Article
Chemistry, Multidisciplinary
Jin Tanaka, Yuki Nagashima, Antonio Junio Araujo Dias, Ken Tanaka
Summary: A novel photoinduced in situ reduction reaction of half-sandwich metal [Rh(III)] complexes to low-valent anionic metal [Rh(II)] ate complexes has been reported, enabling room temperature ortho-C-H borylation of arenes. This strategy was facilitated by using a functionalized cyclopentadienyl (Cp-A3) Rh(III) catalyst developed by the researchers.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Han Li, Oliver S. Wenger
Summary: Our study demonstrates the concept that single excitation of the two-electron reduced forms of perylene diimides (PDIs) with green photons can produce excited states with similar or greater reducing power than the shorter-lived excited states of PDI radical monoanions. By performing multi-electron reduction of a photocatalyst with a sacrificial reagent before irradiation with low-energy photons, we can generate highly reactive excited states for photocatalytic reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Multidisciplinary
Natalie G. K. Wong, Caroline E. H. Dessent
Summary: This mini review provides an overview of recent advanced laser spectroscopic studies on organic sunscreens, focusing on their molecular-level processes and the effects of pH, metal cations, and solvation on their structures and non-radiative decay pathways.
FRONTIERS IN CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Rohit Kumar, Sanjukta Pahar, Joy Chatterjee, Soumya Ranjan Dash, Rajesh G. Gonnade, Kumar Vanka, Sakya S. Sen
Summary: In this study, two magnesium complexes supported by 2,2'-pyridylpyrrolide ligands (PyPyrH) were reported. These complexes exhibit bright luminescence with quantum yields of 22% and 14% in the solid state, respectively. Theoretical calculations indicate that their emissive properties originate from intra- and inter-ligand charge transfer.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Yang Cheng, Qingqing Yang, Jiang He, Wenjie Zou, Keyu Liao, Xiaoyong Chang, Chao Zou, Wei Lu
Summary: This article introduces a series of substituted anionic ligands containing Cr(iii) complexes, which exhibit phosphorescent properties in degassed fluid solutions.
DALTON TRANSACTIONS
(2023)
Article
Biochemistry & Molecular Biology
Jack Saltiel, Sumesh B. Krishnan, Shipra Gupta, Anjan Chakraborty, Edwin F. Hilinski, Xinsong Lin
Summary: Cholesta-5,7,9(11)-trien-3 beta-ol (9,11-dehydroprovitamin D-3, CTL) is used as a fluorescent probe to track the presence and migration of cholesterol in vivo. The photochemistry and photophysics of CTL in degassed and air-saturated tetrahydrofuran (THF) solution, an aprotic solvent, have been studied. The zwitterionic nature of the singlet excited state, (CTL)-C-1*, is revealed in ethanol, a protic solvent. In the presence of air, peroxide formation is a major reaction channel, similar to THF.
Article
Chemistry, Multidisciplinary
Sapna Ahuja, Sruthy Baburaj, Lakshmy Kannadi Valloli, Sarvar Aminovich Rakhimov, Kavyasree Manal, Aakrati Kushwaha, Steffen Jockusch, Malcolm D. E. Forbes, Jayaraman Sivaguru
Summary: Aryl-maleimides undergo a novel [2+4]-photodimerization instead of the expected [2+2]-photodimerization, and the stereochemistry of the photodimer formed complements the product observed under thermal conditions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Sarah Walden, Joshua Carroll, Andreas-Neil Unterreiner, Christopher Barner-Kowollik
Summary: This article reveals a fundamental mismatch between the absorption spectrum of a chromophore and its photochemical reactivity, highlighting the limitations of the assumption that effective photochemical reactions require strong overlap between the absorption spectrum and the excitation wavelength. The article proposes future directions for understanding action plots and explores the importance of action plots in designing precise photochemical applications.
