Article
Chemistry, Inorganic & Nuclear
David A. A. Shultz, Riley Stephenson, Martin L. L. Kirk
Summary: The synthesis and characterization of dinuclear ligand-to-ligand charge transfer complexes with platinum(ii) coordinated to tert-butyl-orthocatecholate donor and di-tert-butyl-2,2'-bipyridine acceptor were described. The complexes exhibited ligand-to-ligand charge transfer bands in the visible spectrum and showed intramolecular interaction between the platinum centres. The excited state lifetimes of these complexes were twofold longer than the mononuclear parent complex. The properties of these complexes were discussed and compared to similar complexes in the literature.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Flavio L. Portwich, Yves Carstensen, Anindita Dasgupta, Stephan Kupfer, Ralf Wyrwa, Helmar Goerls, Christian Eggeling, Benjamin Dietzek, Stefanie Graefe, Maria Waechtler, Robert Kretschmer
Summary: This article describes a dinuclear aluminium(III) complex with enhanced photoluminescence properties. It shows an unprecedented photoluminescence quantum yield near unity and a short excited-state lifetime in solution. Embedding the complex in non-woven fabrics results in highly fluorescent fleece.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Shishi Fang, Michael Ho-Yeung Chan, Vivian Wing-Wah Yam
Summary: A new series of dinuclear anthracene-containing alkynylplatinum(ii) terpyridine complexes exhibit intriguing photo-modulated self-assembly behaviors in solutions, forming supramolecular assemblies with interesting spectroscopic responses and distinct nanostructures. Further, these complexes undergo photooxygenation upon UV excitation, altering their self-assembly behaviors as confirmed by electron microscopic and DLS studies.
MATERIALS CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Multidisciplinary
Mohammadjavad Karimi, Elham S. Tabei, Remi Fayad, Mohamed R. Saber, Evgeny O. Danilov, Cameron Jones, Felix N. Castellano, Francois P. Gabbai
Summary: The study found that both isomeric complexes cleanly converted into the platinum germyl complex in the presence of a chlorine trap, with high quantum yields. The conversion of the Ge-IV-Pt-II isomer into the platinum germyl complex is a rare example of a light-induced transition-metal/main-group-element bond-forming process. Transient-absorption-spectroscopy studies on the Ge-III-Pt-III isomer suggest a ligand arene-Cl- charge-transfer complex as an intermediate.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Shishi Fang, Michael Ho-Yeung Chan, Vivian Wing-Wah Yam
Summary: A series of dinuclear coumarin-containing alkynylplatinum(II) terpyridine complexes exhibit solvent-induced self-assembly behaviors and display color changes from yellow to red in their DMSO solutions with increasing water content. The aggregation-assisted photodimerization of the coumarin moieties is facilitated by the directional Pt center dot center dot center dot Pt interaction, which brings the C=C bonds of the photo-responsive coumarin moieties in close proximity to each other for topochemical photodimerization upon UV excitation. The importance of supramolecular assembly of the Pt(II) complexes in switching on the photodimerization reaction is demonstrated by various spectroscopic and microscopic techniques.
MATERIALS CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Carlota Bozal-Ginesta, Reshma R. Rao, Camilo A. Mesa, Yuanxing Wang, Yanyan Zhao, Gongfang Hu, Daniel Anton-Garcia, Ifan E. L. Stephens, Erwin Reisner, Gary W. Brudvig, Dunwei Wang, James R. Durrant
Summary: The kinetics of water oxidation in molecular and heterogeneous catalysis differ due to the cooperative effects between oxidized iridium centers in heterogeneous catalysts. The specific coordination environment around the iridium centers in molecular catalysts allows for water oxidation without cooperative effects. These distinctions explain the differences in water oxidation electrocatalytic performance observed under different potential conditions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Inorganic & Nuclear
Stanislav Bezzubov, Kirill Ermolov, Alexander Gorbunov, Paulina Kalle, Ivan Lentin, Gennadij Latyshev, Vladimir Kovalev, Ivan Vatsouro
Summary: Conventional cyclometalation of calix[4]arene bis(aryltriazoles) with iridium(iii) chloride hydrate results in unique meso architectures, where the dinuclear complexes contain independent or coupled iridium pairs which can be further modified by replacing chloride bridges with ancillary ligands.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Inorganic & Nuclear
Rui Zhang, Jin-Wang Liu, Wei-Yong Zhong, Jing-Lin Chen, Feng Zhao, Sui-Jun Liu, He-Rui Wen
Summary: The article reports the mechanochromic and selective vapochromic solid-state luminescence properties of a new bimetallic cuprous complex. The response mechanisms are elucidated by investigating the different solvated polymorphs. It is found that the luminescence properties can be controlled by different solvents and grinding-induced breakage of hydrogen bonds.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Julio Corredoira-Vazquez, Cristina Gonzalez-Barreira, Matilde Fondo, Ana M. Garcia-Deibe, Jesus Sanmartin-Matalobos, Silvia Gomez-Coca, Eliseo Ruiz, Enrique Colacio
Summary: A new synthetic method has been developed to isolate a series of fluoride-bridged complexes, which exhibit interesting magnetic properties and provide theoretical insights into the structure-magnetism relationship for this type of compounds.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Jackson S. McCarthy, Mary Jo McCormick, John H. Zimmerman, H. Rhodes Hambrick, Wilson M. Thomas, Colin D. McMillen, Paul S. Wagenknecht
Summary: This study investigates the photophysics of square-planar Pt-II complexes with strongly electron-withdrawing ligands. The results show that these complexes exhibit emission in both solution and films, with the emission being attributed to the intraligand charge transfer. The study also reveals that the emission from films is enhanced due to a decrease in nonradiative relaxation. Additionally, concentration-dependent excimer emission is observed in some complexes, providing a means for tuning the emission color. However, excimer emission is not observed in cured films, indicating a diffusional nature of excimer formation.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Julio Corredoira-Vazquez, Cristina Gonzalez-Barreira, Matilde Fondo, Ana M. Garcia-Deibe, Jesus Sanmartin-Matalobos, Silvia Gomez-Coca, Eliseo Ruiz, Enrique Colacio
Summary: A new synthetic method has been developed to isolate dinuclear compounds with fluoride bridging, and the crystal structures and magnetic properties have been studied to explore the relationship between structure and properties.
