Article
Chemistry, Inorganic & Nuclear
Analia Mercedes Peyrot, Maria Priscila Zelaya, Pablo Albores, Florencia Fagalde
Summary: In this work, a series of new mononuclear Ru (II) complexes with chloro and aqua ligands were synthesized and characterized. The structure of [Ru(tptz)(dpp)Cl]PF6 was determined by X-ray diffraction. The aqua complexes showed catalytic activity for water oxidation at pH 1 using cerium ammonium nitrate as an oxidant. The experimental results were in good agreement with theoretical calculations.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Niklas Noll, Frank Wuerthner
Summary: The cyclic dinuclear ruthenium complex with oligo(ethylene glycol)-functionalized axial calix[4]arene ligands showed enhanced catalytic activity in water oxidation compared to the mononuclear reference compound. The kinetic studies revealed a unimolecular water nucleophilic attack mechanism for this novel dinuclear water oxidation catalyst, demonstrating its potential for artificial photosynthesis. The photocatalytic performance of this complex was reported to be the highest among Ru(bda) complexes, indicating its promising application in the field of water oxidation research.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Aaron G. Nash, Colton J. Breyer, Brett D. Vincenzini, Gregory I. Elliott, Jens Niklas, Oleg G. Poluektov, Arnold L. Rheingold, Diane K. Smith, Djamaladdin G. Musaev, Douglas B. Grotjahn
Summary: This study reports a catalyst that maintains high electrocatalytic turnover frequency at very low pH values, with high current densities and excellent durability. Preliminary computational studies suggest that the sulfonate group in the active site acts as a proton relay even in strong acid.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Ana-Lucia Meza-Chincha, Dorothee Schindler, Mirco Natali, Frank Wuerthner
Summary: The study revealed that the process of photocatalytic water oxidation is influenced by various factors such as the choice of photosensitizer, reaction media, buffer concentration, light intensity, and sensitizer concentration. The catalytic activities of Ru macrocycles are not only limited by their intrinsic catalytic activities, but also by the efficiency of photogeneration of oxidant PS(+) and its ability to act as an oxidizing agent to the catalysts, both of which strongly depend on the choice of photosensitizer and the amount of employed organic co-solvent.
Article
Chemistry, Multidisciplinary
Arabinda Muley, Kalai Selvan Karumban, Sadananda Kumbhakar, Bishnubasu Giri, Somnath Maji
Summary: In this study, two cobalt mononuclear complexes were successfully synthesized and thoroughly characterized using various spectroscopic and analytical techniques. Both complexes exhibited high phenoxazinone synthase activity and excellent reactivity, with turnover numbers significantly higher than those of previously reported similar complexes. The research provides in-depth insight into the metal ion involvement and the extent of phenoxazinone synthase activity.
NEW JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Preeti Devi, Muthukumar Kannan, Kiran, Virender, Ashwani Kumar, Senthilkumar Muthaiah
Summary: A highly efficient oxidation of secondary alcohols has been achieved using three different in situ catalyst systems, all of which are environmentally friendly and highly atom economical. These catalyst systems were generated from commercially available ruthenium(II)benzenedichloride dimer, dichloro(1,5-cyclooctadiene)ruthenium(II) polymer, and ruthenium(II)(p-cymene)dichloride dimer, in combination with the additive hexamethylenetetramine. The catalyst systems showed high activity even at low catalyst loadings, and the oxidation reactions proceeded via a dehydrogenative pathway to produce hydrogen as the sole product. The developed catalyst systems have potential applications in the release of hydrogen from liquid organic hydrogen carriers.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2022)
Article
Chemistry, Applied
Alexander B. Sorokin
Summary: Catalytic chemistry of phthalocyanine complexes is a rapidly growing field, showing remarkable catalytic properties in oxidation reactions and other reactions. The recent discovery of u-nitrido diiron phthalocyanines as promising bio-inspired catalysts has led to new developments and increased potential for applications in challenging reactions, with expanding possibilities for further development.
Article
Chemistry, Multidisciplinary
Jully Patel, Gabriel Bury, Alireza K. Ravari, Roman Ezhov, Yulia Pushkar
Summary: This study investigates the descriptors correlated with catalytic activity through the synthesis and characterization of two catalysts. The results show that the introduction of an ethoxy group can enhance the catalytic activity in chemically driven and photocatalytic water oxidation, and it is related to the configuration of the Ru-oxo unit.
