Article
Chemistry, Inorganic & Nuclear
Chenggang Jiang, Louise M. Canada, Ngoc Bao Nguyen, Thomas S. Teets
Summary: This work describes the synthesis and characterization of a series of neutral Chugaev-type chelating dicarbene iridium complexes with different cyclometalating ligands. The effects of these ligands on the emission properties of the complexes are evaluated, and it is found that the complexes exhibit blue-shifted phosphorescence compared to previously described analogues. The study also investigates the electrochemical properties of the compounds and determines the dependence of HOMO and LUMO energies on the cyclometalating ligands.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Sergej Stipurin, Thomas Strassner
Summary: A total of six novel platinum complexes were successfully synthesized from saturated N-heterocyclic carbene precursors, showing strong emissive properties in the sky-blue region of the visible spectrum with quantum yields up to 71% in a PMMA matrix. The structures were characterized by NMR experiments and solid-state analyses, confirming the cyclometalation and saturated backbone of the NHC motif. DFT calculations were used to examine the photophysical and electrochemical properties of the platinum complexes.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2021)
Article
Materials Science, Multidisciplinary
Tianjian Yang, Aihua Zhou, Yinming He, Zhichao Yao, Xiaochen Song, Xianwang Tao, Youtian Tao
Summary: In this study, three cyclometalated heavy metal complexes were designed as electron donor materials for organic solar cells, and their optoelectronic properties and photovoltaic performances were systematically investigated. Among them, tTBz3Ir exhibited the best photovoltaic performance, mainly due to its more significant 3D geometry.
MATERIALS ADVANCES
(2023)
Article
Chemistry, Physical
Marcia R. Goncalves, Karina P. M. Frin
Summary: This study reports the synthesis and characterization of mer-[Ir(ppy)(2)(Ipic)], investigating its electronic absorption spectra and electrochemical properties. The introduction of a halogen atom significantly affects the LUMO energy, while the emission behavior varies between room temperature and 77 K.
JOURNAL OF MOLECULAR STRUCTURE
(2021)
Article
Chemistry, Multidisciplinary
Jiayi Zhu, Yan Liu, Zhao Zhang, Xili Yang, Feng Qiu
Summary: In this study, we designed and synthesized two complexes as photosensitizers, which exhibited strong phosphorescence and high toxicity against cancer cells. These complexes rapidly accumulated in lysosomes after entering cancer cells, and when exposed to light irradiation, they produced a large amount of oxidizing stress substances, eventually leading to cancer cell death. This provides promising potential application in photodynamic therapy.
Article
Chemistry, Inorganic & Nuclear
Neetu Singh, Ga Hee Noh, Hanif Mubarok, Chang Woo Kim, Min Hyung Lee, Junseong Lee
Summary: In this study, five cyclometalated iridium complexes with phenyl-azole ancillary ligands were synthesized and their photophysical properties were studied. Complex 1 showed a higher phosphorescence quantum efficiency compared to complexes 2-4, attributed to its relatively small non-radiative decay rate constant.
Article
Chemistry, Applied
Giulia De Soricellis, Francesco Fagnani, Alessia Colombo, Claudia Dragonetti, Dominique Roberto, Daniele Marinotto, David H. Hartnell, Mark J. Hackett, Massimiliano Massi, Bertrand Carboni, Veronique Guerchais
Summary: Three novel luminescent iridium(III) dyes with tryptophan amino acid and cyclometalated 2-phenylpyridines, 2-(2,4-difluorophenyl)pyridines or 2-phenylquinolines have been synthesized. They exhibit emissions at 522-561 nm with luminescence quantum yields ranging from 0.33 to 0.98. These dyes can effectively stain neuronal cells in rat cerebellum tissue, showing strong affinity for granule neurons. The complexes with cyclometalated 2-(2,4-difluorophenyl)pyridines or 2-phenylquinolines also exhibit good affinity for brain white matter. Among them, the dye with two cyclometalated 2-phenylquinolines has the highest luminescence quantum yield (0.98) and demonstrates the strongest affinity for purkinje neurons in cerebellum tissue.
