Article
Chemistry, Multidisciplinary
Wen-Jun Xie, Jin-Mei Chen, Zhi-Wen Yang, Liang-Nian He
Summary: A novel molecular catalyst, cobalt 5,15-diazaporphyrin, was developed and immobilized onto carbon nanotubes for highly efficient electrocatalytic CO2 reduction to CO. The catalyst exhibited a faradaic efficiency above 99% at -0.7 V and -0.8 V versus a reversible hydrogen electrode. The decrease in electronegative nitrogen atoms at the meso position effectively increased the electron density of the central metal, facilitating the reaction with Lewis acid CO2.
Article
Chemistry, Inorganic & Nuclear
W. Ryan Osterloh, Nicolas Desbois, Claude P. Gros, Karl M. Kadish
Summary: A series of cobalt nitrophenylcorroles were examined and found to exhibit hypercorrole spectra, which depends on the substitution position and electronic structure of the corrole.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Haruki Nagae, Saki Matsushiro, Jun Okuda, Kazushi Mashima
Summary: We discovered that a cationic hetero tetranuclear complex with a calcium and three cobalt ions demonstrated high catalytic activity for the alternating copolymerization of propylene oxide (PO) and carbon dioxide (CO2). The tertiary anilinium salt [PhNMe2H][B(C6F5)(4)] was identified as the best additive to generate the cationic species and maintain polymer selectivity and carbonate linkage, even at 1.0 MPa CO2. Density functional theory calculations revealed that the reaction pathway mediated by the cationic complex is more favorable than that mediated by the neutral complex, with an energy difference of 1.0 kcal mol(-1). Additionally, we found that the exchange of flexible ligands between calcium and cobalt ions is crucial for the smooth proceeding of the alternating copolymerization.
Article
Chemistry, Inorganic & Nuclear
Paulpandiyan Rajakkani, Arunadevi Alagarraj, Senthil A. Gurusamy Thangavelu
Summary: A new tetraaza macrocyclic Knoevenagel Schiff base and its metal complexes were synthesized and characterized, showing potential biological activities and binding properties with DNA. Multiple spectroscopic and analytical techniques were used to study the compounds, including experiments to determine the type of binding with nucleic acids.
INORGANIC CHEMISTRY COMMUNICATIONS
(2021)
Article
Chemistry, Inorganic & Nuclear
Janusz Gregolinski, Katarzyna Slepokura, Julia Ktak, Maciej Witwicki
Summary: In this study, a series of hexanuclear chloride and sulfate Ni(II) and Cu(II) complexes were successfully synthesized from appropriate metal salts and octadecaaza macrocyclic ligands. The obtained coordination compounds were characterized using various methods, including elemental analysis, spectroscopic methods, magnetic measurements, and X-ray crystallography. The X-ray crystal structures revealed different coordination modes of the metal cations in the obtained coordination compounds. The folding conformation of the macrocyclic ligand depended on the number of metal cations bound within the macrocycle. All Ni(II) and Cu(II) coordination compounds exhibited paramagnetic behavior. The magnetic measurements showed that the magnetic behavior of certain complexes was dominated by the magnetic anisotropy of the metal ion, while others revealed small antiferromagnetic interactions within the metal units. The EPR experiments indicated that the predominant contribution to the orbitals occupied by the unpaired electrons in the ground state originated from d(x2-y2) orbitals.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Multidisciplinary
Shivaprasad Achary Balahoju, Yogesh Kumar Maurya, Piotr J. Chmielewski, Tadeusz Lis, Mateusz Kondratowicz, Joanna Cybinska, Marcin Stepien
Summary: Peripheral substitution of a pi-extended porphyrin with bulky groups can control its curvature and stereochemistry. The coordination of large metal ions and the variation of substituents and ligands affect this control. Experiments have shown that stable enantiopure porphyrin propellers can be synthesized by adjusting experimental conditions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Electrochemistry
Shaymaa Al Shehimy, Denis Frath, Elise Dumont, Floris Chevallier, Christophe Bucher
Summary: CF3-substituted porphyrins have attracted increasing interest. This study reports the synthesis of a series of free base porphyrins incorporating one, two, and three CF3 substituents, including a never-before-described 5,10,15-tris(CF3) substituted porphyrin. Detailed electrochemical and spectroscopic analyses were carried out to assess the electron-withdrawing properties of CF3 substituents compared to C6F5. The study proposes an interpretation of the unusual electrochemical signature of these molecules featuring three successive one-electron reduction waves.
