Article
Chemistry, Multidisciplinary
Mengfei Wang, Kei Murata, Yosuke Koike, Gediminas Jonusauskas, Amaury Furet, Dario M. Bassani, Daisuke Saito, Masako Kato, Yuushi Shimoda, Kiyoshi Miyata, Ken Onda, Kazuyuki Ishii
Summary: A recent study has demonstrated the photo-induced CO-releasing capabilities of the complex Re1Pc, which is composed of a [Re(CO)(3)](+) unit and a phthalocyanine ligand. The complex exhibited efficient spin-orbit coupling and large Franck-Condon factors, resulting in short excited-state lifetimes and ultrafast intersystem crossing. This research provides promising insights into the development of red-light-driven photoCORMs for biomedical applications.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Jin Tanaka, Yuki Nagashima, Antonio Junio Araujo Dias, Ken Tanaka
Summary: A novel photoinduced in situ reduction reaction of half-sandwich metal [Rh(III)] complexes to low-valent anionic metal [Rh(II)] ate complexes has been reported, enabling room temperature ortho-C-H borylation of arenes. This strategy was facilitated by using a functionalized cyclopentadienyl (Cp-A3) Rh(III) catalyst developed by the researchers.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Inorganic & Nuclear
Meiqiong Tang, Lee Cameron, Eve M. Poland, Li-Juan Yu, Stephen A. Moggach, Rebecca O. Fuller, Hai Huang, Jianwei Sun, Stuart C. Thickett, Massimiliano Massi, Michelle L. Coote, Curtis C. Ho, Alex C. Bissember
Summary: This report presents the synthesis and characterization of a family of chromium, molybdenum, tungsten, manganese, and iron complexes with N-heterocyclic carbene and carbonyl supporting ligands. The properties of these complexes were studied using experiment and theory, including their solid-state, spectroscopic, electrochemical, and photophysical properties. It was found that these complexes undergo decarbonylation when exposed to ultraviolet light.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Jingqi Han, Shun-Cheung Cheng, Shek-Man Yiu, Man-Kit Tse, Chi-Chiu Ko
Summary: These new luminescent complexes with environmentally-sensitive dimerization equilibrium can be used as gas sensors for detecting humidity, ammonia, and amine vapors, thanks to their strong interaction with H-bonding donor/acceptor molecules involving diaminocarbene ligand orbitals in the emissive excited state. By responding to amines and humidity and changing the luminescence properties accordingly, a proof-of-principle for binary optical data storage with reversible concealment process has been demonstrated.
Article
Chemistry, Multidisciplinary
Hannah Kurz, Konstantin Schoetz, Ilias Papadopoulos, Frank W. Heinemann, Harald Maid, Dirk M. Guldi, Anna Koehler, Gerald Hoerner, Birgit Weber
Summary: The study presents a family of planar nickel(II) complexes with sensitive CISSS tracked by fluorescence detection. These complexes fluoresce in noncoordinating solvents but are fluorescence-silent in the presence of axial ligands. FD-CISSS shows higher sensitivity compared to absorption-based CISSS.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Han Li, Oliver S. Wenger
Summary: Our study demonstrates the concept that single excitation of the two-electron reduced forms of perylene diimides (PDIs) with green photons can produce excited states with similar or greater reducing power than the shorter-lived excited states of PDI radical monoanions. By performing multi-electron reduction of a photocatalyst with a sacrificial reagent before irradiation with low-energy photons, we can generate highly reactive excited states for photocatalytic reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Nils W. Rosemann, Linnea Lindh, Iria Bolano Losada, Simon Kaufhold, Om Prakash, Aleksandra Ilic, Jesper Schwarz, Kenneth Waernmark, Pavel Chabera, Arkady Yartsev, Petter Persson
Summary: Steady state and ultrafast spectroscopy were used to study [Fe-III(phtmeimb)(2)]PF6 over a broad range of temperatures. The intramolecular deactivation dynamics of the luminescent doublet ligand-to-metal charge-transfer ((LMCT)-L-2) state were analyzed, revealing the direct deactivation of the (LMCT)-L-2 state as a key limitation to its lifetime. Photoinduced disproportionation and subsequent bimolecular recombination of Fe(iv) and Fe(ii) complex pairs were observed in selected solvent environments. The efficient photoinduced intermolecular charge separation over a wide temperature range highlights the potential of [Fe-III(phtmeimb)(2)]PF6 for photocatalytic bimolecular reactions.
