Article
Biochemistry & Molecular Biology
Chen Sun, Jennifer L. Jaimes, Alec H. Follmer, Joseph W. Ziller, Andrew S. Borovik
Summary: Non-heme Fe monooxygenases activate C-H bonds using intermediates with high-spin Fe-IV-oxido centers. A new tripodal ligand [pop](3-) was prepared to mimic these sites and stabilize metal centers in high oxidation states. The ligand was used to generate [Fe(IV)pop(O)](-), which showed reactivity with benzyl alcohol, suggesting the importance of hydrogen bonding interactions for reactivity.
Article
Chemistry, Multidisciplinary
Bijoy Dey, Jordi Cirera, Sakshi Mehta, Liliana P. Ferreira, Ramar Arumugam, Abhishake Mondal, Paulo N. Martinho, Vadapalli Chandrasekhar
Summary: Steric effects of ligand substituents on Fe(III) complexes were investigated, revealing that larger substituents maintain a high-spin state while smaller substituents exhibit spin-crossover behavior, due to the distortion of the complex structure.
CRYSTAL GROWTH & DESIGN
(2023)
Article
Chemistry, Multidisciplinary
Valentina Milasinovic, Kresimir Molcanov
Summary: The structural analysis of six new co-crystals revealed the presence of sandwich-like I-quinone-I- structures, with the competition between this motif and halogen bonding being described for the first time. The black color of the crystals indicates charge transfer from iodide to the quinoid ring, interpreted as n -> pi*. Intermolecular interactions were analyzed using Hirshfeld surfaces and Voronoi-Dirichlet polyhedra.
Article
Chemistry, Physical
Vyshnavi Vennelakanti, Michael G. Taylor, Aditya Nandy, Chenru Duan, Heather J. Kulik
Summary: In this study, the electronic and Gibbs free energies associated with spin crossover in 95 Fe(II) SCO complexes were investigated using density functional theory (DFT) with 30 different functionals. It was found that a modified version of B3LYP, M06-L, and TPSSh functionals accurately predict the spin crossover behavior of most complexes, while the MN15-L functional fails to predict any spin crossover behavior.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Peter Comba, George Nunn, Frederik Scherz, Paul H. Walton
Summary: The study focuses on the reactivity and comparison with hemoglobin iron enzymes of a nonheme iron (IV)-oxido complex.
FARADAY DISCUSSIONS
(2022)
Article
Chemistry, Multidisciplinary
Cuiju Yu, Qingqing Feng, Xingxing Li, Jinlong Yang
Summary: This study reveals the significant influence of the spinterface between magnetic electrodes and molecules on spin filtering efficiency through first-principles calculations. The results show that interface configurations can modulate and reverse the spin polarization of tunnelling electrons. The performance of single molecule spintronic devices, such as the spin filtering channel, can be flexibly tuned through suitable interface design.
Editorial Material
Chemistry, Multidisciplinary
Dipankar Sahoo, Diana A. Iovan
Summary: A recent study reported the isolation and characterization of an N-trifluoromethyl-substituted Fe(IV) bisimido species that undergoes intramolecular C-H activation. This discovery opens up new possibilities for N-group-transfer chemistry.
Article
Chemistry, Inorganic & Nuclear
Tomoyo Misawa-Suzuki, Hirotaka Nagao
Summary: Ru(iv)-Ru(iv) complexes with a doubly oxido-bridged diamond core and bridging carbonate or hydrogen carbonate ligands were synthesized from the corresponding carbonato-bridged Ru(iii)-Ru(iv) complex. The structures of [IV,IV](ClO4)(2) and [IV,IV_1H](ClO4)(3) were characterized. The electrochemical and spectroscopic properties of [IV,IV](2+) and [IV,IV_1H](3+) in organic solvents and aqueous solutions, as well as their reactivity towards organic solvents and substrates, were investigated. This is the first systematic comparison of Ru(iv)-Ru(iv) species and corresponding Ru(iii)-Ru(iv) complexes in the same tridentate ligand system.