Article
Chemistry, Inorganic & Nuclear
Tingting Sun, Xiuyan Jin, Luyang Duanmu, Hongzhuang Guo, Deming Han, Yuanhua Yu
Summary: Using TDDFT approach, the electronic structure and photophysical properties of five cyclometalated Ir(III) complexes with different substituted acetylacetone moieties were calculated and investigated. The calculated geometry structure of complex 2 agrees well with experimental data. The HOMO distribution of complex 1 differs from complexes 2-5, with contributions from Ir's d-orbital, acac's pi-orbital, and L ligands. The S0 -> S1 transition of complex 1 is different from complexes 2-5, occurring from HOMO -> LUMO and HOMO-1 -> LUMO. The lowest energy emissions for these complexes from CAM-B3LYP level are at 591, 581, 576, 574, and 571, respectively. Complex 4 may have the largest kr value among the studied complexes. This study is important for the development of efficient OLEDs using Ir(III) emitters.
Article
Biochemistry & Molecular Biology
Yuzhen Yang, Han Zhao, Weiqiao Zhou, Qin Zeng, Zihao Zhang, Junjie Jiang, Yongyang Gong, Yanqin Miao, Song Guo, Yuanli Liu
Summary: Two novel neutral phosphorescent iridium(III) complexes (Ir1 and Ir2) were designed and synthesized with high yields using 10,11,12,13-tetrahydrodibenzo[a,c]phenazine as the main ligand. The complexes exhibited bright-red phosphorescence, high-luminescence quantum efficiency, solvatochromism, and good thermostability. They were successfully utilized to fabricate high-efficiency red OLEDs, achieving promising performance in terms of current efficiency, power efficiency, and external quantum efficiency.
Article
Chemistry, Multidisciplinary
Mansoor Akhtar, Ali Muhammad Arif, Shifa Ullah Khan, Guo-Gang Shan, Hong-liang Xu, Zhong-Min Su
Summary: Density functional theory calculations were employed to investigate the geometric structures, electronic properties, and second-order nonlinear optical (NLO) properties of two synthesized iridium(iii) complexes with different substituted ancillary ligands. The first hyperpolarizabilities were found to be easily modulated by the introduction of different units, and the changes in properties could be qualitatively explained by means of the charge transfer pattern. The theoretical investigation of these complexes is expected to aid in designing high-performance and versatile NLO materials.
NEW JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Physical
Peng Tao, Xiao-Kang Zheng, Xiao-Zhen Wei, Mei-Tung Lau, Yuk-Ki Lee, Zi-Kang Li, Ze-Ling Guo, Fang-Qing Zhao, Xing Liu, Shu-Juan Liu, Qiang Zhao, Yan-Qin Miao, Wai-Yeung Wong
Summary: Three efficient yellow iridium(III) complexes were designed using a chlorine-functionalization method, exhibiting extremely broad emission bandwidths and bright yellow phosphorescence in N-2-saturated dichloromethane with high photoluminescence efficiency. These complexes show great potentials in developing high-performance yellow and white electroluminescence, with high external quantum efficiency realized in the prepared OLEDs.
MATERIALS TODAY ENERGY
(2021)
Article
Biochemistry & Molecular Biology
Anastasia I. Solomatina, Daria O. Kozina, Vitaly V. Porsev, Sergey P. Tunik
Summary: In this study, four iridium complexes containing cyclometallated N^C ligand and various bidentate L^L ligands were synthesized and characterized. These complexes exhibit moderate to strong phosphorescence in the 550-670 nm range, with emission properties strongly dependent on pH. The complexes localize in lysosomes and acidified endosomes within living cells, demonstrating low toxicity.
Article
Biochemistry & Molecular Biology
Deming Han, Xiaoqiang Ji, Lihui Zhao, Chunying Pang
Summary: The electronic structure and photophysical properties of a series of cyclometalated iridium(III) complexes bearing the substituted phenylpyrazole were theoretically investigated using DFT and TDDFT. The study found that electron-donating substituent groups have a significant effect on the properties of these complexes, providing valuable guidance for the design of new OLED materials.
PHOTOCHEMICAL & PHOTOBIOLOGICAL SCIENCES
(2021)
Article
Chemistry, Inorganic & Nuclear
Alexey V. Polukeev
Summary: This study presents the synthesis, characterization and catalytic activity of cyclometalated iridium complexes with a bidentate POC ligand. Metalation of POC-H with [Ir(COD)Cl]2 yielded a mixture of (POC)(POC-H)IrHCl and (POC)(COD)IrHCl, which were further converted to (POC)(L)IrHCl complexes through ligand exchange. The compounds were tested in acceptorless and transfer dehydrogenation reactions and compared with pincer complexes. A dimeric complex was obtained from one of the complexes, explaining its low activity. DFT studies shed light on the metalation mechanism.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Jing Tu, Daniele Veclani, Filippo Monti, Andrea Mazzanti, Letizia Sambri, Nicola Armaroli, Andrea Baschieri
Summary: A new synthetic method has been developed for the preparation of unexpected emissive iridium(iii) complexes (A and B). The structures and reaction mechanisms of these complexes were characterized and analyzed. The findings of higher photoluminescence quantum yield in complex A compared to known analogues provide a potential pathway for the direct synthesis of luminescent complexes.