Article
Chemistry, Multidisciplinary
Mengfei Wang, Kei Murata, Yosuke Koike, Gediminas Jonusauskas, Amaury Furet, Dario M. Bassani, Daisuke Saito, Masako Kato, Yuushi Shimoda, Kiyoshi Miyata, Ken Onda, Kazuyuki Ishii
Summary: A recent study has demonstrated the photo-induced CO-releasing capabilities of the complex Re1Pc, which is composed of a [Re(CO)(3)](+) unit and a phthalocyanine ligand. The complex exhibited efficient spin-orbit coupling and large Franck-Condon factors, resulting in short excited-state lifetimes and ultrafast intersystem crossing. This research provides promising insights into the development of red-light-driven photoCORMs for biomedical applications.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Christian Ley, Antoine Siedel, Tony Bertaux, Celine Croutxe-Barghorn, Xavier Allonas
Summary: Photobase generators are species that can catalyze various reactions such as thiol-Michael, thiol-isocyanate, and ring-opening polymerization reactions. However, the compounds currently available have complex syntheses and low quantum yields. To address these issues, photobase generators based on the photodecarboxylation reaction were developed and studied. The photochemistry and photophysics of two xanthone photobase, their carboxylic acid precursors, and their photoproducts were synthesized and investigated to understand the mechanism of photobase generation. Accurate quantum yields of triplet states and photobase generation were determined. The impact of the intermediate radical before the base release was also demonstrated. The photophysics of the photobase was characterized using femtosecond spectroscopy, revealing a rate constant of 2.2x10(9) s(-1) for the photodecarboxylation process occurring from the second excited triplet state.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Applied
Julia Arnanz, Fernando Romeo-Gella, Juan J. Nogueira, Ines Corral
Summary: The design of novel chromophores with specific photophysical traits is crucial for the development of new dyes and optical devices. Azobenzene derivatives, as the main industrial dyes, are widely used in the design of general-purpose photoactivated switches. In this study, we investigated the optical and photoisomerization properties of two push-push azo derivatives from a theoretical perspective, providing insights for formulating dyes with specific photophysical properties. Both derivatives showed fast photoactivated isomerization with downhill excited-state potential energy surfaces. The trans and cis forms exhibited nearly complementary absorption spectra, offering discriminatory color and differential excitation possibilities.
Article
Chemistry, Physical
Vasilis Petropoulos, Lorenzo Uboldi, Margherita Maiuri, Giulio Cerullo, Lara Martinez-Fernandez, Evangelos Balanikas, Dimitra Markovitsi
Summary: The polarity of DNA has been found to have an impact on the relaxation of DNA electronic excited states, with different nucleotide sequences leading to different optical properties.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Review
Chemistry, Multidisciplinary
Narayan Sinha, Polina Yaltseva, Oliver S. Wenger
Summary: The nephelauxetic effect, which refers to the expansion of d-orbitals as a result of metal-ligand bond covalence, has been recognized for its importance in the design of new photoactive complexes using first-row transition metals. This effect can significantly impact the photophysical properties of 3d metal complexes in solution at room temperature. By exploiting the nephelauxetic effect, red luminescence in Cr-III and Mn-IV complexes has been shifted to the near-infrared spectral region, while charge-transfer excited states in Fe-II and Co-III complexes have been stabilized, improving their properties and application potential.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Biochemistry & Molecular Biology
Lakshmy Kannadi Valloli, Kavyasree Manal, Brieanna Lewis, Steffen Jockusch, Jayaraman Sivaguru
Summary: This study investigates the irradiation reaction of beta-enaminones generated in situ from cyclic 1,3-diketones and activated alkenes and finds that the selectivity of the reaction products depends on the type of cyclic 1,3-diketones used, which is rationalized based on the Dieckmann-Kon rule.
PHOTOCHEMISTRY AND PHOTOBIOLOGY
(2023)
Article
Chemistry, Physical
Debanjana Chakraborty, Chao Yang, Lijuan Wang, Dongping Zhong
Summary: The repair of a CPD structural isomer with a sugar replacement was investigated, and a decrease in binding efficiency and repair quantum yield was observed. Using femtosecond spectroscopy and molecular dynamics simulations, it was found that the sugar replacement disrupted the lesion binding configuration and weakened the electronic coupling between the cofactor and lesion. These findings highlight how CPD photolyases have optimized their interactions to maximize repair yields.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Physical
Juan Carlos Roldao, Eliezer Fernando Oliveira, Begona Milian-Medina, Johannes Gierschner, Daniel Roca-Sanjuan
Summary: State-of-the-art CASPT2 calculations are used to investigate the effect of double excitations on the GSA and ESA spectra of distyrylbenzene. The multi-reference results provide a more accurate description of electronic transitions compared to DFT results. Careful selection of the active space and basis set in the CASPT2 approach allows for a reliable description of spectral features, with cost-effective DFT-based geometries being applicable without significant loss of accuracy. Double excitations play a crucial role in higher excited states in the GSA spectrum, but have minimal impact on discernible spectral features. In the more complex ESA, a multiconfigurational treatment with double (and higher) excitations is essential.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Francesc Bejarano, Diego Gutierrez, Jose Catalan-Toledo, Daniel Roca-Sanjuan, Johannes Gierschner, Jaume Veciana, Marta Mas-Torrent, Concepcio Rovira, Nuria Crivillers
Summary: This study investigates the photoisomerization of an asymmetrically substituted styrene containing a redox-active ferrocene moiety and a terminal alkyne group in solution, and upon forming chemisorbed self-assembled monolayers. The charge transport measurements across the monolayers show that there is an alteration of the isomerization pathway when linked to the gold substrate, favoring trans to cis conversion compared to solution. The experimental results are interpreted based on quantum chemistry calculations.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Geosciences, Multidisciplinary
Alfonso Saiz-Lopez, A. Ulises Acuna, Anoop S. Mahajan, Juan Z. Davalos, Wuhu Feng, Daniel Roca-Sanjuan, Javier Carmona-Garcia, Carlos A. Cuevas, Douglas E. Kinnison, Juan Carlos Gomez Martin, Joseph S. Francisco, John M. C. Plane
Summary: This article presents the first model of stratospheric mercury chemistry and identifies two distinct mercury chemical regimes. The study also reveals that the oxidation of mercury in the stratosphere is faster than previously assumed, but regulated by photo-reduction. The lifetime of mercury in the stratosphere shows a significant variation.