DALTON TRANSACTIONS
(2023)
Review
Chemistry, Multidisciplinary
Kamran T. Mahmudov, Fatali E. Huseynov, Vusala A. Aliyeva, M. Fatima C. Guedes da Silva, Armando J. L. Pombeiro
Summary: Lanthanide complexes have diverse structures and properties, and the design of the secondary coordination sphere is crucial for their development as functional materials. Various interactions, such as hydrogen bonds, halogen bonds, and pi interactions, are used to decorate the secondary coordination sphere of lanthanide complexes.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Nanoscience & Nanotechnology
Ying Zhu, Yifan Gao, Yiqing Lu, Yuanhui Cheng
Summary: This study investigates the effect of noncovalent interactions on the performance of oxygen reduction reaction (ORR) using a synthesized Fe-N-C single-atom catalyst. It is found that TEA(+) plays a positive role in tuning the outer Helmholtz plane, improving oxygen diffusion coefficient, and increasing double-layer capacitance, enhancing the activity, selectivity, and stability of the catalyst towards ORR.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Inorganic & Nuclear
Zhi-Jian Ouyang, Xiao-Ying Mo, Jia-Qi Ye, Xiao-Xuan Yu, Shu-Yuan Huang, Xiao-Ling Liu, Wen-Bin Chen, Song Gao, Wen Dong
Summary: Two ion-pair Fe(iii) complexes were synthesized by employing the tridentate ligand H(3)ATD, with one in low-spin state and the other undergoing high temperature spin crossover between 360 and 500 K. The magnetic measurements and magneto-structural relationship studies reveal the crucial role of interactions between the cation and anion in the high temperature Fe(iii) behavior.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Physical
Alejandro Martinez Serra, Archit Dhingra, Maria Carmen Asensio, Jose Antonio Real, Juan Francisco Sanchez Royo
Summary: Temperature dependent X-ray photoemission spectroscopy (XPS) was used to study the Fe 2p and N 1s core levels of Fe(ii) spin crossover (SCO) complexes. The Fe 2p core-level spectra showed spin state transitions in these SCO complexes, consistent with previous studies. The temperature dependence of the N 1s core-level binding energy provided further insights into the ligand-to-metal charge transfer phenomenon.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Thilini K. Ekanayaka, Hannah Kurz, Kayleigh A. McElveen, Guanhua Hao, Esha Mishra, Alpha T. N'Diaye, Rebecca Y. Lai, Birgit Weber, Peter A. Dowben
Summary: The spin state transition behavior of Fe(ii) spin crossover coordination polymer crystallites at the surface differs from the bulk, possibly due to factors such as oxidation, differences in surface packing, and changes in coordination. Some Fe(ii) spin crossover coordination polymers may be photoactive enough to prevent discernment of the spin state transition using X-ray spectroscopies.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Multidisciplinary
Augustin Braun, Leland B. Gee, Michael W. Mara, Ethan A. Hill, Thomas Kroll, Dennis Nordlund, Dimosthenis Sokaras, Pieter Glatzel, Britt Hedman, Keith O. Hodgson, A. S. Borovik, Michael L. Baker, Edward I. Solomon
Summary: Fe K-edge XAS is widely used for studying high-valent iron intermediates in catalysts. The 4p-mixing into the 3d orbitals complicates the analysis, but understanding it correctly enables deeper insights into the structure and reactivity. This study reveals that the loss of inversion in the equatorial plane leads to 4p mixing into the 3dx2-y2,xy orbitals, providing structural insights for distinguishing 6- vs 5-coordinate active sites. Furthermore, the study investigates the electronic structure of Fe(IV)=O active sites and their reactivity selectivity through O K-edge XAS.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Inorganic & Nuclear
Tomoyo Misawa-Suzuki, Sota Mafune, Hirotaka Nagao
Summary: This study presents a diruthenium(III,IV) complex with a doubly oxido-bridged core and a carbonato bridged between the two ruthenium centers, exploring interactions with cations. In acidic aqueous solutions, the carbonato ligand remained bound to the doubly bridged core, undergoing reversible protonation/deprotonation reactions. The structures of the protonated complexes were successfully characterized.
INORGANIC CHEMISTRY
(2021)
Article
Oncology
Mili Zhang, Can Cao, Xu Li, Qisheng Gu, Yixin Xu, Ziyan Zhu, Duogang Xu, Shanshan Wei, Haonan Chen, Yuqin Yang, Hugh Gao, Liang Yu, Jikun Li
Summary: This study identified the EMT signaling pathway as a representative pathway for predicting the survival of MSI-H gastric cancer (GC) patients. A novel five-gene signature (CALU, PCOLCE2, PLOD2, SGCD, and THBS2) was established from the EMT signaling gene set for disease outcome prediction. The five genes were found to be abundantly expressed in cancer-associated fibroblasts, and patients with different risk groups based on the five-gene signature showed distinct patterns of tumor immune microenvironment.
Article
Chemistry, Multidisciplinary
Pei Zhang, Xinchen Kang, Liming Tao, Lirong Zheng, Junfeng Xiang, Ran Duan, Jikun Li, Peng Chen, Xueqing Xing, Guang Mo, Zhonghua Wu, Buxing Han
Summary: This study discovered a stable radical solution that allows for rapid synthesis of various MOFs with different metal nodes and ligands at room temperature without external energy. MOFs with conjugated ligands achieved instantaneous architecture formation with a 100% yield. The mechanism was thoroughly investigated using multiple techniques.
