Article
Chemistry, Multidisciplinary
Zhongtao Feng, Yuanyuan Chong, Shuxuan Tang, Yong Fang, Yue Zhao, Jun Jiang, Xinping Wang
Summary: This study isolated two borocyclic diradicals with different substituents, one of which was identified as an open shell singlet diradical, while the other was found to be a triplet ground state diradical with a large singlet-triplet energy gap. Both diradicals showed multiple fluorescence peaks and have potential applications in material design and organic semiconductors.
Article
Chemistry, Multidisciplinary
Alim Abdurahman, Jingmin Wang, Yihan Zhao, Ping Li, Li Shen, Qiming Peng
Summary: In this paper, the first stable luminescent Muller's hydrocarbon TTM-PhTTM is reported. Variable-temperature electron paramagnetic resonance spectroscopy measurements and theoretical calculations show that TTM-PhTTM has a 90% diradical character in its open-shell singlet ground state. TTM-PhTTM exhibits room-temperature deep-red emission in various solutions due to a small singlet-triplet energy gap. The unusually high stability of TTM-PhTTM is observed, which is attributed to effective steric hindrance and spin delocalization. Our findings are significant for the rational design and discovery of more stable luminescent diradical materials.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Palash Jana, Sudeep Koppayithodi, Samyadeb Mahato, Sariful Molla, Subhajit Bandyopadhyay
Summary: The diradical character in a molecular architecture can be controlled by modifying the aromaticity through the use of quinoidal pro-aromatic systems or easily accessible triplet states. In this study, a 14 π aromatic framework was perturbed to induce diradical character. The perturbed aromaticity was confirmed by X-ray diffraction, H-1 NMR chemical shifts, and quantum chemical calculations. Upon transition to a biradical structure, the aromaticity was restored. Moreover, the diradical could be converted to a radical anion and dianion upon photoexcitation in the presence of dimethylformamide as a solvent.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Physical
Pengbo Lyu, Ashley M. Wright, Alfredo Lopez-Olvera, Paulo G. M. Mileo, J. Antonio Zarate, Eva Martinez-Ahumada, Vladimir Martis, Daryl R. Williams, Mircea Dinca, Ilich A. Ibarra, Guillaume Maurin
Summary: An unprecedented reversible guest-induced metal-linker bond rearrangement in metal-organic frameworks (MOFs) was discovered through quantum calculations and DRIFT experiments. This mechanism, exemplified by MFM-300(Sc), enables strong metal-guest binding upon ammonia adsorption, ensuring efficient capture of toxic molecules, with full reversibility over multiple cycles. Such unconventional mechanisms in MOFs could lead to novel materials for efficient capture of highly corrosive molecules.
CHEMISTRY OF MATERIALS
(2021)
Article
Chemistry, Multidisciplinary
Qianqian Shi, Zhipeng Pei, Jinshuai Song, Shi-Jun Li, Donghui Wei, Michelle L. Coote, Yu Lan
Summary: A new model named relayed proton-coupled electron transfer (relayed-PCET) for diradical generation is proposed and confirmed in this study, which can open a door for new radical-radical cross-coupling reactions. Quantum mechanics calculations reveal the exact electronic structural changes during the radical processes for the first time.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Sitthichok Kasemthaveechok, Laura Abella, Marion Jean, Marie Cordier, Nicolas Vanthuyne, Thierry Guizouarn, Olivier Cador, Jochen Autschbach, Jeanne Crassous, Ludovic Favereau
Summary: We report a new molecular design for persistent chiral organic open-shell systems, which exhibit configurational stability and an inversion in energy of the singly occupied molecular orbital (SOMO) and the highest doubly occupied molecular orbital (HOMO). The designed extended helical pi-conjugated systems with delocalized unpaired electron resonance play a crucial role in achieving chemical stabilities, which is different from the traditional steric protection approach. The obtained helical monoradicals show unique features that allow for the exploration of chiral intramolecular electron transfer (IET) process in solvents of different polarity, resulting in unprecedented electronic circular dichroism (ECD) sign inversion for radical transitions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Ziqi Zhu, Di Zhang, Tongtong Xiao, Yu-Hui Fang, Xiao Xiao, Xiao-Ge Wang, Shang-Da Jiang, Dahui Zhao
Summary: This study presents a convenient method for integrating stable high-spin radicals into (hetero)aromatic polycycles, forming stable carbon-based polyradicals. The properties of the newly designed polycycles were thoroughly characterized, and a general method for installing stable polyradicals into functional pi-systems was proposed.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Lan-Qing Wu, Zhe Li, Yong Lu, Jin-Ze Hou, Hao-Qin Han, Qing Zhao, Jun Chen
Summary: This study demonstrates that regulating the chelating power and coordination structure can significantly enhance the high-voltage stability of ether-based electrolytes and the lifespan of lithium metal batteries. The use of 1,3-dimethoxypropane (DMP) and 1,3-diethoxypropane (DEP) as solvents in the electrolytes instead of the traditional 1,2-dimethoxyethane (DME) results in the formation of weak Li solvates, contributing to improved reversibility and high-voltage stability in lithium metal batteries. The fabricated high-voltage Li||LiNi0.8Co0.1Mn0.1O2 lithium metal batteries using 2.30 M Lithiumbisfluorosulfonimide (LiFSI)/DMP electrolyte show excellent capacity retention over 90% after 184 cycles, even under lean electrolyte and low anode to cathode ratio conditions.