DALTON TRANSACTIONS
(2023)
Review
Chemistry, Inorganic & Nuclear
Pavel S. Chelushkin, Julia R. Shakirova, Ilya S. Kritchenkov, Vadim A. Baigildin, Sergey P. Tunik
Summary: The application of NIR emitting transition metal complexes in biomedicine has expanded to include oxygen sensing, visualization of biological models, and various therapeutic applications. Challenges remain in improving the photophysical and physico-chemical characteristics of these compounds for further advancements in biomedical applications.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Multidisciplinary
Anastasia Solomatina, Ekaterina E. Galenko, Daria O. Kozina, Alexey A. Kalinichev, Vadim A. Baigildin, Natalia A. Prudovskaya, Julia R. Shakirova, Alexander F. Khlebnikov, Vitaly V. Porsev, Robert A. Evarestov, Sergey P. Tunik
Summary: Five square-planar [Pt(C^N*N 'C ')] complexes with novel nonsymmetric tetradentate ligands were synthesized and characterized, showing substantial changes in photophysical properties and intermolecular interaction mode in solution and in solid state by varying the structure of the metalating aromatic systems. Some of these complexes exhibited aggregation-induced emission phenomenon in water and mechanochromism in the solid state, which were attributed to the excited states of Pt-Pt bonded aggregates of the complexes.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Julia R. R. Shakirova, Vadim A. A. Baigildin, Anastasia I. I. Solomatina, Reza Babadi Aghakhanpour, Vladimir V. V. Pavlovskiy, Vitaly V. V. Porsev, Sergey P. P. Tunik
Summary: A novel pH-responsive phosphorescent probe based on cyclometalated iridium(III) complex is reported, which is covalently conjugated with a water-soluble block-copolymer to prevent oxygen quenching and improve biocompatibility. The resulting polymeric nanoprobe shows a strong response of phosphorescence lifetime to pH variations in the physiological range. Cellular experiments confirm the applicability of this sensor for monitoring intra- and extracellular pH in cell cultures.
ADVANCED FUNCTIONAL MATERIALS
(2023)
Article
Biochemistry & Molecular Biology
Kristina S. Kisel, Vadim A. Baigildin, Anastasia I. Solomatina, Alexey I. Gostev, Eugene V. Sivtsov, Julia R. Shakirova, Sergey P. Tunik
Summary: A series of diphosphine Re(I) complexes Re1-Re4 were designed by decorating the archetypal core {Re(CO)(2)(N boolean AND N)} with phosphines bearing a terminal double bond. These complexes were copolymerized with Macro-RAFT agents to form water-soluble copolymers containing rhenium complexes. The copolymers exhibited phosphorescence from a (MLCT)-M-3 excited state and low sensitivity to molecular oxygen in physiological media.
Article
Chemistry, Multidisciplinary
Vitaly Porsev, Robert Evarestov
Summary: The atomic structure, electronic, and magnetic properties of two zig-zag-edged hexagonal nanohelicenes of the second type [1.2] and [2.2] were investigated using density functional theory. These nanohelicenes exhibit a helical periodicity and belong to the fifth family of line symmetry groups in their global energy minimum. We found that these nanohelicenes are diamagnetic metals that undergo a spontaneous symmetry breaking into antiferromagnetic semiconductors through the Mott-Hubbard metal-insulator transition. However, under torsional stress, a reversible transformation to a diamagnetic metal can occur, which holds promise for the utilization of nanohelicenes in electromagneto-mechanical nanodevices.
Article
Biochemistry & Molecular Biology
Zohreh Hendi, Daria O. Kozina, Vitaly V. Porsev, Kristina S. Kisel, Julia R. Shakirova, Sergey P. Tunik
Summary: A series of bis-metalated phosphorescent complexes were synthesized and characterized. The investigation of the complexes' spectroscopic properties and theoretical calculations revealed the importance of metal-to-ligand charge transfer and intraligand transition in the generation of emissive triplet states. The results showed systematic bathochromic shifts in the absorption and emission spectra upon insertion of electron-withdrawing substituents and expansion of the aromatic system. These findings provide valuable insights into the photophysical processes in complexes of this type and offer useful tools for fine-tuning their emissive characteristics.