Article
Chemistry, Inorganic & Nuclear
Yuta Tsubonouchi, Takeumi Watanabe, Kazuha Yoshida, Shunsuke Watabe, Keisuke Inaba, Masanari Hirahara, Tsubasa Hatanaka, Yasuhiro Funahashi, Debraj Chandra, Norihisa Hoshino, Zaki N. Zahran, Masayuki Yagi
Summary: Geometric isomers of mononuclear ruthenium(II) complexes were synthesized and comprehensively studied to investigate the geometric and electronic structures, as well as unique aspects in various reactions between isomers.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Nour El Harakeh, Ana C. P. de Morais, Neha Rani, Javier A. G. Gomez, Abigail Cousino, Mauricio Lanznaster, Shivnath Mazumder, Claudio N. Verani
Summary: Two heterometallic photocatalysts were designed and tested for water reduction, with one requiring an external photosensitizer to trigger catalytic activity and the other displaying significant coupling between catalytic and light-harvesting units for self-supported photocatalysis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Biochemistry & Molecular Biology
Jose Manuel Veiga del Pino, Franco Scalambra, Cristina Bermejo-Casadesus, Anna Massaguer, Federico Garcia-Maroto, Antonio Romerosa
Summary: A water-soluble ruthenium complex was synthesized and characterized by various techniques. Its optical and biological properties were studied and compared with other ruthenium complexes. The complex showed high anticancer activity under visible light irradiation and exhibited no toxicity against red blood cells.
JOURNAL OF INORGANIC BIOCHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Tim Schlossarek, Vladimir Stepanenko, Florian Beuerle, Frank Wuerthner
Summary: This study investigates water-soluble multinuclear complexes based on ruthenium 2,2'-bipyridine-6,6'-dicarboxylate (bda) and ditopic bipyridine linker units for three-component visible light-driven water oxidation catalysis. The catalytic efficiency is significantly enhanced in the absence of organic co-solvents and with increasing oligomer length, which is attributed to the self-assembly of linear Ru(bda) oligomers into aggregated superstructures. The obtained turnover frequencies (up to 14.9 s(-1)) and turnover numbers (more than 1000) per ruthenium center are the highest reported so far for Ru(bda)-based photocatalytic water oxidation systems.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Atsuki Maeda, Jun-ya Tokumoto, Soichiro Kojima, Keiichi Fujimori, Takayo Moriuchi-Kawakami, Masanari Hirahara
Summary: This study experimentally investigated the formation of adducts between stimuli-responsive ruthenium complexes and a model DNA base. The results showed that these complexes can undergo isomerization and adduct formation under certain temperatures. Additionally, there was a difference in the rate of adduct formation between different complexes, which may be attributed to intramolecular hydrogen bonding and steric hindrance.
Article
Chemistry, Physical
Chong Chen, Li-Song Zhang, Zhe Qian, Ai-Quan Jia, Qian-Feng Zhang
Summary: In this study, four mononuclear bis(o-phenanthroline) ruthenium(II) complexes were synthesized and characterized by various techniques, with the structures of complexes 1-3 being established by single crystal X-ray crystallography. Furthermore, the photocatalytic properties of these complexes towards water oxidation in a three-component system were investigated, driven by visible light.
JOURNAL OF MOLECULAR STRUCTURE
(2021)
Article
Chemistry, Physical
Denise Lovison, Tobias Berghausen, Sophie R. Thomas, Jonathan Robson, Markus Drees, Christian Jandl, Alexander Poethig, Patrick Mollik, Dominik P. Halter, Walter Baratta, Angela Casini
Summary: In this study, water-soluble organometallic Ru(II) complexes were synthesized and found to act as anticancer agents by catalyzing transfer hydrogenation reactions with biomolecules. The structure-activity relationship and reaction mechanism were investigated, and the compounds were also tested for their anticancer activity in vitro.
Article
Chemistry, Analytical
Amani L. Lee, Anil K. Pandey, Sina Chiniforoush, Mukunda Mandal, Jiaqian Li, Christopher J. Cramer, Christy L. Haynes, William C. K. Pomerantz
Summary: Temperature can have significant effects on biological and chemical processes within a body. This study focuses on the development of fluorinated molecular temperature sensors to improve the accuracy and sensitivity of temperature monitoring using F-19 MRI. The new sensors show a nearly 2-fold increase in temperature responsiveness compared to existing methods, and may help advance the use of fluorine magnetic resonance techniques for clinical applications.
