesize three nonaromatic meso-fused thia and selenabenzihomoporphyrin(2.1.1.1)s by condensing it with appropriate 2,5-bis(hydroxymethyl)aryl thiophene or selenophene under acid catalysis. The resulting macrocycles were characterized by various analytical techniques and their nonaromatic nature was confirmed. The macrocycles exhibited absorption bands in the visible and near-infrared regions, and electrochemical studies revealed well-defined oxidations and reductions.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Applied
Katarzyna Choroba, Sonia Kotowicz, Anna Maron, Anna Switlicka, Agata Szlapa-Kula, Mariola Siwy, Justyna Grzelak, Karolina Sulowska, Sebastian Mackowski, Ewa Schab-Balcerzak, Barbara Machura
Summary: In this work, a series of rhenium(I) complexes with different substituents were synthesized and their photophysical properties were studied, with the substitution resulting in a significant red-shift in absorption and emission, contributing to the stabilization of the ligand-centred LUMO orbital.
Article
Chemistry, Multidisciplinary
Robin Giereth, Alexander K. Mengele, Wolfgang Frey, Marvin Kloss, Andreas Steffen, Michael Karnahl, Stefanie Tschierlei
CHEMISTRY-A EUROPEAN JOURNAL
(2020)
Article
Chemistry, Multidisciplinary
Martin Rentschler, Sirma Iglesias, Marie-Ann Schmid, Cunming Liu, Stefanie Tschierlei, Wolfgang Frey, Xiaoyi Zhang, Michael Karnahl, Dooshaye Moonshiram
CHEMISTRY-A EUROPEAN JOURNAL
(2020)
Review
Chemistry, Inorganic & Nuclear
Martin Rentschler, Marie-Ann Schmid, Wolfgang Frey, Stefanie Tschierlei, Michael Karnahl
INORGANIC CHEMISTRY
(2020)
Article
Chemistry, Multidisciplinary
Yingya Yang, Jannik Brueckmann, Wolfgang Frey, Sven Rau, Michael Karnahl, Stefanie Tschierlei
CHEMISTRY-A EUROPEAN JOURNAL
(2020)
Article
Chemistry, Inorganic & Nuclear
Florian Doettinger, Yingya Yang, Marie-Ann Schmid, Wolfgang Frey, Michael Karnahl, Stefanie Tschierlei
Summary: This study extended the backbone of 2,9-dimethyl-1,10-phenanthroline to develop novel heteroleptic Cu(I) complexes with various substituents using specialized cross-coupling reactions. The substituents were found to influence the optical properties and electrochemical properties of the complexes, with alkynyl-based complexes showing red-shifted absorption maxima and increased absorptivity, and phenyl-based complexes affecting emission wavelength and quantum yield.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Robin Giereth, Martin Obermeier, Lukas Forschner, Michael Karnahl, Matthias Schwalbe, Stefanie Tschierlei
Summary: The study investigates the influence of additional photosensitizers on the catalytic performance of a dirhenium complex, highlighting that using [Ir(dFppy)(3)] results in faster CO2 to CO transformation compared to [Cu(xant)(bcp)]PF6. Emission quenching studies and IR spectroscopy provide insights into the electron transfer paths of the intermolecular systems.