GEOPHYSICAL RESEARCH LETTERS
(2022)
Article
Chemistry, Physical
Stefano Battaglia, Lina Fransen, Ignacio Fdez. Galvan, Roland Lindh
Summary: In this work, a new approach called sigma(p)-CASPT2 based on sigma p regularization is proposed to fix the intruder-state problem (ISP) in CASPT2. The effectiveness of sigma(p)-CASPT2 in removing the ISP and the sensitivity of the approach to input parameters are analyzed and compared to previous techniques. It is found that sigma p- CASPT2 performs better compared to previous approaches and different versions have different potential applications. The analysis also reveals the unsuitability of the real level shift technique as a general way to avoid the ISP.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2022)
Article
Chemistry, Physical
Juan Carlos Roldao, Eliezer Fernando Oliveira, Begona Milian-Medina, Johannes Gierschner, Daniel Roca-Sanjuan
Summary: This study investigates the calculation of excited-state absorption spectra using QR TD-DFT and CASPT2 for oligophenylenevinylenes and oligothiophenes. CASPT2 provides a reliable description of the spectra, while QR TD-DFT gives reasonable results under certain conditions. The failure of QR TD-DFT is attributed to incomplete configuration description and improper MO description.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2022)
Article
Chemistry, Physical
Yoshio Nishimoto, Stefano Battaglia, Roland Lindh
Summary: In this study, analytic derivatives of three CASPT2 variants and an RASPT2 extension were developed to locate minimum energy conical intersections. The results showed that the three CASPT2 variants had qualitatively similar predictions, but the recently developed RMS-CASPT2 was least sensitive to the number of states considered. CASPT2 and reference self-consistent field calculations predicted different energetics and bond lengths.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2022)
Article
Multidisciplinary Sciences
Antonio Frances-Monerris, Javier Carmona-Garcia, Tarek Trabelsi, Alfonso Saiz-Lopez, James R. Lyons, Joseph S. Francisco, Daniel Roca-Sanjuan
Summary: This study presents a novel mechanism for the formation of polysulfur compounds in the atmosphere of Venus, demonstrating the production of S-2 and filling critical data gaps.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Jie J. Bao, Matthew R. Hermes, Thais R. Scott, Andrew M. Sand, Roland Lindh, Laura Gagliardi, Donald G. Truhlar
Summary: This paper reports the implementation of analytic gradients for CMS-PDFT in both OpenMolcas and PySCF, and illustrates the use of these gradients by applying the method to the excited states of formaldehyde and phenol.
Article
Chemistry, Medicinal
Daniel Sethio, Vasanthanathan Poongavanam, Ruisheng Xiong, Mohit Tyagi, Duc Duy Vo, Roland Lindh, Jan Kihlberg
Summary: Conformational analysis is crucial for the design of bioactive molecules, and it becomes even more challenging for macrocycles due to their unique characteristics. In this study, we simulated the conformations of five designed macrocycles and verified the results against experimental measurements. Our simulations accurately predicted the intramolecular interactions and revealed a solvent-induced conformational switch of the macrocyclic ring. This provides a foundation for the rational design of molecular chameleons that can adapt to different environments.
