Article
Chemistry, Inorganic & Nuclear
Hai-Jun Li, Rui Feng, Gao-Xiang Wang, Junnian Wei, Zhenfeng Xi
Summary: By reacting semi-rigid PNP ligand with CoBr2, complex PNPCoBr (1) was obtained. The reduction of 1 with excess amounts of KC8 in THE under a N-2 atmosphere yielded binuclear cobalt dinitrogen anion complex [Co(mu-Cy2P)PCyN2](2)K (2) by cleaving the C-P bond of the PNP ligand. Adding 2,2,2-cryptand into complex 2 effectively prepared ion pair Co complex, [Co(mu-Cy2P)PCyN2](2)K(crypt-222) (3). The structures of 1, 2, and 3 were determined by single-crystal X-ray diffraction analysis, and N-2 is moderately activated in complexes 2 and 3. DFT calculations suggest the presence of a Co-Co bond in 2 and 3. Compounds 1 and 2 exhibit catalytic activity for the transformation of N-2 to N(SiMe3)(3).
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Multidisciplinary
Masataka Noguchi, Qiyue Mao, Atsuki Nakagami, Hiroaki Kitagishi
Summary: Iron(ii/iii) porphyrin/cyclodextrin inclusion complexes are used as hemoprotein models in vivo. Our study found that the iron(iii) porphyrin complex is spontaneously reduced to the iron(ii) state in mouse circulation. The reduced complex binds endogenous CO from carboxyhemoglobin and is excreted in urine. The natural reduction system is effective for synthetic heme-model compounds.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Pokhraj Ghosh, Molly Stauffer, Valiallah Hosseininasab, Subrata Kundu, Jeffery A. Bertke, Thomas R. Cundari, Timothy H. Warren
Summary: Copper nitrite reductases convert nitrite ions to nitric oxide and nitrous oxide at high levels of nitrogen oxide flux. The assembly of nitric oxide at a single copper site to form copper cis-hyponitrites has been demonstrated in the presence of an external reductant. Furthermore, the removal of a fraction of the structure in the copper cis-hyponitrite complex can be achieved by adding specific reagents, resulting in the formation of a spectroscopically similar anion. These studies provide insights into the reductive coupling of nitrogen oxides at a single copper center and the utilization of the strong oxidizing power of nitrite.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Martin Keilwerth, Liam Grunwald, Weiqing Mao, Frank W. Heinemann, Joerg Sutter, Eckhard Bill, Karsten Meyer
Summary: A new supporting ligand TIMMNMes was developed to isolate an air-stable iron(V) complex with a terminal nitrido ligand, synthesized by one-electron oxidation from an iron(IV) precursor. Single-crystal X-ray diffraction analyses showed metal-centered oxidation elongating the iron nitride bond, bringing the high-valence iron center closer to a trigonal bipyramid. Fe-57 Mossbauer, EPR, UV/vis electronic absorption spectroscopy, and quantum chemical calculations identified the factors affecting the structure and electronic nature of the complex.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Xiao-Lin Liu, Yi Li, Qing-Dou Xu, Zi-Qin Wei, Xin-Tao Wu, Tian-Lu Sheng
Summary: In this work, a pair of asymmetric cyanido-bridged binuclear Ru-CN-Ru-Cl complexes were reported. The structures and properties of these complexes were well characterized. It was found that 1(2+) is the first structurally characterized asymmetric cyanido-bridged Class III mixed-valence complex.
NEW JOURNAL OF CHEMISTRY
(2022)
Article
Energy & Fuels
Kefeng Xie, Shengyuan Xu, Kai Xu, Jie Wang, Longjun Ma, Jun -Bing Lin
Summary: CO produced by incomplete combustion is a significant threat to the environment and human health. A stable single iron atom two-dimensional porphyrin sheet (Fe-TDPS) was designed to serve as a catalyst for CO oxidation, increasing catalytic activity and reducing costs. The reaction mechanism was investigated using density functional theory, and results indicated that Fe-TDPS can be used as a catalyst for mild CO oxidation.
Article
Chemistry, Physical
Venkatesh Piradi, Guitao Feng, Muhammad Imran, Jianzhang Zhao, Feng Yan, Xunjin Zhu
Summary: Porphyrins are highly adaptable materials for organic photovoltaics due to their adjustable functional groups. In this study, two porphyrin-based small molecule donors, IDT-2TPE and TPE, were synthesized. The device based on the IDT-2TPE donor and IDTCR nonfullerene acceptor showed a broad photoelectron response up to 1000 nm and a power conversion efficiency of 10.41%, while the device based on the TPE donor and IDTCR acceptor had a much lower efficiency of 4.22%. The improved performance of the IDT-2TPE/IDTCR device was attributed to its higher photocurrent generation and more favorable surface morphology with elevated charge carrier mobilities.
ACS APPLIED ENERGY MATERIALS
(2023)
Article
Chemistry, Physical
Mae Feo, Nikki J. Bakas, Aleksa Radovic, William Parisot, Anne Clisson, Lise-Marie Chamoreau, Mansour Haddad, Virginie Ratovelomanana-Vidal, Michael L. Neidig, Guillaume Lefevre
Summary: In this work, the design of stable iron(0) complexes with a phenanthroline-type ligand (phen) for cycloaddition catalysis is explored. The utilization of phen ligand in reduced iron oxidation states is challenging due to its strong noninnocence, resulting in unstable species. However, by strategically protecting the C4 and C7 positions of the phen ring, a stable (N,N)2Fe complex is obtained, which exhibits excellent thermal and kinetic stability and can be easily used as a precursor in catalytic processes. The electronic structure and catalytic activity of this noninnocent complex in alkyne [2 + 2 + 2] cyclizations are discussed.