Article
Chemistry, Multidisciplinary
Marie-Ann Schmid, Jannik Brueckmann, Julian Boesking, Djawed Nauroozi, Michael Karnahl, Sven Rau, Stefanie Tschierlei
Summary: A novel Ru-II photosensitizer, RuipPer, containing a merged perylene dye, shows two emissive excited states and a long-lived dark state. The introduction of the perylene unit results in strongly altered absorption and emission behavior compared to prototype complexes.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Inorganic & Nuclear
Miguel A. Argueello Cordero, Pit Jean Boden, Martin Rentschler, Patrick Di Martino-Fumo, Wolfgang Frey, Yingya Yang, Markus Gerhards, Michael Karnahl, Stefan Lochbrunner, Stefanie Tschierlei
Summary: Ru(II)- and Cu(I)-based photosensitizers utilizing the biipo ligand were thoroughly studied using various spectroscopic methods. Results showed differences in characteristics between the Ru(II) and Cu(I) complexes, despite both involving the same lowest electronically excited states. The emissive (MLCT)-M-3 state and the dark (LC)-L-3 state were found to be populated in both complexes, with a balance between the two states that can be tuned by altering the metal center or thermal energy.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Yingya Yang, Florian Doettinger, Christian Kleeberg, Wolfgang Frey, Michael Karnahl, Stefanie Tschierlei
Summary: This study evaluates and compares two different design approaches to improve copper based photosensitizers. The findings show that one copper complex exhibits enhanced visible light absorption and solvent-dependent excited state lifetimes, as well as exceptional photostability.
FRONTIERS IN CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Jia-Wei Wang, Fan Ma, Tao Jin, Piao He, Zhi-Mei Luo, Stephan Kupfer, Michael Karnahl, Fengyi Zhao, Zihao Xu, Tao Jin, Tianquan Lian, Yong-Liang Huang, Long Jiang, Li-Zhi Fu, Gangfeng Ouyang, Xiao-Yi Yi
Summary: Exploiting noble-metal-free systems for efficient photocatalytic CO2 reduction remains challenging due to the difficulties in developing earth-abundant photosensitizers. This study focuses on a series of homoleptic Al(III) photosensitizers with 2-pyridylpyrrolide ligands for CO2 photoreduction using inexpensive aluminum metal. By introducing methyl groups at the pyrrolide rings, the visible-light absorption, reducing power, and durability of the Al(III) photosensitizers are greatly improved. The optimized system achieves a high quantum efficiency and CO2-to-CO conversion selectivity, making it a promising component in noble-metal-free systems for solar fuel conversion.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Florian Doettinger, Martin Obermeier, Volkan Caliskanyuerek, Lars E. Burmeister, Christian Kleeberg, Michael Karnahl, Matthias Schwalbe, Stefanie Tschierlei
Summary: In this study, the structure-property relationship of heteroleptic Cu-I photosensitizers was investigated in detail. Two structurally closely related complexes were compared, and it was found that even small changes in the molecular structure can significantly affect their photophysical properties. The reasons for the superior photophysical properties of Cu2 were elucidated through a combination of various experimental and computational techniques. Furthermore, both complexes were tested for their activity in photocatalytic water splitting and CO2 reduction, and Cu2 outperformed Cu1, as well as the benchmark system and the noble-metal-based complex [Ir(dFppy)(3)].
Article
Chemistry, Inorganic & Nuclear
Florian Doettinger, Yingya Yang, Michael Karnahl, Stefanie Tschierlei
Summary: The merging of a pyrene moiety with a copper-(I) based photosensitizer has resulted in the development of superior bichromophoric systems. The precise position and type of substitution play a crucial role in determining the properties and photocatalytic activity. Through extensive studies, it has been shown that attaching pyrene via its 1-position and substituting the pyridine rings of phenanthroline in the 4,7-position with the 1-pyrenyl moiety have the strongest impact on the bichromophore, resulting in significant improvements in reduction potential, excited state lifetime, single oxygen quantum yield, and photocatalytic activity.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Ying Zhang, Linda Zedler, Michael Karnahl, Benjamin Dietzek
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2019)
Article
Chemistry, Physical
Robin Giereth, Immanuel Reim, Wolfgang Frey, Henrik Junge, Stefanie Tschierlei, Michael Karnahl
SUSTAINABLE ENERGY & FUELS
(2019)
Article
Chemistry, Inorganic & Nuclear
Marie-Ann Schmid, Martin Rentschler, Wolfgang Frey, Stefanie Tschierlei, Michael Karnahl