ANALYTICAL CHEMISTRY
(2022)
Review
Chemistry, Multidisciplinary
Farihah M. Haque, Jacob S. A. Ishibashi, Claire A. L. Lidston, Huiling Shao, Frank S. Bates, Alice B. Chang, Geoffrey W. Coates, Christopher J. Cramer, Paul J. Dauenhauer, William R. Dichtel, Christopher J. Ellison, Ethan A. Gormong, Leslie S. Hamachi, Thomas R. Hoye, Mengyuan Jin, Julia A. Kalow, Hee Joong Kim, Gaurav Kumar, Christopher J. LaSalle, Stephanie Liffland, Bryce M. Lipinski, Yutong Pang, Riffat Parveen, Xiayu Peng, Yanay Popowski, Emily A. Prebihalo, Yernaidu Reddi, Theresa M. Reineke, Daylan T. Sheppard, Jeremy L. Swartz, William B. Tolman, Bess Vlaisavljevich, Jane Wissinger, Shu Xu, Marc A. Hillmyer
Summary: Transforming how plastics are made, unmade, and remade is crucial for a sustainable future. This review highlights important accomplishments in the field and discusses key themes including feedstocks, polymerization processes and techniques, intended use, and end of use.
Article
Chemistry, Inorganic & Nuclear
Masanari Hirahara, Shota Furutani, Hiroki Goto, Keiichi Fujimori, Takayo Moriuchi-Kawakami
Summary: The study investigated the responsive properties of a host-guest system based on proximal and distal ruthenium aqua complexes. It was found that the two alkyl chains in the complexes had different binding affinities to cyclodextrins, with proximal-1 showing higher affinity. The reversible formation of host-guest complexes could be achieved through repeated external stimuli.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Multidisciplinary
Sreehari Surendran Rajasree, Jierui Yu, Saied Md Pratik, Xinlin Li, Rui Wang, Amar S. Kumbhar, Subhadip Goswami, Christopher J. Cramer, Pravas Deria
Summary: Crystalline metal-organic frameworks (MOFs) serve as promising synthetic analogues of photosynthetic light-harvesting complexes (LHCs) with unique photophysical behaviors including multilinker molecular excitons and super-radiance. The size of multilinker excitons depends on the electronic symmetry of the linker, and the predicted energy transfer rate constant and anisotropy of exciton displacement align well with experimental data. These findings are crucial for the design of low-density solar energy conversion systems by positioning catalysts or electrodes relative to linker orientation.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Inorganic & Nuclear
Huiling Shao, Riddhish Pandharkar, Christopher J. Cramer
Summary: The study investigates the reaction mechanism of 1,3-butadiene polymerization catalyzed by a metal-organic framework (MOF) catalyst. The results suggest that missing-linker defects at the Co(II) nodes are crucial for achieving high 1,4-cis-polybutadiene (PBD) selectivity.
Article
Chemistry, Multidisciplinary
Jenny G. Vitillo, Christopher J. Cramer, Laura Gagliardi
Summary: Highly correlated systems, especially those containing transition metals, are common in catalysis. Existing single determinantal methods using Kohn Sham density functional theory often fail to accurately account for the significant static correlation in such systems. Although more rigorous multiconfigurational methods have been applied in some specific cases, their use in catalysis remains limited. This paper discusses the obstacles hindering the routine application of multireference wave function theoretical calculations to catalytic systems and the current progress in overcoming these obstacles.
ISRAEL JOURNAL OF CHEMISTRY
(2022)
Review
Chemistry, Inorganic & Nuclear
Atsushi Kobayashi, Shin-ya Takizawa, Masanari Hirahara
Summary: This review focuses on the photofunctional molecular assemblies on the surfaces of rigid semiconductors or soft lipid membranes to overcome backward reactions in Z-scheme water-splitting photocatalysis. Approaches based on the dye-sensitization mechanism can improve photoinduced charge-separation efficiency and regulate the reaction field and pathway in photocatalytic O-2 and H-2 evolution reactions, providing powerful techniques for improving photocatalytic activity.