Article
Chemistry, Multidisciplinary
Tingxia Wang, Lulu Guo, Zhuo Jiang, Shengtao Chen, Shuran Xu, Yuexing Zhang, Jing Zhang, Renjie Li, Tianyou Peng
Summary: A novel pincer complex-bridged porphyrin polymer synthesized in this study exhibits excellent electrocatalytic hydrogen evolution reaction (HER) performance and potential for fabricating photoelectrochemical (PEC) cells. The experimental and theoretical studies suggest that the Cu/Ru heterobimetallic centers in the polymer enhance electron transfer and regulate electronic properties, boosting (photo)electrocatalytic activity for HER. This strategy provides a new approach to fabricate porphyrin-based polymers for effective HER (photo)electrocatalysis.
ADVANCED FUNCTIONAL MATERIALS
(2021)
Article
Nanoscience & Nanotechnology
Linyu Cao, Jingjun Li, Zhi-Qiang Zhu, Liang Huang, Jian Li
Summary: This study introduces a stable and efficient near-infrared Pt(II) porphyrin complex, PtTPTNP-F-8, which emits a large portion of photons with wavelengths longer than 900 nm. By introducing fluorine atoms on the meta positions of all four phenyl groups, the complex overcomes thermal instability issues and achieves high sublimation yield and peak device efficiency. The NIR OLED device using PtTPTNP-F-8 as an emissive material exhibits exceptional operational stability with an LT99 lifetime of over 1000 hours.
ACS APPLIED MATERIALS & INTERFACES
(2021)
Article
Chemistry, Physical
Yuqin Dou, Xin Yang, Qi Wang, Zhaodi Yang, Aijian Wang, Long Zhao, Weihua Zhu
Summary: In this study, a novel cobalt porphyrin (CoTAPP)-bridged covalent triazine polymer (CoTAPPCC) was prepared for electrocatalytic hydrogen evolution reaction (HER) by covalently linking CoTAPP with cyanuric chloride (CC). Experimental techniques and density functional theory (DFT) calculations were used to evaluate the correlation of HER activity with molecular structures. The strong electronic interactions between the CC unit and the CoTAPP moiety result in a standard current density of 10 mA cm-2 with a low overpotential of 150 mV in acid, which is comparable to or better than the best records reported previously. Additionally, CoTAPPCC exhibits competitive HER activity in basic medium. This strategy is valuable for designing and developing efficient porphyrin-based HER electrocatalysts.
JOURNAL OF COLLOID AND INTERFACE SCIENCE
(2023)
Article
Chemistry, Multidisciplinary
Akito Nakai, Takayuki Tanaka, Atsuhiro Osuka
Summary: It was found that the internally-bridged octaphyrin underwent rearrangement to form a new metamorphosis of meso-meso linked porphyrin dimer. Extensive examination revealed that hydride-addition played a crucial role in the rearrangements, leading to thermodynamically more stable porphyrin framework. Additionally, beta-tetrabromo[36]octaphyrin was transformed to meso-meso, beta-beta, beta-beta triply linked porphyrin dimer through a similar mechanism combined with Pd-mediated reductive homocoupling.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Yixin Zhang, Jinfeng Zhao, Dawei Yang, Baomin Wang, Yuhan Zhou, Junhu Wang, Hui Chen, Tao Mei, Shengfa Ye, Jingping Qu
Summary: Researchers have discovered a well-described multi-iron nitrido model complex with excellent reactivity towards converting hydrogen and nitrogen gas into high-yield ammonia under ambient conditions. These studies have overcome the previous challenges of converting nitrides to ammonia and provided new insights.
Article
Chemistry, Multidisciplinary
Peng Lin, Shugang Xiong, Yutao Rao, Ling Xu, Mingbo Zhou, Bangshao Yin, Atsuhiro Osuka, Jianxin Song
Summary: Intramolecular fusion reactions of a p-terphenylene-bridged Ni-II porphyrin dimer led to the formation of different products depending on the reaction conditions. Oxidation with Fe(OTf)(3) resulted in the syn- and anti-doubly heptagon-fused Ni-II porphyrin dimers, which exhibited enlarged pi-electronic networks likely through a radical mechanism. Treatment with methanesulfonic acid, on the other hand, produced a spiro-pentagon-bridged Ni-II chlorin dimer via acid-catalyzed Friedel-Crafts type cyclization. Additionally, a doubly octagon-fused Ni-II porphyrin dimer was synthesized through a sequence of double meso-formylation, reduction to corresponding diol, and BF3-catalyzed cyclization.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Sarah E. Braley, Hyuk-Yong Kwon, Song Xu, Evan Z. Dalton, Elena Jakubikova, Jeremy M. Smith
Summary: This study investigates the activation of a cobalt complex in the reduction of aqueous nitrite through a combination of experimental and computational approaches. The presence of phosphate buffer enhances catalytic efficiency, with increased current and decreased overpotential, although high concentrations have an inhibitory effect. Mechanistic investigations reveal the vital role of phosphate buffer as a proton shuttle.
INORGANIC CHEMISTRY
(2022)