INORGANIC CHEMISTRY
(2022)
Article
Materials Science, Multidisciplinary
Giuseppina Anna Corrente, Dora A. Gonzalez, Ece Aktas, Agostina Lina Capodilupo, Gloria Mazzone, Francesco Ruighi, Gianluca Accorsi, Daniela Imbardelli, Cristina Rodriguez-Seco, Eugenia Martinez-Ferrero, Emilio Palomares, Amerigo Beneduci
Summary: Electrochromism/electrofluorochromism is the reversible tuning of absorption/photoluminescence through redox processes. Functional materials possessing both electrochromic and electrofluorochromic properties have wide applications in various fields. This work presents a new molecular approach that combines the properties of stable arylamine radical cation mixed valence species and donor-acceptor systems exhibiting photoinduced intramolecular charge transfer mechanism to achieve dual functionalities and red-NIR electrochromism.
ADVANCED OPTICAL MATERIALS
(2023)
Article
Chemistry, Inorganic & Nuclear
Marsel Z. Shafikov, Ross Martinscroft, Craig Hodgson, Anna Hayer, Armin Auch, Valery N. Kozhevnikov
Summary: This study reports the design, synthesis and luminescent properties of a dinuclear Ir(III) complex, which showed superior photophysical properties compared to its mononuclear analogues. The complex exhibited highly efficient red emission and a faster radiative rate. Temperature-dependent studies revealed behaviors reminiscent of thermally activated delayed fluorescence (TADF) in both the dinuclear and mononuclear complexes.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Piotr Pander, Ruth Daniels, Andrey V. Zaytsev, Ashleigh Horn, Amit Sil, Thomas J. Penfold, J. A. Gareth Williams, Valery N. Kozhevnikov, Fernando B. Dias
Summary: The novel dinuclear platinum(ii) complex exhibits bright luminescence in the red region of the spectrum, with a high photoluminescence quantum yield and short excited state lifetime. It also demonstrates efficient thermally activated delayed fluorescence behavior, making it a promising candidate for OLED applications.
Article
Chemistry, Inorganic & Nuclear
Sarah Kromer, Subhangi Roy, James E. Yarnell, Chelsea M. Taliaferro, Felix N. Castellano
Summary: Dinuclear d(8) Pt(ii) complexes exhibit photophysical properties determined by the distance between the two Pt(ii) centres, showing either metal-to-ligand-(MLCT) or metal-metal-ligand-to-ligand charge transfer (MMLCT) transitions. The novel dinuclear complexes with 8-hydroxyquinoline as the bridging ligand possess similar photophysics to the mononuclear model chromophore. TD-DFT calculations confirm the mixed LC/MLCT nature of the lowest energy absorption and the limited quantum yields of the (LC)-L-3 photoluminescence for these complexes.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Physical
Nobutaka Yoshimura, Osamu Tomita, Ryu Abe, Masaki Yoshida, Atsushi Kobayashi
Summary: The hydrogen evolution activity of PS-double-layered photocatalysts was studied in the presence of redox-reversible electron donors. The polyoxometalates acted as effective electron donors and the photocatalyst showed an apparent quantum yield of 0.39% in the initial hour. Energy transfer deactivation from photoexcited PS* to surface-immobilized polyoxometalates was identified as the reason for lower quantum yield.
