Article
Chemistry, Multidisciplinary
Christoph Wallach, Felix S. Geitner, Antti J. Karttunen, Thomas F. Faessler
Summary: The unique three-dimensional structure of spherical, homoatomic nine-atom germanium clusters allows for various spatial arrangement of functional groups. Recent introduction of ligands with lone pairs and addition of boranyl group to the cluster featuring a Ge-B exo-cluster bond have expanded the possibilities in cluster chemistry. Quantum-chemical calculations have revealed the frustrated Lewis pair character of the boranyl-functionalized cluster.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Shubhajit Das, Roland C. Turnell-Ritson, Paul J. Dyson, Clemence Corminboeuf
Summary: Despite recent progress in the chemistry of frustrated Lewis pairs (FLPs), direct FLP-catalyzed hydrogenation of CO2 remains elusive. The authors propose a mapping method to link the chemical composition of FLPs with their activity in catalytic hydrogenation of CO2, and they experimentally validate a combination with high catalytic turnover.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Multidisciplinary
Minsoo Ju, Zhipeng Lu, Luiz F. T. Novaes, Jesus I. Martinez Alvarado, Song Lin
Summary: Frustrated radical pairs (FRPs) are able to coexist in solution due to steric repulsion or weak bonding association between two distinct radicals, which would otherwise annihilate each other. They are typically formed via spontaneous single-electron transfer between two sterically encumbered precursors and exhibit orthogonal chemical properties. FRPs have been found to be capable of homolytically activating various chemical bonds and are being extensively explored in synthetic organic chemistry, including C-H bond functionalization.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Hui Mao, Zijiang Chen, Longjiu Cheng, Kun Wang
Summary: The article discusses the catalytic effect and hydrogen storage potential of Frustrated Lewis Pairs (FLPs) in the hydrogenation process, emphasizing the influence of acidity and alkalinity on the activity and reversibility of FLPs. The study found that FLPs composed of strong acids and relatively weak bases exhibit better reversibility and reaction rates in hydrogenation.
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
(2021)
Review
Biochemical Research Methods
Gitanjali Sharma, Paul D. Newman, James A. Platts
Summary: This review discusses the power of quantum chemistry, particularly density functional theory (DFT), in unraveling mechanisms in the field of FLP chemistry. It covers various aspects such as hydrogen activation, borylation, silylation, polymerization, formation of heterocycles, reaction with small gaseous molecules, alkenes, terminal alkynes, and the role of DFT in understanding regio-selectivity, steric effects, London dispersion, and covalent interactions in FLPs.
JOURNAL OF MOLECULAR GRAPHICS & MODELLING
(2021)
Review
Biochemistry & Molecular Biology
Qiang Wan, Sen Lin, Hua Guo
Summary: This article reviews recent theoretical advances in understanding FLP-based heterogeneous catalysis in various applications, such as metal oxides, functionalized surfaces, and two-dimensional materials. It emphasizes the importance of a better understanding of the catalytic mechanism for the experimental design of novel heterogeneous FLP catalysts.
Article
Chemistry, Multidisciplinary
Chang-Yin Tan, Myojeong Kim, Inyoung Park, Yuhyun Kim, Sungwoo Hong
Summary: A unified strategy for the deoxygenative or desulfurative pyridylation of various alcohols and thiols has been developed using a single-electron transfer (SET) process mediated by frustrated Lewis pairs (FLPs). The method involves the formation of FLPs between pyridinium salts and PtBu3, and the generation of alkyl radicals through the ionic coupling of phosphine radical cations with in situ generated xanthates. Visible-light irradiation enhances the reaction efficiency. This method offers a previously unrecognized opportunity for the selective heteroarylation of alcohols and thiols with diverse functional groups.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Yan Liang, Zhong Zhang, Xiaofang Su, Xiao Feng, Songzhu Xing, Wei Liu, Rui Huang, Yiwei Liu
Summary: Precisely controlling the structure and spatial distance between Lewis acid and Lewis base sites in a porous system is essential for constructing efficient solid frustrated Lewis pair (FLP) catalysts. In this study, FLP sites were constructed in a polyoxometalate (POM)-based metal-organic framework (MOF) by introducing coordination-defect metal nodes (Lewis acid) and surface-basic POM with abundant oxygen (Lewis base). The resulting FLP catalyst exhibited high hydrogenation activity, with 55 and 2.7 times higher activity compared to defect-free POM-based MOF and defective MOF without POM, respectively. This work offers a new approach for the precise design of multi-site catalysts for specific substrate activation and synergistic catalysis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Huaxun Luo, Boyu Zhu, Xiaomin Liu, Xiaomin Zhang, Tianxiang Zhao, Xingbang Hu
Summary: Through experimental and computational studies, it was found that moderately bulky bases can activate hydrogen and serve as catalysts for the hydrogenation of CO2 to formate. Typical frustrated Lewis pairs (FLPs), known for their high efficiency in H2 activation, were found to be less efficient than non-frustrated Lewis pairs (n-FLPs) for this reaction. These results are expected to inspire the development of novel Lewis pair catalyzed reactions.
