Review
Chemistry, Inorganic & Nuclear
Bowen Ding, Marcello B. Solomon, Chanel F. Leong, Deanna M. D. Alessandro
Summary: The field of coordination polymers and metal-organic frameworks has rapidly developed over the past three decades, with a focus on introducing redox properties to modulate the properties of solid-state electronic devices. A key challenge is the engineering of framework materials with desired redox properties for specific functions, while emergent redox-active ligands offer new opportunities for improving the performance of solar cells, photo switches, photoelectrocatalysts, and charge transfer in MOF materials.
COORDINATION CHEMISTRY REVIEWS
(2021)
Article
Chemistry, Inorganic & Nuclear
Yoshinobu Kamakura, Satoshi Fujisawa, Koki Takahashi, Hiroki Toshima, Yuka Nakatani, Hirofumi Yoshikawa, Akinori Saeki, Kazuyoshi Ogasawara, Daisuke Tanaka
Summary: This study reports the preparation and characterization of two Sn-MOF crystal structures, KGF-4 and KGF-10, with thiolates as coordinating functional groups. KGF-10, isolated as a pure phase, exhibits redox properties and a semiconducting band structure as confirmed by first-principles calculations.
INORGANIC CHEMISTRY
(2021)
Article
Environmental Sciences
Serhat Uzan
Summary: The existing reducing agents for methylene blue decolorization are soluble in water and the reduction process is carried out in a homogeneous redox reaction medium. However, these reducing agents often remain in the reaction medium after decolorization, leading to chemical pollution of textile wastewater. To address this issue, a water-insoluble redox active azo polymer was synthesized for heterogeneous reduction of methylene blue. The kinetic parameters of this redox reaction were investigated and compared with those of the azo polymer monomer (1,4-dihydroxybenzene).
ENVIRONMENTAL POLLUTION
(2023)
Article
Polymer Science
Hao-Xuan Guo, Yuriko Takemura, Daisuke Tange, Junichi Kurata, Hiroyuki Aota
Summary: In this study, redox-active polymers were synthesized step by step on a gold electrode to optimize their electrochemical performance. An automatic sequential polymerization equipment was designed to minimize human intervention in the stepwise polymerization reaction. The degree of polymerization of the polymer grown on the gold electrode can be controlled by adjusting the cycle of the sequential operation. As the number of cycles increases, the amount of accumulated charge increases proportionally, indicating the potential for enhanced electrochemical performance.
Article
Chemistry, Multidisciplinary
Yuwen Luo, Jinlong Liu, Lei Zhang
Summary: In this study, the researchers selected a high-capacity carbonyl compound as the organic ligand and successfully synthesized copper(II) chloranilate with layered structure and high electronic conductivity by coordinating with high-voltage transition metal nodes. The resulting material exhibits multiple redox centers, fast ion diffusion kinetics, and excellent electrochemical performance, making it a promising cathode material for high-performance lithium-ion batteries.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Energy & Fuels
Qinzheng Hu, Shuzhen Cui, Kanjun Sun, Xiuting Shi, Wenxing Miao, Xiangbing Wang, Hui Peng, Guofu Ma
Summary: The focus of recent research on flexible supercapacitors is to improve their energy density. A recent study has reported an improved energy storage method by adding suitable redox additives to gel electrolytes to enhance their redox activity. This study presents a novel stretchable and redox-active hydrogel electrolyte, prepared through polymerization and solvent displacement, which shows superior stretchability and high energy density. The introduction of a redox additive further enhances the specific capacitance and energy density. This study provides a new strategy for designing multifunctional redox hydrogel electrolytes.