Article
Biochemistry & Molecular Biology
Li Gao, Joyce C. M. Meiring, Yvonne Kraus, Maximilian Wranik, Tobias Weinert, Stefanie D. Pritzl, Rebekkah Bingham, Evangelia Ntouliou, Klara Jansen, Natacha Olieric, Jorg Standfuss, Lukas C. Kapitein, Theobald Lohmuller, Julia Ahlfeld, Anna Akhmanova, Michel O. Steinmetz, Oliver Thorn-Seshold
Summary: Researchers have designed a photoswitchable SBT scaffold to create metabolically stable and fully GFP/YFP-orthogonal SBTub photopharmaceuticals for precise control of microtubule dynamics and organization. These photopharmaceuticals have great potential applications in cell biology and are favorable for intracellular biological control in in vivo settings. The robustness and imaging orthogonality of the SBT scaffold may inspire further derivatizations for photocontrol of a range of other biological targets.
CELL CHEMICAL BIOLOGY
(2021)
Article
Chemistry, Multidisciplinary
Rohit Kumar, Sanjukta Pahar, Joy Chatterjee, Soumya Ranjan Dash, Rajesh G. Gonnade, Kumar Vanka, Sakya S. Sen
Summary: In this study, two magnesium complexes supported by 2,2'-pyridylpyrrolide ligands (PyPyrH) were reported. These complexes exhibit bright luminescence with quantum yields of 22% and 14% in the solid state, respectively. Theoretical calculations indicate that their emissive properties originate from intra- and inter-ligand charge transfer.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Alessandro Marotta, Hao Fang, Callum E. Adams, Kailey Sun Marcus, Constantin G. Daniliuc, John J. Molloy
Summary: Operationally simple strategies using visible light and a simple Lewis base are disclosed for the facile activation of α-halo boronic esters, leading to the construction of versatile E-allylic boronic esters via intermolecular addition to styrenes. This activation method can be strategically merged with selective energy transfer catalysis for the complimentary stereodivergent synthesis of Z-allylic boronic esters.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Inorganic & Nuclear
Javier Fajardo, Josef Schwan, Wesley W. Kramer, Michael K. Takase, Jay R. Winkler, Harry B. Gray
Summary: Homoleptic tungsten(0) arylisocyanides exhibit photophysical and photochemical properties comparable to archetypal ruthenium(II) and iridium(III) polypyridine complexes. By systematically varying the arylisocyanide ligands, it is possible to modulate the photophysical properties of these complexes while maintaining high optical performance.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Yang Cheng, Qingqing Yang, Jiang He, Wenjie Zou, Keyu Liao, Xiaoyong Chang, Chao Zou, Wei Lu
Summary: This article introduces a series of substituted anionic ligands containing Cr(iii) complexes, which exhibit phosphorescent properties in degassed fluid solutions.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Matthias Dorn, Jens Kalmbach, Pit Boden, Ayla Kruse, Chahinez Dab, Christian Reber, Gereon Niedner-Schatteburg, Stefan Lochbrunner, Markus Gerhards, Michael Seitz, Katja Heinze
Summary: Luminescent transition metal complexes with Earth-abundant metals are rare, especially those with 3d transition metals showing near-infrared emission. This study investigates the excited state dynamics of a d(2)-vanadium(iii) complex, providing insights for designing molecular materials with spin-flip luminescence and photoinduced metal-ligand bond homolysis.
Article
Biochemistry & Molecular Biology
Jack Saltiel, Sumesh B. Krishnan, Shipra Gupta, Anjan Chakraborty, Edwin F. Hilinski, Xinsong Lin
Summary: Cholesta-5,7,9(11)-trien-3 beta-ol (9,11-dehydroprovitamin D-3, CTL) is used as a fluorescent probe to track the presence and migration of cholesterol in vivo. The photochemistry and photophysics of CTL in degassed and air-saturated tetrahydrofuran (THF) solution, an aprotic solvent, have been studied. The zwitterionic nature of the singlet excited state, (CTL)-C-1*, is revealed in ethanol, a protic solvent. In the presence of air, peroxide formation is a major reaction channel, similar to THF.