Article
Chemistry, Multidisciplinary
Ke Li, Zhongtao Feng, Huapeng Ruan, Quanchun Sun, Yue Zhao, Xinping Wang
Summary: A singlet bis(triarylamine) diradical dication catenated by silver cations was isolated and characterized. The coordination of carbonyls with Ag+ revealed that the diradical character can be modulated by Lewis acid-base coordination and interchain intermolecular coupling interactions.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Zi-Yuan Wang, Ya-Zhong Dai, Li Ding, Bo-Wei Dong, Shang-Da Jiang, Jie-Yu Wang, Jian Pei
Summary: High-spin conjugated radicals have great potential in magnetic materials and organic spintronics, but their poor stability remains a challenge in obtaining them. Researchers have successfully synthesized a stable triplet conjugated diradical, m-DIP, with significant aromatic character and specific spin distribution characteristics.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Tsuyoshi Murata, Shinji Nakanishi, Hideki Nakayama, Hiroshi Ito, Miwa Morita, Ryotaro Tsuji, Yasushi Morita
Summary: This paper presents rechargeable batteries with a cathode of 100% organic active material using highly conductive vapor-deposited films of 4,8,12-trioxotriangulene (TOT) neutral radical. These cathodes contained neither a binder nor a conductive additive and showed high capacities close to the theoretical value of the active material. The face-on films had better rate and cycle characteristics due to their anisotropic conductivities.
ACS APPLIED ENERGY MATERIALS
(2022)
Article
Chemistry, Multidisciplinary
Yun-Shuai Huang, Yang Zhou, Xiaolong Zeng, Dachuan Zhang, Si Wu
Summary: Recyclable thermoset plastics are prepared using a commodity polyacrylonitrile and reversible crosslinker via reversible metal-ligand coordination. The thermosets are mechanically robust, and they are recyclable via reversible coordination upon light irradiation in a solvent and heating. This reversible coordination method enables the preparation of recyclable materials using other commodity polymers and polymer composites.
ADVANCED MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Yun-Shuai Huang, Yang Zhou, Xiaolong Zeng, Dachuan Zhang, Si Wu
Summary: Thermoset plastics, known for their stability, durability, and chemical resistance, are widely used around the world, with an annual consumption of over 60 million tons. However, their crosslinked structures make them difficult to recycle. This study presents a new method for preparing recyclable thermoset plastics by crosslinking a commodity polymer, polyacrylonitrile (PAN), with a small percentage of a Ru complex via nitrile-Ru coordination. The resulting thermoset plastics exhibit impressive mechanical performance and can be de-crosslinked and re-crosslinked, enabling recycling from plastic waste mixtures.
ADVANCED MATERIALS
(2023)
Article
Chemistry, Inorganic & Nuclear
Wenke Yuan, Weize Wang, Peipei Cen, Huifang Zhou, Xiangyu Liu, Bo Liu
Summary: Using adenine and metal ions to construct secondary building units, further connected by a highly symmetrical multicarboxylic linker, two stable amino-modified porous frameworks with high porosity and stability have been successfully synthesized. These frameworks exhibit high selectivity and capacity for adsorption and separation functions.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Dan Qi, Jinrui Bai, Haoxiang Zhang, Bin Li, Zhuoheng Song, Na Ma, Lin Guo, Lijuan Song, Wujiong Xia
Summary: A versatile photochemical ring contraction method for the synthesis of oxetanes under catalyst-free conditions is reported. The reaction utilizes 2,5-dihydrofurans and diazo compounds under visible light irradiation, producing functionalized 3-vinyloxetanes as major products.