COORDINATION CHEMISTRY REVIEWS
(2022)
Article
Chemistry, Inorganic & Nuclear
Yuta Tsubonouchi, Takeumi Watanabe, Kazuha Yoshida, Shunsuke Watabe, Keisuke Inaba, Masanari Hirahara, Tsubasa Hatanaka, Yasuhiro Funahashi, Debraj Chandra, Norihisa Hoshino, Zaki N. Zahran, Masayuki Yagi
Summary: Geometric isomers of mononuclear ruthenium(II) complexes were synthesized and comprehensively studied to investigate the geometric and electronic structures, as well as unique aspects in various reactions between isomers.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Riddhish Pandharkar, Matthew R. Hermes, Christopher J. Cramer, Laura Gagliardi
Summary: This paper introduces a localized active space-state interaction (LASSI) method that can reduce the computational cost of multireference calculations and improve interpretability. The method utilizes the local nature of electron-electron correlation and expresses the composite wave function as an antisymmetrized product of unentangled wave functions in local active subspaces. The use of LASSI allows for more compact and selective inclusion of states, providing a quantitative analysis of specific types of interactions.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2022)
Article
Nanoscience & Nanotechnology
Xinlin Li, Ryther Anderson, H. Christopher Fry, Saied Md Pratik, Wenqian Xu, Subhadip Goswami, Taylor G. Allen, Jierui Yu, Sreehari Surendran Rajasree, Christopher J. Cramer, Garry Rumbles, Diego A. Gomez-Gualdron, Pravas Deria
Summary: Solar energy conversion requires materials with high potential and charge delivery ability. In this study, a semiconducting metal-organic framework (MOF) was synthesized with improved charge conductivity and optical band gap. The MOF showed stable 3D-porous structure and had a band gap of 1.57 eV. Transient absorption spectroscopy revealed long-lived photo-generated charge-transfer state.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Analytical
Keiichi Fujimori, Akira Izutani, Kenta Tsujimoto, Masanari Hirahara, Takayo Moriuchi-Kawakami, Masato Ueda, Takahiko Suzue, Hideshi Kimoto, Kei Okamura
Summary: We developed a new chemiluminescence (CL) method for quantifying sulfide in seawater. A terbium-pipemidic acid complex was used as a CL enhancer. The method had a sensitivity eight times higher than previous methods and a limit of detection of 21 nmol/L sulfide. Interfering conservative ions, such as Br-, were investigated, as well as the effects of salinity, temperature, and interfering chemicals. The method was also validated using sulfite-spiked natural seawater samples.
ANALYTICAL SCIENCES
(2023)
Article
Chemistry, Multidisciplinary
Atsuki Maeda, Jun-ya Tokumoto, Soichiro Kojima, Keiichi Fujimori, Takayo Moriuchi-Kawakami, Masanari Hirahara
Summary: This study experimentally investigated the formation of adducts between stimuli-responsive ruthenium complexes and a model DNA base. The results showed that these complexes can undergo isomerization and adduct formation under certain temperatures. Additionally, there was a difference in the rate of adduct formation between different complexes, which may be attributed to intramolecular hydrogen bonding and steric hindrance.
Correction
Chemistry, Multidisciplinary
Emily A. Prebihalo, Anna M. Luke, Yernaidu Reddi, Christopher J. LaSalle, Vijay M. Shah, Christopher J. Cramer, Theresa M. Reineke
Summary: Correction: This study provides important theoretical guidance for the synthesis of high-performance polymer materials with special structures by the radical ring-opening polymerization of sustainably-derived thionoisochromanone.
Article
Chemistry, Multidisciplinary
Emily A. Prebihalo, Anna M. Luke, Yernaidu Reddi, Christopher J. LaSalle, Vijay M. Shah, Christopher J. Cramer, Theresa M. Reineke
Summary: In this study, we report the synthesis, characterization, and radical ring-opening polymerization (rROP) capabilities of thionoisochromanone (TIC), a fungi-derivable thionolactone. TIC is the first reported six-membered thionolactone that undergoes homopolymerization under free radical conditions without the need for a dormant comonomer or repeated initiation. The resulting polymer is fully degradable under mild, basic conditions.
Article
Chemistry, Multidisciplinary
Mayuri K. Porwal, Yernaidu Reddi, Derek J. Saxon, Christopher J. Cramer, Christopher J. Ellison, Theresa M. Reineke
Summary: This study demonstrates the facile synthesis of functional stereoregular polysaccharides with 1,6-alpha linkages from biomass-derived levoglucosan through cationic ring-opening polymerization. Computational studies show that metal triflate catalysts exhibit high coordination efficiency with levoglucosan derivatives and low toxicity compared to previous catalysts. The reported polymers have good thermal stability and a wide glass transition temperature window.