Article
Chemistry, Multidisciplinary
De-Hui Tuo, Shuxuan Tang, Pengfei Jin, Jikun Li, Xinping Wang, Chuang Zhang, Yu-Fei Ao, Qi-Qiang Wang, De-Xian Wang
Summary: This article presents the synthesis, crystal structures, and physical properties of novel benzene triimide (BTI) radical anions, focusing on the relationship between molecular structure, spin-spin intermolecular interactions, and physical properties in the crystalline state. The radical species exhibited diverse intermolecular stackings in the crystalline state, resulting in different spin-spin interactions and various physical properties. The structure-property relationship was studied in terms of magnetism and conductivity, showing that the radical pi-pimers and pi-stacks with effective charge transport exhibited paramagnetic property and conductivity at room temperature.
Article
Chemistry, Multidisciplinary
Ji-Kun Li, Xing-Yu Chen, Wen-Long Zhao, Yun-Long Guo, Yi Zhang, Xin-Chang Wang, Andrew C. -H. Sue, Xiao-Yu Cao, Meng Li, Chuan-Feng Chen, Xiao-Ye Wang
Summary: In this study, a new design strategy is proposed to achieve chiral nanographenes with high fluorescence quantum yields by helical pi-extension of strongly luminescent chromophores. The synthesized chiral nanographene, with perylene as the core and two dibenzo[6]helicene fragments as the wings, exhibits a record high fluorescence quantum yield of 93% among reported chiral nanographenes and excellent circularly polarized luminescence brightness of 32 M-1 cm(-1).
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Tongtong Jia, Di Meng, Ran Duan, Hongwei Ji, Hua Sheng, Chuncheng Chen, Jikun Li, Wenjing Song, Jincai Zhao
Summary: Prospects in light-driven water activation have led to rapid progress in hydrogenation reactions. In this study, a Ni2+-N-4 site built on carbon nitride was used for catalyzing the semihydrogenation of alkynes with water providing protons, powered by visible-light irradiation. Importantly, this photocatalytic approach enabled the production of diverse deuterated alkenes in D2O with excellent deuterium incorporation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Materials Science, Multidisciplinary
Xing-Yu Chen, Ji-Kun Li, Wen-Long Zhao, Cheng-Zhuo Du, Meng Li, Chuan-Feng Chen, Xiao-Ye Wang
Summary: By using aza[7]helicene as the chiral donor and triazine as the acceptor, a new type of circularly polarized luminescence material has been developed. The influence of the dihedral angle between the donor and acceptor moieties on the dissymmetry factors has been revealed for the first time, offering a novel strategy to enhance dissymmetry factors through engineering the dihedral angles in donor-acceptor type chiral materials.
JOURNAL OF MATERIALS CHEMISTRY C
(2023)
Article
Materials Science, Multidisciplinary
Cheng-Zhuo Du, Yang Lv, Hengyi Dai, Xiangchen Hong, Jianping Zhou, Ji-Kun Li, Rong-Rong Gao, Dongdong Zhang, Lian Duan, Xiao-Ye Wang
Summary: A new family of indole-fused multi-resonance thermally activated delayed fluorescence materials have been developed, which exhibit narrowband blue emission with a small full width at half maximum of 22-23 nm. High maximum external quantum efficiencies of up to 16.8% have been achieved in organic light-emitting diodes. Furthermore, it is unveiled that peripheral substitutions can not only promote device efficiency but also help to maintain narrowband emission under high dopant concentrations.
JOURNAL OF MATERIALS CHEMISTRY C
(2023)
Article
Chemistry, Multidisciplinary
Yucui Zhao, Tingting Lu, Yanwei Song, Yanqin Wen, Zheng Deng, Jiahui Fan, Minghui Zhao, Ruyi Zhao, Yuntao Luo, Jianzhu Xie, Binjie Hu, Haoran Sun, Yiwei Wang, Sijia He, Yanping Gong, Jin Cheng, Xinjian Liu, Liang Yu, Jikun Li, Chuanyuan Li, Yongyong Shi, Qian Huang
Summary: Cancer cells enter a radiation-tolerant persister state by poly- and de-polyploidization to survive radiotherapy and repopulate the tumor, suggesting a new therapeutic concept to improve outcome of patients receiving radiotherapy.