Article
Chemistry, Organic
Peter R. Schreiner, Lars Rummel, Kai Hanke, Jonathan Becker
Summary: In this study, the thermodynamic stability of cis- and trans-alkenes substituted with dispersion energy donor (DED) groups was investigated through a combination of experimental and computational methods. The equilibrium between the two isomers was found to shift towards the more crowded cis-alkene as the substituent size increased. Noncovalent interactions, particularly long-range dispersion (LD) and Pauli exchange repulsion, were identified as the dominant factors influencing the equilibrium between cis- and trans-alkenes.
Article
Chemistry, Inorganic & Nuclear
Ruifang Wang, Chun -Sing Lee, Zhenpin Lu
Summary: Boron-doped polycyclic aromatic hydrocarbons are a new class of materials with modified electronic properties, resulting in new photophysical and optoelectronic properties. They have great potential in the field of organic optoelectronics.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
David King, Tatjana Sumanovac, Steven Murkli, Peter R. Schreiner, Marina Sekutor, Lyle Isaacs
Summary: We synthesized quaternary (di)cationic triamantane derivatives G1 and G3 by permethylating the corresponding primary ammonium ions G2 and G4. The complexation behaviors of G1-G4 with CB[7] and CB[8] were examined using H-1 NMR spectroscopy. CB[8] fully encapsulated G1-G4 while CB[7] formed inclusion complexes with G1, G2, and G4 but could not fully encapsulate the central hydrophobic core of G3. The geometries of the CB[n]-guest complexes were determined by analyzing complexation-induced changes in chemical shifts and confirmed using molecular modeling.
NEW JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Weiyu Qian, Raffael C. Wende, Peter R. Schreiner, Artur Mardyukov
Summary: The interstellar candidate phosphorus mononitride PN, a metastable species, was generated through high-vacuum flash pyrolysis of (o-phenyldioxyl)phosphinoazide in cryogenic matrices. Although the PN stretching band was not directly detected because of its low infrared intensity and possible overlaps with other strong bands, o-benzoquinone, carbon monoxide, and cyclopentadienone as additional fragmentation products were clearly identified. Moreover, an elusive o-benzoquinone-PN complex formed when (o-phenyldioxyl)phosphinoazide was exposed to UV irradiation at lambda=254 nm. Its recombination to (o-phenyldioxyl)-lambda(5)-phosphinonitrile was observed upon irradiation with the light at lambda=523 nm, which demonstrates for the first time the reactivity of PN towards an organic molecule. Energy profile computations at the B3LYP/def2-TZVP density functional theory level reveal a concerted mechanism. To provide further evidence, UV/Vis spectra of the precursor and the irradiation products were recorded and agree well with time-dependent DFT computations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Julia Ruhl, Nils Oberhof, Andreas Dreuw, Hermann A. Wegner
Summary: The incorporation of heteroatoms into hydrocarbon compounds greatly expands the chemical space of molecular materials. B-N doping has gained significant attention due to its isosterism with a C=C bond. In this study, a new and modular synthetic concept was presented to access novel diazadiborabenzo[b]triphenylenes using B-N doped biradical as intermediate. The photophysical properties revealed that the emission spectra of the diazadibora compounds can be conveniently tuned by small changes in the boron atom substitution. The new synthetic strategy provides an elegant route to various novel B-N doped acenes with great potential for applications in molecular materials.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Jack McAlpine, Alex Bloemendal, Jeremy E. Dahl, Robert M. K. Carlson, Ilia A. Guzei, Catherine F. M. Clewett, Boryslav O. Tkachenko, Peter R. Schreiner, Matthew A. Gebbie
Summary: As the deployment of large-scale lithium-ion batteries accelerates, the use of flammable organic electrolytes exacerbates the problem of battery fires during operation and disposal. Ionic liquid-derived electrolytes promise to be safe and nonflammable alternatives, but their use is hindered by poor lithium transport. However, a new study reports the design and characterization of novel ionic liquid-inspired organic electrolytes that leverage the unique self-assembly properties of diamondoids to enhance lithium-ion mobility.