JOURNAL OF CHEMICAL INFORMATION AND MODELING
(2023)
Article
Chemistry, Physical
Ignacio Fdez Galvan, Roland Lindh
Summary: In this study, a pseudodiabatic surrogate model is developed based on Gaussian process regression, which accurately reproduces the adiabatic surfaces and significantly reduces the computational effort required to obtain minimum energy crossing points using the restricted variance optimization method.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Physical
Giovanni Li Manni, Ignacio Fdez. Galvan, Ali Alavi, Flavia Aleotti, Francesco Aquilante, Jochen Autschbach, Davide Avagliano, Alberto Baiardi, Jie J. Bao, Stefano Battaglia, Letitia Birnoschi, Alejandro Blanco-Gonzalez, Sergey I. Bokarev, Ria Broer, Roberto Cacciari, Paul B. Calio, Rebecca K. Carlson, Rafael Carvalho Couto, Luis Cerdan, Liviu F. Chibotaru, Nicholas F. Chilton, Jonathan Richard Church, Irene Conti, Sonia Coriani, Juliana Cuellar-Zuquin, Razan E. Daoud, Nike Dattani, Piero Decleva, Coen de Graaf, Mickael G. Delcey, Luca De Vico, Werner Dobrautz, Sijia S. Dong, Rulin Feng, Nicolas Ferre, Michael Filatov (Gulak), Laura Gagliardi, Marco Garavelli, Leticia Gonzalez, Yafu Guan, Meiyuan Guo, Matthew R. Hennefarth, Matthew R. Hermes, Chad E. Hoyer, Miquel Huix-Rotllant, Vishal Kumar Jaiswal, Andy Kaiser, Danil S. Kaliakin, Marjan Khamesian, Daniel S. King, Vladislav Kochetov, Marek Krosnicki, Arpit Arun Kumaar, Ernst D. Larsson, Susi Lehtola, Marie-Bernadette Lepetit, Hans Lischka, Pablo Lopez Rios, Marcus Lundberg, Dongxia Ma, Sebastian Mai, Philipp Marquetand, Isabella C. D. Merritt, Francesco Montorsi, Maximilian Morchen, Artur Nenov, Vu Ha Anh Nguyen, Yoshio Nishimoto, Meagan S. Oakley, Massimo Olivucci, Markus Oppel, Daniele Padula, Riddhish Pandharkar, Quan Manh Phung, Felix Plasser, Gerardo Raggi, Elisa Rebolini, Markus Reiher, Ivan Rivalta, Daniel Roca-Sanjuan, Thies Romig, Arta Anushirwan Safari, Aitor Sanchez-Mansilla, Andrew M. Sand, Igor Schapiro, Thais R. Scott, Javier Segarra-Marti, Francesco Segatta, Dumitru-Claudiu Sergentu, Prachi Sharma, Ron Shepard, Yinan Shu, Jakob K. Staab, Tjerk P. Straatsma, Lasse Kragh Sorensen, Bruno Nunes Cabral Tenorio, Donald G. Truhlar, Liviu Ungur, Morgane Vacher, Valera Veryazov, Torben Arne Voss, Oskar Weser, Dihua Wu, Xuchun Yang, David Yarkony, Chen Zhou, J. Patrick Zobel, Roland Lindh
Summary: This article describes the developments of the open-source OpenMolcas chemistry software environment since spring 2020, focusing on the novel functionalities in the stable branch and interfaces with other packages. These developments cover a wide range of topics in computational chemistry and provide an overview of the chemical phenomena and processes that OpenMolcas can address.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Multidisciplinary Sciences
Yee Jun Tham, Nina Sarnela, Siddharth Iyer, Qinyi Li, Helene Angot, Lauriane L. J. Quelever, Ivo Beck, Tiia Laurila, Lisa J. Beck, Matthew Boyer, Javier Carmona-Garcia, Ana Borrego-Sanchez, Daniel Roca-Sanjuan, Otso Perakyla, Roseline C. Thakur, Xu-Cheng He, Qiaozhi Zha, Dean Howard, Byron Blomquist, Stephen D. Archer, Ludovic Bariteau, Kevin Posman, Jacques Hueber, Detlev Helmig, Hans-Werner Jacobi, Heikki Junninen, Markku Kulmala, Anoop S. Mahajan, Andreas Massling, Henrik Skov, Mikko Sipila, Joseph S. Francisco, Julia Schmale, Tuija Jokinen, Alfonso Saiz-Lopez
Summary: Observations report the presence of HClO3 and HClO4 in the atmosphere, showing their widespread occurrence over the pan-Arctic during spring. These findings provide further insights into atmospheric chlorine cycling in the polar environment. The increase in HClO3 and HClO4 is linked to the increase in bromine levels, indicating the role of bromine chemistry in their formation and suggesting a previously missing atmospheric sink for reactive chlorine.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Gemma M. Rodriguez-Muniz, Ana B. Fraga-Timiraos, Miriam Navarrete-Miguel, Ana Borrego-Sanchez, Daniel Roca-Sanjuan, Miguel A. Miranda, Virginie Lhiaubet-Vallet
