Observation of Proton Transfer Coupled Spin Transition and Trapping of Photoinduced Metastable Proton Transfer State in an Fe(II) Complex
- Takumi NakanishiTakumi NakanishiInstitute for Materials Chemistry and Engineering & IRCCS, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 819-0395, JapanMore by Takumi Nakanishi,
- Yuta HoriYuta HoriInstitute for Materials Chemistry and Engineering & IRCCS, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 819-0395, JapanCenter for Computational Sciences, University of Tsukuba, Tsukuba 305-8577, JapanMore by Yuta Hori,
- Hiroyasu SatoHiroyasu SatoRigaku Corporation, 3-9-12 Matsubaracho, Akishima, Tokyo 196-8666, JapanMore by Hiroyasu Sato,
- Shu-Qi WuShu-Qi WuInstitute for Materials Chemistry and Engineering & IRCCS, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 819-0395, JapanMore by Shu-Qi Wu,
- Atsushi OkazawaAtsushi OkazawaDepartment of Basic Science, Graduation School of Arts and Sciences, The University of Tokyo, 3-8-1 Komaba, Meguro-ku, Tokyo 153-8902, JapanMore by Atsushi Okazawa,
- Norimichi KojimaNorimichi KojimaToyota Physical and Chemical Research Institute, Yokomichi, Nagakute, Aichi 480-1192, JapanMore by Norimichi Kojima,
- Takashi YamamotoTakashi YamamotoDepartment of Chemistry, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama, Kanagawa 223-8522, JapanMore by Takashi Yamamoto,
- Yasuaki EinagaYasuaki EinagaDepartment of Chemistry, Faculty of Advanced Science and Technology, Kumamoto University, 2-39-1 Kurokami, Chuo-ku, Kumamoto 860-8555, JapanMore by Yasuaki Einaga,
- Shinya HayamiShinya HayamiDepartment of Chemistry, Faculty of Advanced Science and Technology, Kumamoto University, 2-39-1 Kurokami, Chuo-ku, Kumamoto 860-8555, JapanInstitute of Pulsed Power Science (IPPS), Kumamoto University, 2-39-1 Kurokami, Chuo-ku, Kumamoto 860-8555, JapanMore by Shinya Hayami,
- Yusuke HorieYusuke HorieGraduate School of Science and Engineering, Aoyama Gakuin University, 5-10-1 Fuchinobe, Chuo-ku, Sagamihara, Kanagawa 252-5258, JapanMore by Yusuke Horie,
- Hajime OkajimaHajime OkajimaGraduate School of Science and Engineering, Aoyama Gakuin University, 5-10-1 Fuchinobe, Chuo-ku, Sagamihara, Kanagawa 252-5258, JapanMore by Hajime Okajima,
- Akira SakamotoAkira SakamotoGraduate School of Science and Engineering, Aoyama Gakuin University, 5-10-1 Fuchinobe, Chuo-ku, Sagamihara, Kanagawa 252-5258, JapanMore by Akira Sakamoto,
- Yoshihito ShiotaYoshihito ShiotaInstitute for Materials Chemistry and Engineering & IRCCS, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 819-0395, JapanMore by Yoshihito Shiota,
- Kazunari YoshizawaKazunari YoshizawaInstitute for Materials Chemistry and Engineering & IRCCS, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 819-0395, JapanMore by Kazunari Yoshizawa, and
- Osamu Sato*Osamu Sato*[email protected]Institute for Materials Chemistry and Engineering & IRCCS, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 819-0395, JapanMore by Osamu Sato
Abstract
An important technique to realize novel electron- and/or proton-based functionalities is to use a proton–electron coupling mechanism. When either a proton or electron is excited, the other one is modulated, producing synergistic functions. However, although compounds with proton-coupled electron transfer have been synthesized, crystalline molecular compounds that exhibit proton-transfer-coupled spin-transition (PCST) behavior have not been reported. Here, we report the first example of a PCST Fe(II) complex, wherein the proton lies on the N of hydrazone and pyridine moieties in the ligand at high-spin and low-spin Fe(II), respectively. When the Fe(II) complex is irradiated with light, intramolecular proton transfer occurs from pyridine to hydrazone in conjunction with the photoinduced spin transition via the PCST mechanism. Because the light-induced excited high-spin state is trapped at low temperatures in the Fe(II) complex—a phenomenon known as the light-induced excited-spin-state trapping effect—the light-induced proton-transfer state, wherein the proton lies on the N of hydrazone, is also trapped as a metastable state. The proton transfer was accomplished within 50 ps at 190 K. The bistable nature of the proton position, where the position can be switched by light irradiation, is useful for modulating proton-based functionalities in molecular devices.
