TY - JOUR
T1 - Electronic States of Quinones for Organic Energy Devices
T2 - The Effect of Molecular Structure on Electrochemical Characteristics
AU - Nagamura, Naoka
AU - Taniki, Ryosuke
AU - Kitada, Yuta
AU - Masuda, Asuna
AU - Kobayashi, Hiroaki
AU - Oka, Nobuto
AU - Honma, Itaru
N1 - Funding Information:
This work was supported by the Japan Society for the Promotion of Science (JSPS) through a “Grant-in-Aid for Scientific Research B” (Grant No. 15K17463), and a “Grant-in-Aid for Challenging Exploratory Research” (Grant No.
Funding Information:
15K14153); by the Ministry of Education, Culture, Sports, Science and Technology (MEXT) through a “Grant-in-Aid for Scientific Research on Innovative Areas” (Grant No. 26107503); and by the Research Program for the CORE laboratory of “Dynamic Alliance for Open Innovation Bridging Human, Environment and Materials” in “Network Joint Research Center for Materials and Devices”. This work was performed using a facility of the Institute of Materials Structure Science in Photon Factory, KEK (2014G616, 2016G108, and 2016G656). We thank Dr. Yasunobu Ando in the National Institute of Advanced Industrial Science and Technology (AIST) for DFT calculations. We also thank Prof. Takaaki Tomai in Tohoku University for further discussions and Mr. Shotaro Kawamura for electrochemical analysis. We are also grateful to Dr. Daisuke Asakura and Dr. Eiji Hosono in AIST for XAS measurements.
Publisher Copyright:
© 2018 American Chemical Society.
PY - 2018/7/23
Y1 - 2018/7/23
N2 - The molecular design of organic energy-storage devices relies on correlations between the electrochemical properties of organic materials and their molecular structures. Here we report a systematic study of the fundamental electronic states of the quinone family of redox-active materials. Poly(ethylene oxide) coatings, as elution inhibitors, facilitated the evaluation of the electrochemical properties of single quinone molecules. Moreover, we confirmed experimentally how LUMO energies and their corresponding redox potentials depend on molecular structure, including the number of aromatic rings, the positions of functional groups, and coordination structures; this was achieved by elemental and chemical-state-selective X-ray absorption spectroscopy, and DFT calculations. We introduce an energy diagram depicting a segmentalized reduction process; this diagram considers the intermediate states during redox reactions to discuss processes that dominate changes in electrochemical properties as molecular structures are altered. Our results and analysis strategy are widely applicable to the material design of future organic molecular-based devices.
AB - The molecular design of organic energy-storage devices relies on correlations between the electrochemical properties of organic materials and their molecular structures. Here we report a systematic study of the fundamental electronic states of the quinone family of redox-active materials. Poly(ethylene oxide) coatings, as elution inhibitors, facilitated the evaluation of the electrochemical properties of single quinone molecules. Moreover, we confirmed experimentally how LUMO energies and their corresponding redox potentials depend on molecular structure, including the number of aromatic rings, the positions of functional groups, and coordination structures; this was achieved by elemental and chemical-state-selective X-ray absorption spectroscopy, and DFT calculations. We introduce an energy diagram depicting a segmentalized reduction process; this diagram considers the intermediate states during redox reactions to discuss processes that dominate changes in electrochemical properties as molecular structures are altered. Our results and analysis strategy are widely applicable to the material design of future organic molecular-based devices.
KW - DFT calculation
KW - X-ray absorption spectroscopy
KW - X-ray photoemission spectroscopy
KW - energy diagram
KW - organic redox-active material
KW - quinone
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U2 - 10.1021/acsaem.7b00156
DO - 10.1021/acsaem.7b00156
M3 - Article
AN - SCOPUS:85058442111
VL - 1
SP - 3084
EP - 3092
JO - ACS Applied Energy Materials
JF - ACS Applied Energy Materials
SN - 2574-0962
IS - 7
ER -