JOURNAL OF ENERGY STORAGE
(2023)
Article
Chemistry, Multidisciplinary
Yusheng Shi, Peiyuan Wang, Mochen Li, Tiexin Zhang, Gang Han, Chunying Duan
Summary: Redox logic materials provide new approaches to modulate intracellular pathologic redox environment in specific areas, but the unambiguity and repetitive switchability of redox logic states are difficult to achieve. A multistable coordination polymer (CP) was constructed by combining a bistable diisophthalic phenazine dye ligand with Cu-II salt, and its dye-Cu anisotropic junction achieved diode-like unidirectional electron transfer and logic state ratchet for the first time. The radical cationic CP remained in the OFF state with low toxicity in healthy tissues, but was reduced to the neutral SERVO state by overexpressed glutathione (GSH) in hypoxic tumors. After photoirradiation, the stabilized charge-separated ON state promoted photo-Fenton reaction for reactive oxygen species (ROS) signal transduction, while simultaneously recovering the initial state for catalytic signal amplification of ROS, providing intratumor redox photomodulation for therapy.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Applied
Elmira Payami, Reza Teimuri-Mofrad
Summary: The research focused on the preparation of redox-active porous polymers and composite materials with high specific capacitance and excellent charge storage retention, using a cost-effective synthetic route.
APPLIED ORGANOMETALLIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Neetu Yadav, Nitish Yadav, S. A. Hashmi
Summary: The study introduces a quasi-solid-state supercapacitor with a nonaqueous gel polymer electrolyte (GPE) containing redox additive hydroquinone, showing high ionic conductivity and wide electrochemical stability window, making it a potential electrolyte for high-energy-density supercapacitors.
ACS APPLIED ENERGY MATERIALS
(2021)
Article
Chemistry, Inorganic & Nuclear
Lotfali Saghatforoush, Mohammad Hakimi, Ali Gholipour, Akbar Bakhtiari, Keyvan Moeini, Vaclav Eigner, Michal Dusek
Summary: Two lead(II) 1D-coordination polymers were synthesized, with one exhibiting the first example of lead(II) ion coordination with a tetrazine ligand. The ligands around the lead (II) ions are arranged in a hemidirected mode, and in the crystal network of the complexes, there are hydrogen bonds and pi-pi stacking interactions between pyridine rings.
Review
Polymer Science
Philip Rohland, Erik Schroeter, Oliver Nolte, George R. Newkome, Martin D. Hager, Ulrich S. Schubert
Summary: Renewable organic batteries are valuable for storing sustainably generated energy and phasing out carbon-based energy production. Over the past 80 years, various approaches using organic redox materials in batteries have emerged, with polymers gaining considerable interest. Polymers offer fast redox chemistry, straightforward synthesis, and tunable solubility, making them suitable for diverse electronic devices. Redox-active polymers were studied as early as 1944 and have evolved from an interesting phenomenon to a promising family of tailor-made battery materials, with commercial applications. This review focuses on the design of interesting polymeric, redox-active materials, discussing polymerization techniques, architectures, and practical properties, as well as their applications in solid-state batteries, pseudo-capacitors, and redox-flow batteries.
PROGRESS IN POLYMER SCIENCE
(2022)
Article
Polymer Science
Hongxing Wang, Feng Qiu, Chenbao Lu, Jinhui Zhu, Changchun Ke, Sheng Han, Xiaodong Zhuang
Summary: This study successfully prepared ultrathin polymer films with flexible properties, good redox activity, and narrow bandgap using a liquid-liquid interfacial polymerization method. These films were then utilized for microsized energy storage devices, exhibiting superior performance.
Article
Chemistry, Multidisciplinary
Jun Ying, Liang Jin, Hai-Yan Yu, Ai-Xiang Tian, Xiu-Li Wang
Summary: Six polyoxometalate-based complexes were synthesized by changing transition metals and polyanions for potential applications in sensing and catalysis.
Article
Nanoscience & Nanotechnology
Alicia M. Battaglia, Paniz Pahlavanlu, Eloi Grignon, So Young An, Dwight S. Seferos
Summary: Organic electrodes are promising candidates for next generation lithium-ion batteries, but often suffer from low conductivity and active material loadings. In this study, a new organic polymer binder PEDOT-b-PEG was developed, which showed higher capacities and lower impedance compared to traditional binders, offering potential for achieving higher active material loadings in organic electrodes.