Article
Chemistry, Multidisciplinary
Mehmet Can, Macon J. Abernathy, Seth Wiley, Claire Griffith, Christopher D. James, Jin Xiong, Yisong Guo, Brian M. Hoffman, Stephen W. Ragsdale, Ritimukta Sarangi
Summary: The Wood-Ljungdahl Pathway is a biological mechanism that fixes carbon dioxide and carbon monoxide through nickel-based organometallic intermediates. The key steps in this metabolic cycle involve CO dehydrogenase and acetyl-CoA synthase (CODH/ACS), which are complex nickel-iron-sulfur proteins. This study characterizes the nickel-methyl and nickel-acetyl intermediates in ACS, completing the understanding of all proposed organometallic intermediates. It suggests that the Ni-p intermediates undergo redox changes and equilibrate among different states, while geometric changes control the entry of CO and the methyl group.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Wenjuan Zhu, Akhilesh Kumar, Jin Xiong, Macon J. Abernathy, Xiao-Xi Li, Mi Sook Seo, Yong-Min Lee, Ritimukta Sarangi, Yisong Guo, Wonwoo Nam
Summary: The nature of reactive intermediates and the cis-dihydroxylation mechanism of arenes and olefins have been studied extensively in the past few decades. In this study, the reaction between a spectroscopically characterized mononuclear nonheme iron(III)-peroxo complex and olefins and naphthalene derivatives has been investigated. The results show that the nonheme iron(III)-peroxo complex is a nucleophile and reacts with olefins and naphthalenes to yield cis-diol products. This study presents the first example of cis-dihydroxylation of substrates by a nonheme iron(III)-peroxo complex.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Jared C. Paris, Sha Hu, Aiwen Wen, Andrew C. Weitz, Ronghai Cheng, Leland B. Gee, Yijie Tang, Hyomin Kim, Arturo Vegas, Wei-chen Chang, Sean J. Elliott, Pinghua Liu, Yisong Guo
Summary: This study reports the first observation of a spin iron(IV) species in non-heme iron enzymes, which enables the formation of C-S bond catalyzed by OvoA in Methyloversatilis thermotolerans. This finding paves the way for understanding the mechanism of enzymatic oxidative C-S bond formation in the OSHA biosynthesis pathway.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Bingnan Wang, Yong Lu, Lide Cha, Tzu-Yu Chen, Philip M. Palacios, Liping Li, Yisong Guo, Wei-chen Chang, Chuo Chen
Summary: In this study, it was discovered that mononuclear nonheme iron(II) and 2-oxoglutarate (Fe/2OG)-dependent oxygenases and halogenases can catalyze diverse oxidative reactions, including hydroxylation, halogenation, epoxidation, and desaturation. In addition to known reactions, these enzymes were found to catalyze the Mukaiyama hydration, which proceeds via a hydrogen atom transfer pathway without involvement of 2OG. Unlike conventional inorganic catalysts, the Fe/2OG enzymes utilize a mononuclear iron center for this reaction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Inorganic & Nuclear
Reese A. Clendening, Stephanie S. Delancey, Andrew T. Poore, Shan Xue, Yisong Guo, Shiliang Tian, Tong Ren
Summary: Ferric bis-alkynyl complexes bearing redox-active substituents were characterized and the mixed valent properties of the singly oxidized species were investigated. The nature of the supporting macrocyclic ligand strongly influenced the degree of valence delocalization through the metal center. A tetraimine macrocycle enhanced valence delocalization, which was related to the altered ground state of the unoxidized complexes. The study provides insights into macrocyclic ligand-dependent valence delocalization and the role of π-acidity in the electronic structure of the complexes.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Richiro Ushimaru, Lide Cha, Shotaro Shimo, Xiaojun Li, Jared C. Paris, Takahiro Mori, Kazunori Miyamoto, Lindsay Coffer, Masanobu Uchiyama, Yisong Guo, Wei-chen Chang, Ikuro Abe
Summary: In this study, the catalytic mechanism and stereodivergency of BelL and HrmJ enzymes were investigated. The results showed that the nitroalkane moiety of the substrate is deprotonated to produce the nitronate form, and an iron(IV)-oxo species abstracts proS-H from C4 to initiate intramolecular C-C bond formation. Additionally, the study discovered new homologues that generate cis-configured Ncpa products with different stereochemistries, and identified the critical amino acid residues controlling the stereoselectivity of cyclopropanation.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Multidisciplinary Sciences
Shichao Xu, Haifeng Wu, Siyuan Liu, Peidong Du, Hui Wang, Haijun Yang, Wenjie Xu, Shuangming Chen, Li Song, Jikun Li, Xinghua Shi, Zhen-Gang Wang
Summary: In this study, a supramolecular mimetic enzyme with catechol oxidase-like copper-cluster active sites was synthesized. This catalyst exhibits catalytic functions similar to those of copper cluster-dependent oxidases, and its performance surpasses previously reported artificial complexes.
NATURE COMMUNICATIONS
(2023)