Cited By
This article is cited by 8 publications.
- Andrei V. Astashkin, Rachel D. Utterback, Yu-Shien Sung, Elisa Tomat. Iron Complexes of an Antiproliferative Aroyl Hydrazone: Characterization of Three Protonation States by Electron Paramagnetic Resonance Methods. Inorganic Chemistry 2020, 59 (16) , 11377-11384. https://doi.org/10.1021/acs.inorgchem.0c01120
- Ruihua Zhao, Jiandong Guo, Chaoshen Zhang, Yu Lu, Wasihun Menberu Dagnaw, Zhi-Xiang Wang. DFT Mechanistic Insight into the Dioxygenase-like Reactivity of a CoIII-peroxo Complex: O–O Bond Cleavage via a [1,3]-Sigmatropic Rearrangement-like Mechanism. Inorganic Chemistry 2020, 59 (3) , 2051-2061. https://doi.org/10.1021/acs.inorgchem.9b03470
- Tesfay Gebretsadik, Qianqian Yang, Jinjiang Wu, Jinkui Tang. Hydrazone based spin crossover complexes: Behind the extra flexibility of the hydrazone moiety to switch the spin state. Coordination Chemistry Reviews 2021, 431 , 213666. https://doi.org/10.1016/j.ccr.2020.213666
- Verónica Jornet-Mollá, Carlos Giménez-Saiz, Laura Cañadillas-Delgado, Dmitry S. Yufit, Judith A. K. Howard, Francisco M. Romero. Interplay between spin crossover and proton migration along short strong hydrogen bonds. Chemical Science 2021, 12 (3) , 1038-1053. https://doi.org/10.1039/D0SC04918B
- Takumi Nakanishi, Yuta Hori, Shuqi Wu, Hiroyasu Sato, Atsushi Okazawa, Norimichi Kojima, Yusuke Horie, Hajime Okajima, Akira Sakamoto, Yoshihito Shiota, Kazunari Yoshizawa, Osamu Sato. Three‐Step Spin State Transition and Hysteretic Proton Transfer in the Crystal of an Iron(II) Hydrazone Complex. Angewandte Chemie 2020, 132 (35) , 14891-14897. https://doi.org/10.1002/ange.202006763
- Takumi Nakanishi, Yuta Hori, Shuqi Wu, Hiroyasu Sato, Atsushi Okazawa, Norimichi Kojima, Yusuke Horie, Hajime Okajima, Akira Sakamoto, Yoshihito Shiota, Kazunari Yoshizawa, Osamu Sato. Three‐Step Spin State Transition and Hysteretic Proton Transfer in the Crystal of an Iron(II) Hydrazone Complex. Angewandte Chemie International Edition 2020, 59 (35) , 14781-14787. https://doi.org/10.1002/anie.202006763
- Hye Jin Cho, TaeWoo Kim, Hyunwoo Kim, Changsik Song. Solid-State Emissive Metallo-Supramolecular Assemblies of Quinoline-Based Acyl Hydrazone. Sensors 2020, 20 (3) , 600. https://doi.org/10.3390/s20030600
- Na Li, Jin-Peng Xue, Jing-Lin Liu, Yao-Yao Wang, Zi-Shuo Yao, Jun Tao. Switchable on–off spin-crossover properties of iron( ii ) compounds by trimming intermolecular hydrogen bonds. Dalton Transactions 2020, 49 (4) , 998-1001. https://doi.org/10.1039/C9DT04685B