Article
Chemistry, Applied
Ayman A. Abdel A. Aziz, Ramadan M. M. Ramadan, Mina E. E. Sidqi, Mostafa A. A. Sayed
Summary: New mononuclear metal complexes derived from a tetradentate Schiff base ligand were successfully synthesized and characterized. The complexes exhibited strong binding affinity and antioxidant activity, particularly for Mn(II) and Cu(II) complexes. In vitro cell experiments demonstrated that the complexes had good anti-proliferative activity against tumor cells. The molecular geometry and DNA-interaction of the complexes were investigated using computational simulations and molecular docking experiments.
APPLIED ORGANOMETALLIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Ekaterina A. Kuchuk, Badma N. Mankaev, Kirill Zaitsev, Maxim Zabalov, Ekaterina A. Zakharova, Yuri F. Oprunenko, Andrei Churakov, Elmira Kh. Lermontova, Galina S. Zaitseva, Sergey S. Karlov
Summary: The synthesis of heteroleptic and homoleptic complexes was achieved by designing the ligands. Heteroleptic ethyl zinc complexes 1a-3a were obtained by eliminating ethane. However, only homoleptic complexes 3b and 4b could be isolated from the reaction of proligands 3 and 4 with Zn[N(SiMe3)2]2 at room temperature. Surprisingly, proligand 2 cleanly produced the amide heteroleptic zinc complex 2c in the reaction with Zn[N(SiMe3)2]2, and 2c showed the most promising activity in ring-opening polymerization (ROP) among the tested initiators.
Article
Chemistry, Inorganic & Nuclear
W. Ryan Osterloh, Nicolas Desbois, Paul Fleurat-Lessard, Yuanyuan Fang, Claude P. Gros, Karl M. Kadish
Summary: A mono-DMSO cobalt meso-CF3 corrole was synthesized and characterized, and its spectral and electrochemical properties in nonaqueous media were investigated. The results indicated that the presence of electron-withdrawing trifluoromethyl substituents at the meso-carbon atoms of the macrocycle enhanced the ease of reduction and hindered oxidation. The effects of DMSO, pyridine, and cyanide anions on the compound's electrochemistry and spectral properties were examined, showing the formation of a bis-CN adduct with only two molar equivalents.
INORGANIC CHEMISTRY
(2023)
Review
Chemistry, Physical
Yaoshuai Hong, Longbin Li, Bingyu Huang, Xiannong Tang, Weijuan Zhai, Ting Hu, Kai Yuan, Yiwang Chen
Summary: Fuel cells and metal-air batteries have great potential for sustainable energy technologies due to their zero pollution and high efficiency. However, the high cost and scarcity of Pt-based materials as cathode catalysts limit their scalability. Recent progress in nonprecious-metal catalysts has addressed some of these challenges.
ADVANCED ENERGY MATERIALS
(2021)
Article
Chemistry, Inorganic & Nuclear
Ashley J. Schuman, Adharsh Raghavan, Susannah D. Banziger, You Song, Zhao-Bo Hu, Brandon L. Mash, Andrew L. Williams, Tong Ren
Summary: This study presents the synthesis and characterization of Cr-III(HMC) catecholate and semiquinonate complexes, along with their structural, electrochemical, spectroscopic, and magnetic properties. The reversible oxidation of catecholate and strong antiferromagnetic coupling in the semiquinonate complex were observed. Additionally, density functional theory analysis revealed differences in the electronic structures of the complexes.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Huan Wang, Mahbod Morshedi, Mahesh S. Kodikara, Yovan de Coene, Koen Clays, Chi Zhang, Mark G. Humphrey
Summary: Metal-alkynyl donor/nitro acceptor-functionalized porphyrins are promising candidates for nonlinear optical (NLO) applications, exhibiting exceptional properties such as record quadratic optical nonlinearity, remarkable two-photon absorption, and outstanding three-photon absorption, as well as being the first porphyrins to exhibit four-photon absorption. The absorption peaks for two-, three-, and four-photon absorption correspond to multiples of linear absorption bands associated with porphyrin-localized pi*<-pi transitions and donor-porphyrin to porphyrin-acceptor charge transfer transitions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Tetsuo Okujima, Hayato Inaba, Shigeki Mori, Masayoshi Takase, Hidemitsu Uno, Yoshiaki Chino, Yusuke Okada, Nagao Kobayashi
Summary: A novel compound was synthesized through a series of reactions and its molecular structure and properties were confirmed by various analytical methods.