ACS APPLIED MATERIALS & INTERFACES
(2022)
Article
Chemistry, Multidisciplinary
Tomoaki Tanase, Kanako Nakamae, Haruka Miyano, Yasuyuki Ura, Yasutaka Kitagawa, Shiho Yada, Tomokazu Yoshimura, Takayuki Nakajima
Summary: A series of octapalladium chains supported by meso-dpmppm ligands were synthesized and characterized. The structures and electronic states of the Pd-8 chains were found finely tunable by varying the terminal capping ligands. Theoretical calculations elucidated the relationship between the HOMO-LUMO energy gap and the central Pd-Pd distance, reflected in NIR absorption energy.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Physical
Samuel R. Wenger, Eleanor R. Kearns, Kaleb L. Miller, Deanna M. D'Alessandro
Summary: In this study, we conducted a techno-economic analysis on a green mechanochemical synthesis process for the typical metal-organic framework UiO-66-NH2. The analysis revealed the significant role of labor costs in manufacturing expenses and emphasized the importance of scaling production from a batch method to a more continuous synthesis mechanism. Through our work, we achieved a mechanochemical production rate of 4.52 grams per 90 minutes with a 43% yield, resulting in a levelized cost of approximately US $6,498 per kilogram, which is comparable to other typical MOFs available in the market.
ACS APPLIED ENERGY MATERIALS
(2022)
Article
Chemistry, Physical
Eleanor R. Kearns, Jack K. Clegg, William Lewis, Ada Fang, Bun Chan, Deanna M. D'Alessandro
Summary: As complex materials are widely used in emerging technologies for environmental and energy applications, it is important to be able to quantify their stimuli-response behaviors. In this study, a double [2 + 2] photocyclization reaction in a photoactive material was utilized as a powerful platform to quantitatively investigate solid-state photocyclization kinetics. The results showed a maximum rate observed between 0 degrees C and 20 degrees C of approximately 0.172 s-1, providing the first example of quantification of photocyclization kinetics in a MOF. Density functional theory calculations supported a singlet reaction mechanism for the double [2 + 2] photocyclization.
CHEMISTRY OF MATERIALS
(2022)
Article
Chemistry, Physical
Kimihiko Hirao, Takahito Nakajima, Bun Chan, Ho-Jin Lee
Summary: The core ionization energies of second-period and third-period elements are investigated using Lambda SCF and Slater's transition state (STS) theory with Hartree-Fock (HF) and Kohn-Sham (KS) approximations. Electron correlation increases the estimated core ionization energies, while the self-interaction error (SIE) decreases them, especially for the third-period elements. HF predictions of core ionization energies are reasonably accurate due to the lack of SIE, while KS calculations are sensitive to the functional used. Overall, the study highlights the importance of considering electron correlation and SIE when predicting core ionization energies. Rating: 7 out of 10.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Multidisciplinary
Bun Chan, Seiji Shirakawa
Summary: In this study, computational quantum chemistry was used to investigate the cation affinity of various nucleophiles. The results suggest that organochalcogens may serve as catalysts for cation transfer. The study also found that certain DFT methods, such as DSD-PBEP86, can be used to study these cation transfer processes.
CANADIAN JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Physical
Bun Chan
Summary: In this study, the performance of various small basis sets and their geometric counterpoise (gCP) corrections for DFT computations were examined. It was found that a simplified scheme, unity-gCP, using a single scaling parameter, can yield fair results for an arbitrary basis set. The optimal balance between accuracy and computational efficiency was found to be 6-31+G(2d) for medium-sized basis sets. On the other hand, less balanced basis sets, even larger ones, can show significantly worse accuracy, and the inclusion of gCP may lead to overcorrections.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Multidisciplinary
Samuel R. R. Wenger, Lyndon A. A. Hall, Deanna M. M. D'Alessandro
Summary: This paper describes the facile synthesis of a redox-active MOF/quinone composite, which can be used as a cathodic material for the electrochemical capture of CO2. Conventional adsorbents for CO2 capture typically utilize swings in temperature and/or pressure to adsorb and desorb CO2. In this work, the authors demonstrate the synthesis of a redox-active MOF-based adsorbent for the electrochemical capture of CO2, using spectroelectrochemistry to study the interaction between the adsorbent and CO2. This represents an advancement towards the scalable production of electro-swing adsorbents and shows the potential of MOFs for this process.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2023)
Article
Nanoscience & Nanotechnology
Yakui Mu, Tan Wang, Zeyu Deng, Bun Chan, Tiesheng Wang
Summary: Organic crystals assembled by TTF-based molecules hold potential for electronics, smart materials, and superconductors. A fragment charge difference method was used to investigate the charge transfer properties of these crystals, and the results were consistent with another established method. The study also demonstrated the influence of structure and chemistry on charge transfer properties.