Summary: The desire to achieve simple systems that can photoreductively split four-membered ring compounds is of interest in both inorganic chemistry and biochemistry, with the aim to mimic the activity of DNA photorepair enzymes. In this study, dyads containing the cyclobutane thymine dimer and guanine or 8-oxoguanine are synthesized, and their photoreactivities are compared. The results show that both dyads can split the ring, resulting in the formation of thymine, but with a lower quantum yield for the guanine derivative.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Giovanni Li Manni, Ignacio Fdez. Galvan, Ali Alavi, Flavia Aleotti, Francesco Aquilante, Jochen Autschbach, Davide Avagliano, Alberto Baiardi, Jie J. Bao, Stefano Battaglia, Letitia Birnoschi, Alejandro Blanco-Gonzalez, Sergey I. Bokarev, Ria Broer, Roberto Cacciari, Paul B. Calio, Rebecca K. Carlson, Rafael Carvalho Couto, Luis Cerdan, Liviu F. Chibotaru, Nicholas F. Chilton, Jonathan Richard Church, Irene Conti, Sonia Coriani, Juliana Cuellar-Zuquin, Razan E. Daoud, Nike Dattani, Piero Decleva, Coen de Graaf, Mickael G. Delcey, Luca De Vico, Werner Dobrautz, Sijia S. Dong, Rulin Feng, Nicolas Ferre, Michael Filatov(Gulak), Laura Gagliardi, Marco Garavelli, Leticia Gonzalez, Yafu Guan, Meiyuan Guo, Matthew R. Hennefarth, Matthew R. Hermes, Chad E. Hoyer, Miquel Huix-Rotllant, Vishal Kumar Jaiswal, Andy Kaiser, Danil S. Kaliakin, Marjan Khamesian, Daniel S. King, Vladislav Kochetov, Marek Krosnicki, Arpit Arun Kumaar, Ernst D. Larsson, Susi Lehtola, Marie-Bernadette Lepetit, Hans Lischka, Pablo Lopez Rios, Marcus Lundberg, Dongxia Ma, Sebastian Mai, Philipp Marquetand, Isabella C. D. Merritt, Francesco Montorsi, Maximilian Morchen, Artur Nenov, Vu Ha Anh Nguyen, Yoshio Nishimoto, Meagan S. Oakley, Massimo Olivucci, Markus Oppel, Daniele Padula, Riddhish Pandharkar, Quan Manh Phung, Felix Plasser, Gerardo Raggi, Elisa Rebolini, Markus Reiher, Ivan Rivalta, Daniel Roca-Sanjuan, Thies Romig, Arta Anushirwan Safari, Aitor Sanchez-Mansilla, Andrew M. Sand, Igor Schapiro, Thais R. Scott, Javier Segarra-Marti, Francesco Segatta, Dumitru-Claudiu Sergentu, Prachi Sharma, Ron Shepard, Yinan Shu, Jakob K. Staab, Tjerk P. Straatsma, Lasse Kragh Sorensen, Bruno Nunes Cabral Tenorio, Donald G. Truhlar, Liviu Ungur, Morgane Vacher, Valera Veryazov, Torben Arne Voss, Oskar Weser, Dihua Wu, Xuchun Yang, David Yarkony, Chen Zhou, J. Patrick Zobel, Roland Lindh
Summary: This article describes the recent developments in the open-source chemistry software environment, OpenMolcas, since spring 2020. It focuses on the new functionalities and interfaces with other packages. The article presents various topics in computational chemistry, including electronic structure theory, electronic spectroscopy simulations, molecular structure optimizations, ab initio molecular dynamics, and other new features. Overall, it highlights the capabilities of OpenMolcas in addressing chemical phenomena and processes, making it an attractive platform for advanced atomistic computer simulations.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Physical
Javier Segarra-Marti, Thierry Tran, Michael J. Bearpark
Summary: UV and VUV-induced processes in DNA/RNA nucleobases play a crucial role in understanding the photo-damaging and photo-protecting mechanisms in genetic material. This study models the events following photoionisation and electronic excitation in uracil and its methylated derivatives, finding that 3-methylation has the largest impact on photoionised decay compared to uracil itself, while 1- and 5-methylation only give differences in detail.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)