Article
Biochemistry & Molecular Biology
Guangchuan Ou, Qiong Wang, Yingzhi Tan, Qiang Zhou
Summary: Four one-dimensional complexes were synthesized by reacting nickel/copper macrocyclic complexes with K2[Ni(CN)(4)] and characterized using various analytical techniques. The structures of the complexes were determined to have a six-coordinated octahedral coordination geometry, with the nickel/copper ions coordinated by [Ni(CN)(4)](2-) and the macrocyclic ligands. The complexes exhibited weak antiferromagnetic exchange coupling, as confirmed by the Curie-Weiss law.
Article
Chemistry, Inorganic & Nuclear
K. Karunanithi, P. Bhyrappa
INORGANICA CHIMICA ACTA
(2015)
Article
Chemistry, Inorganic & Nuclear
P. Bhyrappa, U. K. Sarangi, B. Varghese
INORGANICA CHIMICA ACTA
(2015)
Article
Chemistry, Inorganic & Nuclear
Veerapandian Velkannan, Puttaiah Bhyrappa
Article
Chemistry, Physical
Velu Jeyalakshmi, Selvaraj Tamilmani, Rajaram Mahalakshmy, Puttaiah Bhyrappa, Konda Ramasamy Krishnamurthy, Balasubramanian Viswanathan
JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL
(2016)
Article
Spectroscopy
P. Bhyrappa, M. Sankar
SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY
(2018)
Article
Chemistry, Multidisciplinary
Yuanyuan Fang, P. Bhyrappa, Zhongping Ou, Karl M. Kadish
CHEMISTRY-A EUROPEAN JOURNAL
(2014)
Article
Chemistry, Inorganic & Nuclear
Puttaiah Bhyrappa, Ujwal K. Sarangi, Babu Varghese
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2014)
Article
Chemistry, Inorganic & Nuclear
Puttaiah Bhyrappa, Ujwal K. Sarangi, Veerapandian Velkannan, Venkatachalam Ramkumar
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2014)
Article
Chemistry, Inorganic & Nuclear
P. Bhyrappa, K. Karunanithi
INORGANICA CHIMICA ACTA
(2011)
Article
Chemistry, Inorganic & Nuclear
P. Bhyrappa, V. Velkannan
INORGANICA CHIMICA ACTA
(2012)
Article
Chemistry, Physical
Basanth S. Kalnoor, Prem B. Bisht, Kailash C. Jena, V. Velkannan, P. Bhyrappa
JOURNAL OF PHYSICAL CHEMISTRY A
(2013)
Article
Chemistry, Multidisciplinary
P. Bhyrappa, V. Velkannan
JOURNAL OF PORPHYRINS AND PHTHALOCYANINES
(2011)
Article
Chemistry, Multidisciplinary
Bhyrappa Puttaiah, Velkannan Veerapandian, Sarangi Ujwal Kumar
JOURNAL OF CHEMICAL SCIENCES
(2016)
Article
Chemistry, Multidisciplinary
Bhyrappa Puttaiah, Karuppaiah Karunanithi
JOURNAL OF CHEMICAL SCIENCES
(2016)
Article
Chemistry, Multidisciplinary
Bhyrappa Puttaiah, Velkannan Veerapandian
JOURNAL OF CHEMICAL SCIENCES
(2015)