Article
Chemistry, Multidisciplinary
Sapna Ahuja, Sruthy Baburaj, Lakshmy Kannadi Valloli, Sarvar Aminovich Rakhimov, Kavyasree Manal, Aakrati Kushwaha, Steffen Jockusch, Malcolm D. E. Forbes, Jayaraman Sivaguru
Summary: Aryl-maleimides undergo a novel [2+4]-photodimerization instead of the expected [2+2]-photodimerization, and the stereochemistry of the photodimer formed complements the product observed under thermal conditions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Ken-ichi Yamanaka, Kosuke Sato, Shunsuke Sato, Shunsuke Nozawa, Sunghee Lee, Ryo Fukaya, Hironobu Fukuzawa, Daehyun You, Shu Saito, Tsukasa Takanashi, Tetsuo Katayama, Tadashi Togashi, Takamasa Nonaka, Kazuhiko Dohmae, Shin-ichi Adachi, Kiyoshi Ueda, Makina Yabashi, Takeshi Morikawa, Ryoji Asahi
Summary: The visible-light excitation process in a known CO2-reduction photocatalyst was investigated using TR-XANES spectroscopy. Ultrafast intersystem crossing and the excited state lifetime of the metal-to-ligand-charge-transfer state were observed.
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Maria Takahashi, Tsuyoshi Asatani, Tatsuki Morimoto, Yoshinobu Kamakura, Kotaro Fujii, Masatomo Yashima, Naoki Hosokawa, Yusuke Tamaki, Osamu Ishitani
Summary: In this study, new redox photosensitisers were synthesized, which can supply different numbers and reduction potentials of electrons to the catalyst in photocatalytic reactions, providing a new approach for the reduction of CO2.
Article
Chemistry, Multidisciplinary
Hiroshi Miyasaka, Syoji Ito, Hikaru Sotome
Summary: Multiphoton absorption and multiple excitation can form highly electronically excited states of molecules, which are difficult to achieve using normal one-photon absorption. This review introduces specific photochemical reactions in the condensed phase, such as two-photon-gated cycloreversion and one-color control of reactions in photochromic systems. It also discusses the rapid capture of an electron ejected from the higher excited state leading to the generation of charge-separated states with a long lifetime.
PURE AND APPLIED CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Hiroi Sei, Kouki Oka, Hikaru Sotome, Hiroshi Miyasaka, Norimitsu Tohnai
Summary: This study presents the use of cage-like sodalite-type porous organic salts as host materials for luminescent molecules to induce room-temperature phosphorescence (RTP). The addition of luminescent molecule pyrene to the construction of porous organic salts enables the incorporation of the molecule, and the presence of heavy halogen atoms on the porous surface allows for heavy atom effects and protection of the incorporated molecule, inducing RTP even in air.
Article
Chemistry, Physical
Kei Kamogawa, Antonio Santoro, Ambra M. Cancelliere, Yuushi Shimoda, Kiyoshi Miyata, Ken Onda, Fausto Puntoriero, Sebastiano Campagna, Yusuke Tamaki, Osamu Ishitani
Summary: Supramolecular photocatalysts, connected redox photosensitizer and catalyst molecules, have higher photocatalytic activity compared to separated systems. By introducing a bridging ligand, the photocatalyst's durability and efficiency can be improved.
Article
Chemistry, Physical
Daiki Saito, Yusuke Tamaki, Osamu Ishitani
Summary: Various hybrid systems of metal-complex photocatalysts and semiconductor materials have been developed for photocatalytic CO2 reduction using the Z-scheme mechanism. This study focused on the photocatalytic activity of RuRu/Al2O3 in CO2 reduction by varying the adsorption density of RuRu. Increasing the adsorption density of RuRu led to a decrease in the production of the main product, HCOOH, due to the formation of Ru polymers. The addition of mononuclear Ru(II)-complex photosensitizers improved the photocatalytic activity of RuRu by supplying electrons to suppress its decomposition.
Article
Chemistry, Physical
Hongwu Yu, Yoichi Okimoto, Atsuya Morita, Shuhei Shimanuki, Kou Takubo, Tadahiko Ishikawa, Shin-ya Koshihara, Ryusei Minakami, Hirotake Itoh, Shinichiro Iwai, Naoshi Ikeda, Takumi Sakagami, Mayu Nozaki, Tatsuo Fujii
Summary: An epitaxial film of YbFe2O4 was fabricated on YSZ substrate by magnetron sputtering technique, and second harmonic generation and terahertz radiation signal were observed. The polarization structure and the relationship between the YbFe2O4 film structure and the crystal axes of the YSZ substrate were revealed through analyses of the SHG profiles. The anisotropic polarization dependence of the observed terahertz pulse suggested that YbFe2O4 can be used as a terahertz wave generator.