Article
Chemistry, Multidisciplinary
Eleanor R. Kearns, Deanna M. D'Alessandro
Summary: This work investigates the application of two different solid-state kinetic models in the [2 + 2] photocyclization reaction of MOF materials, and finds that the Finke-Watzky model provides a more accurate fit for the data.
CRYSTAL GROWTH & DESIGN
(2023)
Article
Chemistry, Multidisciplinary
Kimihiko Hirao, Takahito Nakajima, Bun Chan, Ho-Jin Lee
Summary: This study calculates the core ionization energies of various molecules using different methods and compares the results. The use of the shifted STS methods is shown to be effective in predicting the core ionization energies.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2023)
Article
Chemistry, Physical
Bun Chan
Summary: In this study, computational quantum chemistry is used to obtain lattice energies (LEs) for various ionic clusters with the NaCl structure. Different methods are applied to small and large clusters, and species-specific adjustments are made to account for systematic deviations. The results provide a straightforward means to estimate LEs for similarly structured ionic compounds.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Review
Chemistry, Multidisciplinary
Lyndon A. Hall, Deanna M. D'Alessandro, Girish Lakhwani
Summary: Recently, there is growing interest in the use of chiral metal-organic frameworks (MOFs) and coordination polymers (CPs) for photonics applications. These materials offer the ability to tune their properties and realize new functionalities through the selection of metal and ligand components. This review focuses on the synthesis of chiral MOFs and CPs, their recent innovations in optical and photonics applications, as well as the challenges and potential solutions in this field. Overall, chiral MOFs and CPs show great promise for future technologies such as optical communication and computing, optical displays, and all-optical devices.
CHEMICAL SOCIETY REVIEWS
(2023)
Article
Chemistry, Physical
Bun Chan, Amir Karton
Summary: In this study, the energy differences between singlet and triplet states of small fullerenes were investigated using density functional theory (DFT), along with the ionization energy (IE) and electron affinity (EA). The DFT methods consistently showed qualitative observations. Among the 812 fullerene isomers, approximately 80-90% had a singlet ground state, while the rest had ground-state triplets. Some of these may enhance the efficiency of singlet-fission materials for light harvesting. The triplet-singlet energy difference correlated well with the IE-EA differences, which serve as indicators for charge-transfer capabilities. Larger fullerenes were surveyed to identify candidates with superior charge-transfer properties, suggesting that optimally shaped medium-sized fullerenes are the most promising.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Materials Science, Multidisciplinary
Qinyi Gu, Zi-Han Zhao, Bun Chan, Tong Yan, Jing-Lin Zuo, Deanna M. D'Alessandro, Cheng-Hui Li
Summary: A new Ni-dithiolene ligand was used to prepare a photothermal metal-organic framework (MOF) that showed efficient conversion of light into heat. The MOF had strong absorption in the near-infrared region due to the radical monoanion of the ligands, and the structure played an important role in the photothermal properties. The photothermal MOF was then doped into a self-healing polymer, enabling the composites to recover from dynamic damage using the heat generated by photostimulus.
ACS MATERIALS LETTERS
(2023)
Article
Multidisciplinary Sciences
Chisato Terada, Kaho Oh, Ryutaro Tsubaki, Bun Chan, Nozomi Aibara, Kaname Ohyama, Masa-Aki Shibata, Takehiko Wada, Mariko Harada-Shiba, Asako Yamayoshi, Tsuyoshi Yamamoto
Summary: In this study, a toehold-bearing ASO architecture is developed to mitigate a broad spectrum of off-target interactions, significantly enhancing the safety profile of ASO drugs.
NATURE COMMUNICATIONS
(2023)