CHEMISTRY OF MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Felix Bernt, Hermann A. Wegner
Summary: Breaking the centrosymmetry of [n]cycloparaphenylenes ([n]CPPs) by one meta connection, leads to bright emission in the typically non-fluorescent smaller derivatives, while maintaining their size-dependent emissive properties. Nitrile-substituted meta[n]CPPs (n=6, 8, 10) were prepared using the building block strategy for [n]CPPs. The nitrile substituent offers a convenient handle for functional group conversions and the photophysical properties of these novel m[n]CPP derivatives were characterized. The host-guest ability of cyano-m[10]CPP with fullerene C-60 was also explored, revealing new applications in synthetic organic chemistry, material sciences, and biomedical research.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Agriculture, Multidisciplinary
Fabio F. Brescia, Maximilian Koch, Raffael C. Wende, Peter R. Schreiner, Holger Zorn, Marco A. Fraatz
Summary: Among the aroma compounds formed by Cystostereum murrayi, highly potent bicyclic benzofuran derivatives are found. In addition to dill ethers, the fungus also produces two stereoisomers of a rare compound called dihydromenthofurolactones and a C3-unsaturated analogue. Analysis of reference standards allowed for the identification of the formed stereoisomers.
JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY
(2023)
Editorial Material
Chemistry, Multidisciplinary
Karsten Danielmeier, Peter R. Schreiner
Summary: The German Chemical Society (GDCh) has chosen "Rethinking Chemistry" as the guiding principle to address challenges related to climate change, loss of natural resources, and geopolitical conflicts. By encouraging scientists to approach chemistry from different perspectives, the GDCh aims to foster innovative and sustainable advancements in the field. This motto is also reflected in the upcoming GDCh Science Forum Chemistry (WiFo) 2023 and a dedicated Special Collection in Angewandte Chemie, showcasing the various aspects of Rethinking Chemistry.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Multidisciplinary
Haokun Li, Gan Xu, Shuchang Li, Yuhao Wu, Zhenpin Lu
Summary: Electron-precise B-B bonded compounds are valuable reagents in organic syntheses, and can be used as key starting material for the synthesis of functionalized organoboranes. Recently, many well-designed/reactive electron-precise B-B bonded compounds have been developed, which could facilitate direct reactions with small molecules, unsaturated substrates, and electrophiles. This review highlights the synthesis, structure, and reactivity of neutral and anionic B-B bonded compounds.
Article
Chemistry, Physical
Marcel Ruth, Dennis Gerbig, Peter R. Schreiner
Summary: To meet the demand for fast and accurate electronic energies of larger systems, a database of optimized small organic monomers and dimers was created, including various levels of theory calculations. Machine learning models based on graph neural networks were trained using this database, achieving high accuracy in energy predictions for both monomers and dimers. The models were validated and tested on different databases and challenging systems.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Organic
Andrey A. Fokin, Vladyslav V. Bakhonsky, Alexander E. Pashenko, Emirali Bakhiiev, Jonathan Becker, Simon Kunz, Peter R. Schreiner
Summary: In this study, anti- and syn-sesquihomodiamantenes (SDs) were synthesized and their structural characteristics were investigated. The experimental oxidation potentials obtained from cyclic voltammetry showed a good correlation with the density functional theory-computed ionization potentials of unsaturated diamondoid dimers. The similar geometries of both reduced and ionized SD states were supported by the spatial sheltering of the beta-hydrogen, making SDs promising building blocks for highly stable and carrier mobile diamond materials.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Guanqi Qiu, Peter R. Schreiner
Summary: This study introduces the concepts of intrinsic and thermodynamic contributions to the barrier width in chemical reactions. Experimental and theoretical studies are used to demonstrate their distinct roles. The findings shed light on conflicting trends in chemical reactivities and contribute to a more comprehensive understanding of chemical reactions.
ACS CENTRAL SCIENCE
(2023)
Review
Materials Science, Multidisciplinary
Yuhao Wu, Shuchang Li, Haokun Li, Ruquan Ye, Zhenpin Lu
Summary: In recent years, there has been significant research interest in boron-containing macrocycles. This review summarizes reported examples of boron macrocycles with alkyl/aryl borane units, B-O bonds, and B-N bonds, highlighting their synthesis and structure. Additionally, potential applications of these boron-containing macrocycles in anion sensing, host-guest interactions, and supramolecular catalysis are briefly introduced.
JOURNAL OF MATERIALS CHEMISTRY C
(2023)
Article
Chemistry, Multidisciplinary
Torben Sassmannshausen, Anne Kunz, Nils Oberhof, Friederike Schneider, Chavdar Slavov, Andreas Dreuw, Josef Wachtveitl, Hermann A. Wegner
Summary: By synthesizing novel azobenzene-spiropyran dyads, we achieved complex photochemical control of molecular materials and nanostructures. Two different orthogonally photoswitchable systems were obtained through different connectivity patterns.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