Article
Chemistry, Multidisciplinary
Ryo Ohtani, Jianeng Xu, Junichi Yanagisawa, Yuudai Iwai, Takumi Ehara, Kiyoshi Miyata, Ken Onda, Jenny Pirillo, Yuh Hijikata, Tomoaki Hiraoka, Shinya Hayami, Benjamin Le Ouay, Masaaki Ohba
Summary: We synthesized an organic-inorganic hybrid material that undergoes drastic structural changes upon exposure to water vapor. The change in structure results in different photo-physical properties, with one form emitting near-infrared light and shifting to blue with increasing temperature, while the other form emits visible light and shifts to red.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Materials Science, Multidisciplinary
Samiran Banu, Mone Kato, Kou Takubo, Yoichi Okimoto, Shinya Koshihara, Kaoru Iwano, Wataru Kosaka, Hitoshi Miyasaka, Tadahiko Ishikawa
Summary: This study reports on a type of electron donor-acceptor metal-organic framework that exhibits rapid charge transfer and lattice structure changes under photoexcitation. A new electronic state, known as a photoinduced hidden state, appears upon photoexcitation.
ADVANCED OPTICAL MATERIALS
(2023)
Article
Chemistry, Physical
Marcella Bonchio, Julien Bonin, Osamu Ishitani, Tong-Bu Lu, Takeshi Morikawa, Amanda J. Morris, Erwin Reisner, Debashrita Sarkar, Francesca M. Toma, Marc Robert
Summary: Visible-light-driven conversion of CO2 to fuels and valuable compounds has been highly active in recent years. However, these processes and catalytic systems are still in early stages of development, with fundamental mechanistic challenges needing to be addressed. Collaborative efforts are needed to explore various approaches and establish robust practices to advance our understanding of these necessary processes.
Article
Chemistry, Multidisciplinary
Shiori Miyazaki, Kenichi Goushi, Yuichi Kitagawa, Yasuchika Hasegawa, Chihaya Adachi, Kiyoshi Miyata, Ken Onda
Summary: Trivalent lanthanide complexes are attractive light emitters due to their high color purity. Sensitization using ligands with high absorption efficiency can enhance photoluminescence intensity, but the development of antenna ligands is limited. A system composed of triazine-based host molecules and Eu(hfa)(3)(TPPO)(2) significantly increased the total photoluminescence intensity compared to conventional luminescent Eu(iii) complexes. Energy transfer from the host molecules to Eu(iii) occurs via triplet states with nearly 100% efficiency, as shown by time-resolved spectroscopic studies. This discovery enables efficient light harvesting of Eu(iii) complexes through a simple solution process.
Article
Chemistry, Physical
Masashi Sanga, Kosuke Nakamura, Munetaka Iwamura, Koichi Nozaki, Hiroyuki Takeda, Yu Monma, Osamu Ishitani
Summary: In this work, the emission spectra of Cu(i)(dmp)(P)2+ complexes were studied using femtosecond fluorescence up-conversion and nanosecond time-resolved emission spectroscopy. The results showed that there is a structural change of the complex with a time constant of 0.78 ps in acetonitrile solution, and 1.4 ps in butyronitrile solution. The mechanism of different processes was explained by analyzing the oscillator strengths.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Multidisciplinary
Haruka Yoshino, Masaki Saigo, Kiyoshi Miyata, Ken Onda, Jenny Pirillo, Yuh Hijikata, Wataru Kosaka, Hitoshi Miyasaka
Summary: A luminescent three-dimensional coordination polymer (CP) of [Cd-II(pmd){Ag-I(CN)(2)}(2)] (1; pmd = pyrimidine) with two different coordination modes of Ag+ ions was synthesized. 1 exhibited thermochromic luminescence with positive thermal elongation of the Ag center dot center dot center dot Ag distance. Moreover, 1 showed a bright phosphorescence with the highest photoluminescence quantum yield (Phi(em)), approximately 60% at room temperature, among previously reported phosphorescent Ag-based CPs or metal-organic frameworks.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Youichi Tsuchiya, Keito Mizukoshi, Masaki Saigo, Tomohiro Ryu, Kiyoshi Miyata, Ken Onda, Chihaya Adachi
Summary: In recent years, there has been increasing attention on the development of thermally activated delayed fluorescence (TADF) materials to improve the performance of OLED devices. Advanced molecular design can reduce the radiative rate constant by decreasing the HOMO-LUMO overlap, S1-T1 energy difference, and activation energy, while accelerating the reverse intersystem crossing rate constant. In addition, a peculiar thermal behavior similar to negative gap materials has been observed in a specific TADF molecule.
FARADAY DISCUSSIONS
(2023)