MOLECULAR CATALYSIS
(2023)
Article
Multidisciplinary Sciences
Zhipeng Lu, Minsoo Ju, Yi Wang, Jonathan M. Meinhardt, Jesus I. Martinez Alvarado, Elisia Villemure, Jack A. Terrett, Song Lin
Summary: This study demonstrates the functionalization of C(sp(3))-H bonds using frustrated radical pairs (FRPs) generated from disilazide donors and an N-oxoammonium acceptor. The FRPs cleave unactivated C-H bonds to provide aminoxylated products, and the reaction selectivity towards tertiary, secondary, or primary C-H bonds can be controlled by tuning the structure of the donor. Mechanistic studies confirm the formation and involvement of radical pairs in the target reaction.
Article
Chemistry, Physical
Yong Zou, Mingkai Zhang, Yuxuan Liu, Yuanyuan Ma, Sai Zhang, Yongquan Qu
Summary: Interfacial frustrated Lewis pairs constructed on the CeO2 surface have been demonstrated as novel catalytic active sites for highly selective transfer hydrogenation, showing great potential for the conversion of biomass.
JOURNAL OF CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Ze-Ming Xu, Zhuoyi Hu, Yali Huang, Shu-Jin Bao, Zheng Niu, Jian-Ping Lang, Abdullah M. Al-Enizi, Ayman Nafady, Shengqian Ma
Summary: Hydrogenated nitrogen heterocyclic compounds are critical in various industries. Previous studies on the partial hydrogenation of these compounds have focused on costly and toxic precious metal catalysts. This research introduces a novel P/B type MOF-FLP catalyst achieved through a solvent-assisted linker incorporation approach, which significantly enhances catalytic hydrogenation reactions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Inorganic & Nuclear
Pallavi Sarkar, Shubhajit Das, Swapan K. Pati
Summary: Research findings show that utilizing neutral tetrel atoms as acceptor sites in FLP can achieve the required Lewis acidity through antibonding orbitals, impacting the synchronicity of bond breaking and formation during H-2 activation. Varying the identity of the donor site can significantly affect the energetics of H-2 activation. Additionally, the study explores the potential extension of H-2 activation to catalytic hydrogenation by these FLPs.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Shubhajit Das, Swapan K. Pati
Summary: This study investigates a family of intramolecular stannylium/nitrogen FLPs for catalytic hydrogenation of organic compounds with unsaturated functional groups. The activation of H-2 by these FLPs proceeds through the cooperative action of the Sn and N centers, allowing for catalytic hydrogenation of organic substrates. The reactivity of these FLPs can be tuned by varying substituents and counter anions on the Sn center.
Article
Chemistry, Physical
Panpan Wu, Hui Mao, Zijiang Chen, Longjiu Cheng, Kun Wang
Summary: In this study, Frustrated Lewis pairs (FLPs) with different acidity/basicity were selected and designed. It was found that FLPs composed of soft strong Lewis acid (LA) and hard moderate Lewis base (LB) showed the best activity and reversibility in hydrogenation. The cooperativity between LA and LB was demonstrated to determine the catalytic performance in hydrogen activation.
Article
Chemistry, Multidisciplinary
Tianjun Liu, Wenda Shi, Weidong Tang, Zilu Liu, Bob C. Schroeder, Oliver Fenwick, Matthew J. Fuchter
Summary: A CPL detector based on quasi-2D chiral perovskite films is reported, which exhibits both a high dissymmetry factor and responsivity, showcasing the potential of chiral perovskites in CPL-dependent photonic technologies.
Article
Materials Science, Multidisciplinary
Matthew D. Ward, Jessica Wade, Xingyuan Shi, Jenny Nelson, Alasdair J. Campbell, Matthew J. Fuchter
Summary: A simple bilayer organic photodiode with high sensitivity to circularly polarized light has been developed, demonstrating fast switching speeds, large dynamic range, and high photocurrent dissymmetry.
ADVANCED OPTICAL MATERIALS
(2022)
Correction
Nanoscience & Nanotechnology
Li Wan, Jessica Wade, Xingyuan Shi, Shengda Xu, Matthew J. Fuchter, Alasdair J. Campbell
ACS APPLIED MATERIALS & INTERFACES
(2022)
Correction
Chemistry, Multidisciplinary
Li Wan, Jessica Wade, Francesco Salerno, Oriol Arteaga, Beth Laidlaw, Xuhua Wang, Thomas Penfold, Matthew J. Fuchter, Alasdair J. Campbell
Article
Chemistry, Multidisciplinary
Jose Cammarata, Daniel J. Scott, Robert Wolf
Summary: This study presents a practical method for synthesizing monophosphorus compounds directly from red phosphorus. The reactions are conducted under relatively mild conditions and use inexpensive and readily available reagents, making it accessible in most laboratory settings.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Optics
Li Wan, Yizhou Liu, Matthew J. Fuchter, Binghai Yan
Summary: Researchers have discovered that the handedness of circularly polarized light in OLEDs can be switched by reversing the current flow. This direction-dependent emission greatly increases the polarization rate and addresses the issue of symmetry loss in CP-OLEDs. The anomalous CP emission is attributed to the topological electronic property known as orbital-momentum locking in chiral materials.