Article
Chemistry, Analytical
Mozhgan Samandarsangari, Ilya S. Kritchenkov, Daria O. Kozina, Anastasia D. Komarova, Marina V. Shirmanova, Sergey P. Tunik
Summary: The design, synthesis, and investigation of new molecular oxygen probes for bioimaging, based on phosphorescent transition metal complexes, have been studied. Three new iridium complexes with different ligands have been synthesized and characterized. These complexes exhibited phosphorescence and showed potential for use in bioimaging experiments. Furthermore, they were found to be internalized into cancer cells and localized in mitochondria and lysosomes.
Correction
Nanoscience & Nanotechnology
Boris V. Vasil'ev, Ruslan Yu. Smyslov, Demid A. Kirilenko, Ilya S. Kritchenkov, Alexander N. Bugrov
Summary: This paper is a corrigendum related to the article Vasil'ev B.V., Smyslov R.Yu., Kirilenko D.A., Bugrov A.N. Synthesis and magnetic properties of cobalt ferrite nanoparticles formed under hydro and solvothermal condition. Nanosystems: Phys. Chem. Math., 2021,12 (4), P. 492-504.
NANOSYSTEMS-PHYSICS CHEMISTRY MATHEMATICS
(2023)
Article
Physics, Condensed Matter
Anton Domnin, Vitaly V. Porsev, Robert A. Evarestov
Summary: The work presents a comparison of armchair and zigzag terminated nanohelicenes in terms of their structural, mechanical, electronic, and magnetic properties. The study shows that these nanohelicenes are metals in their most symmetric state but undergo a spontaneous symmetry breaking, resulting in a metal-insulator transition. It is found that the type of edge termination (armchair or zigzag) determines the type of metal-insulator transition in the global energy minima. The study also reveals that the edge terminations and transition types influence the helical electronic bands, and that the van der Waals forces between coils are stronger in the case of zigzag termination.
COMPUTATIONAL CONDENSED MATTER
(2023)
Article
Chemistry, Inorganic & Nuclear
Evgeniia E. Luneva, Daria O. Kozina, Anna V. Mozzhukhina, Vitaly V. Porsev, Anastasia I. Solomatina, Sergey P. Tunik
Summary: A series of new platinum square planar complexes with various ligands have been synthesized and characterized. These complexes exhibit strong blue emission with high quantum yields and long excited state lifetimes in solid, solution, and polymeric matrix. The molecular architecture can transform to give a heteronuclear complex with the Pt-Ag-Pt coordination core.
Article
Chemistry, Inorganic & Nuclear
Kristina S. Kisel, Julia R. Shakirova, Vladimir V. Pavlovskiy, Robert A. Evarestov, Vladislav V. Gurzhiy, Sergey P. Tunik
Summary: Binuclear transition-metal complexes based on conjugated systems containing coordinating functions have potential applications in various fields. This study presents the synthesis, characterization, photophysical, and theoretical studies of rare rhenium-(I) and rhenium-(I)-iridium-(III) dyads.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Analytical
Mozhgan Samandarsangari, Daria O. Kozina, Victor V. Sokolov, Anastasia D. Komarova, Marina V. Shirmanova, Ilya S. Kritchenkov, Sergey P. Tunik
Summary: In this study, new phosphorescent iridium complexes were synthesized with water-soluble and biocompatible properties. The major photophysical characteristics were determined by two cyclometallating ligands based on 2-pyridine-benzothiophene. The use of various diimine ligands influenced the quantum yield of phosphorescence and the sensitivity to oxygen. The complexes demonstrated low toxicity and good water solubility.
Article
Chemistry, Inorganic & Nuclear
Svetlana A. Katkova, Daria O. Kozina, Kristina S. Kisel, Maria A. Sandzhieva, Dmitriy A. Tarvanen, Sergey V. Makarov, Vitaly V. Porsev, Sergey P. Tunik, Mikhail A. Kinzhalov
Summary: A series of cyclometalated platinum(ii) complexes with acyclic diaminocarbene (ADC) ancillary ligands were designed and synthesized. Their photophysical properties were investigated both experimentally and theoretically. The complexes showed green phosphorescence with high quantum efficiency of up to 45% in 2 wt% doped PMMA film at room temperature. These complexes were further utilized as light-emitting dopants for OLED fabrication. The resulting devices demonstrated green emission with a maximum current efficiency of 2.9 cd A(-1) and a luminance of 2700 cd m(-2), highlighting the potential of these cyclometalated platinum(ii) complexes as efficient green emitters for OLED devices.
DALTON TRANSACTIONS
(2023)