Article
Nanoscience & Nanotechnology
Yusuke Higashida, Shin-ya Takizawa, Masaki Yoshida, Masako Kato, Atsushi Kobayashi
Summary: In this study, a hydrophobic Ru-(II) dye-sensitized Pt-TiO2 nanoparticle photocatalyst was synthesized and integrated into DPPC lipid bilayer vesicles. The photocatalytic H-2 production activity was significantly enhanced in the presence of DPPC vesicles, indicating that the highly dispersed state of the hydrophobic Ru-(II) dye-sensitized Pt-TiO2 nanoparticles in the DPPC bilayer vesicles is crucial for achieving enhanced H-2 production activity in aqueous solution.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Physical
Taku Shimamura, Nobutaka Yoshimura, Hiroki Otsuka, Masaki Yoshida, Atsushi Kobayashi
Summary: To enhance solar-fuel production, a new heteroleptic Ru (II)-picolinate complex, Rupic, was synthesized as a red light-absorbing molecular photosensitizer. Rupic exhibited metal-to-ligand charge-transfer absorption and emission over a longer wavelength region than its bipyridine derivative, Rubpy. The Rupic-sensitized Pt-TiO2 nanoparticles showed significantly higher photocatalytic H2 evolution reaction activity under red light illumination compared to Rubpy-sensitized analog, indicating the superior photosensitizing performance of Rupic for H2 production under sunlight.
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY
(2023)
Editorial Material
Chemistry, Multidisciplinary
Nobutaka Yoshimura, Masaki Yoshida, Atsushi Kobayashi
Summary: One-directional electron transport is crucial for efficient Z-scheme water-splitting photocatalysis. A photoredox cascade catalyst was synthesized to mimic natural photosynthesis's electron transport chain, using Pt-TiO2 nanoparticle catalyst, two photosensitizers (RuCP6 and RuP6), and a visible-light-transparent electron mediator (HCRu). The catalyst, named PRCC-1, exhibited the highest initial apparent quantum yield (iAQY = 2.23%) among dye-sensitized TiO2 photocatalysts, and successfully produced hydrogen using hydroquinone monosulfonate as the hydrogen source.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Atsushi Kobayashi
Summary: Biomass photoreforming is a promising method for clean energy production. A new photoredox cascade catalyst was fabricated to improve contact between heterogeneous photocatalysts and biomass substrates. Under blue-light irradiation, this catalyst efficiently produced hydrogen and regenerated the catalytically active species.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Tamami Morimoto, Masaki Yoshida, Ayana Sato-Tomita, Shunsuke Nozawa, Junichi Takayama, Satoshi Hiura, Akihiro Murayama, Atsushi Kobayashi, Masako Kato
Summary: This study reports the successful water-vapor-induced assembly of anionic PtII complex onto cationic layered double hydroxide nanoparticles, leading to stable assembly even in dilute aqueous media. The increased mobility of PtII complexes caused by water adsorption resulted in their assembly on the LDH nanoparticles and a significant change in luminescence.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Verner Saask, Yi-An Chen, Tse-Fu Huang, Li-Yu Ting, Ting-An Luo, Saki Fujii, Kaija Pohako-Esko, Masaki Yoshida, Masako Kato, Tien-Lin Wu, Ho-Hsiu Chou
Summary: This study synthesized and investigated ten ionic manganese(II) complexes in terms of their thermal and photophysical properties. It was found that the complexes with the [BnMIm]+ cation exhibited higher crystallinity and superior photoluminescent quantum yields. Additionally, efficient tunability of photophysical parameters was demonstrated in complexes with chlorine and bromine ligands.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Nobutaka Yoshimura, Masaki Yoshida, Atsushi Kobayashi
Summary: By synthesizing a photoredox cascade catalyst, which mimics the electron transport chain in natural photosynthesis, one-directional electron transport between a photocatalyst and redox mediator was achieved, leading to highly active Z-scheme water-splitting photocatalysis. The synthesized catalyst, PRCC-1, composed of Pt-TiO2 nanoparticle catalyst, two photosensitizers (RuCP6 and RuP6), and a visible-light-transparent electron mediator (HCRu), exhibited the highest reported initial apparent quantum yield (iAQY = 2.23%) among dye-sensitized TiO2 photocatalysts to date. Moreover, PRCC-1 successfully produced hydrogen using hydroquinone monosulfonate (H2QS-) as the hydrogen source.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Inorganic & Nuclear
Yusuke Makino, Masaki Yoshida, Shotaro Hayashi, Toshiyuki Sasaki, Satoshi Takamizawa, Atsushi Kobayashi, Masako Kato
Summary: Molecular crystals of Pt(ii) complexes with metallophilic interactions can exhibit bright assembly-induced luminescence with colour tunability. However, their brittleness hinders their application in flexible optical materials. In this study, the elastic deformation of crystals of polyhalogenated Pt(ii) complexes was achieved, resulting in bright luminescence. The crystal of [Pt(bpic)(dFppy)] showed ligand-centred emission, while the co-crystal of [Pt(bpic)(dFppy)] and [Pt(bpic)(ppy)] exhibited metal-metal-to-ligand charge transfer emission with a significantly higher emission quantum yield.
DALTON TRANSACTIONS
(2023)