Article
Chemistry, Medicinal
Louis Minion, Jessica Wade, Juan Manuel Moreno-Naranjo, Sean Ryan, Giuliano Siligardi, Matthew J. Fuchter
Summary: We synthesized a fluorene-bithiophene co-polymer with chiral side chains and studied its chiroptical properties using synchotronradiation circular dichroism. Thin films of the polymer showed an intense circular dichroism of opposite handedness compared to similar polyfluorenes with the same enantiomeric chiral side chains. Comparing the polymer with a chiral side chain fluorene homopolymer, significant differences in thin film morphology were observed. Evidence of polymer chain bending in cPFT2 was uncovered through photoluminescence spectroscopy and theoretical calculations, providing an explanation for the observed inverted optical activity.
Article
Chemistry, Physical
Wenda Shi, Qiang Zhuang, Rui Zhou, Xueyan Hou, Xiaoming Zhao, Jie Kong, Matthew J. Fuchter
Summary: The use of chiral fullerenes as electron transport layers in perovskite solar cells has shown improved performance and operational stability.
ADVANCED ENERGY MATERIALS
(2023)
Editorial Material
Nanoscience & Nanotechnology
Jeanne Crassous, Matthew J. Fuchter, Danna E. Freedman, Nicholas A. Kotov, Jooho Moon, Matthew C. Beard, Sascha Feldmann
Summary: Solution-processable semiconductors based on small molecules, polymers or halide perovskites combine sustainable manufacturing with exceptional optoelectronic properties that can be chemically tailored to achieve flexible and highly efficient optoelectronic and photonic devices. A new exciting research direction is the study of the influence of chirality on light-matter interactions in these soft materials and its exploitation for the simultaneous control of charge, spin and light. In this Viewpoint, researchers working on different types of chiral semiconductors discuss the most interesting directions in this rapidly expanding field.
NATURE REVIEWS MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Kieran Griffiths, Jake L. Greenfield, Nathan R. Halcovitch, Matthew J. Fuchter, John M. Griffin
Summary: Arylazopyrazole-loaded metal-organic frameworks were synthesized and their contraction and expansion properties were studied. The shape and pendant groups of the guest molecules influenced the framework contraction, and the framework expanded under light illumination. Confinement within the framework extended the thermal stability of the isomer.
CRYSTAL GROWTH & DESIGN
(2023)
Article
Chemistry, Physical
Samuel J. Horsewill, Gabriele Hierlmeier, Zahra Farasat, Joshua P. Barham, Daniel J. Scott
Summary: Photoredox catalysis (PRC) has attracted significant interest but its mechanism is still uncertain. This study demonstrates the isolation of one-electron reduction products of representative PRC catalysts, allowing for controlled study of their reactivity and mechanistic roles. This provides a foundation for future investigation into the mechanism of PRC and other related reactions.
Article
Chemistry, Multidisciplinary
Samuel J. Horsewill, Chengyang Cao, Noah Dabney, Eric S. Yang, Stephen Faulkner, Daniel J. Scott
Summary: In this study, we address the lack of mechanistic understanding in the field of photoredox catalysis by isolating and characterising one of the intermediates of the iconic photocatalyst [Ru(bipy)(3)](2+), and testing its initial photoreactivity towards common substrates.
CHEMICAL COMMUNICATIONS
(2023)
Review
Materials Science, Multidisciplinary
Matthew D. Ward, Wenda Shi, Nicola Gasparini, Jenny Nelson, Jessica Wade, Matthew J. Fuchter
Summary: Circularly polarised light has the potential to revolutionise emerging technologies, but standardised reporting and testing protocols limit its translation into real-world applications. This mini-review provides an accessible introduction to the working principles of circularly polarised photodetectors and proposes a rigorous device characterisation procedure to accelerate research and investment in this field.
JOURNAL OF MATERIALS CHEMISTRY C
(2022)
Article
Materials Science, Multidisciplinary
Hao Yan, Jessica Wade, Li Wan, Sooncheol Kwon, Matthew J. Fuchter, Alasdair J. Campbell, Ji-Seon Kim
Summary: This study demonstrates the use of a small amount of chemically modified electrochemical doping agent to improve the performance of circularly polarized polymer light-emitting diodes. By controlling unbalanced charge transport and energetics, the efficiency of charge injection and device performance is improved.
JOURNAL OF MATERIALS CHEMISTRY C
(2022)
Article
Materials Science, Multidisciplinary
Li Wan, Jessica Wade, Xuhua Wang, Alasdair J. Campbell, Matthew J. Fuchter
Summary: Researchers have reported the development of circularly polarized organic light-emitting diodes (CP-OLEDs) that demonstrate high efficiency and strong circularly polarized electroluminescence. The addition of a chiral small molecule additive greatly improves the performance of the CP-OLEDs. The findings provide new opportunities for the optimization of chiroptical properties in films and devices.
JOURNAL OF MATERIALS CHEMISTRY C
(2022)
