Article
Chemistry, Multidisciplinary
Ming-Liang Gao, Luyan Li, Zi-Xuan Sun, Jia-Rui Li, Hai-Long Jiang
Summary: The exposed facets of supported catalysts are crucial in catalysis, but they are usually ignored. This study demonstrates that crystal facet engineering of supports can modulate the microenvironment and electronic state of supported metal nanoparticles, leading to enhanced catalysis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Inorganic & Nuclear
Samrah Kamal, Mohd Khalid, M. Shahnawaz Khan, M. Shahid
Summary: Fortification of the environment is necessary for ensuring safety. This review article discusses the development of advanced detection methods and sensory materials using coordination chemistry. Metal-organic frameworks (MOFs) have attracted significant attention due to their functional tunability and potential applications. The article focuses on the current trends, chemical nature, structural tunability, and sensing of hazardous substances related to tuning the MOF structure. The use of MOFs as fluorescent sensor materials for detecting explosives, hazardous metal ions, and anions is explored, as well as the tuning of MOFs for improved sensing ability, durability, and recyclability.
COORDINATION CHEMISTRY REVIEWS
(2023)
Article
Chemistry, Physical
Qin Wang, Jun-Zhuo Guo, Cheng Zhang, Wen-Qi Sun, Rui-Lian Lin, Ming-Fu Ye, Jing-Xin Liu
Summary: In this study, the formation of inclusion complexes between cyclodextrins and pyridinium chloride was demonstrated, showing photochromic properties suitable for erasable inkless printing and anticounterfeiting. The color of printing on filter paper can be tuned by controlling the mass proportions of different inclusion complexes.
JOURNAL OF PHYSICAL CHEMISTRY C
(2022)
Article
Chemistry, Multidisciplinary
Hoai T. B. Pham, Ji Yong Choi, Shaofeng Huang, Xubo Wang, Adam Claman, Michael Stodolka, Sadegh Yazdi, Sandeep Sharma, Wei Zhang, Jihye Park
Summary: The development of 2D electrically conductive metal-organic frameworks (EC-MOFs) has expanded the applications of MOFs. This study presents a new EC-MOF with a large surface area, high electrical conductivity, and tunable particle size. The framework also utilizes functional groups to host heterometal ions, providing new opportunities for expanding the library of EC-MOFs and exploring electronic applications.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Petru Apostol, Sai Manoj Gali, Alice Su, Da Tie, Yan Zhang, Shubhadeep Pal, Xiaodong Lin, Vasudeva Rao Bakuru, Darsi Rambabu, David Beljonne, Mircea Dinca, Alexandru Vlad
Summary: Two-dimensional electrically conducting metal-organic frameworks (2D-e-MOFs) are a promising class of functional materials with various applications. This study reports two isostructural 2D-e-MOFs that can be chemically functionalized and exhibit temperature-activated charge transport.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Review
Chemistry, Multidisciplinary
Jiajie Chen, Yufang Zhu, Stefan Kaskel
Summary: Metal-organic frameworks (MOFs) have received increasing attention in recent years, and the introduction of porphyrin molecules into MOFs has allowed for overcoming the limitations of porphyrins in biomedical applications. Porphyrin-based MOFs have made significant achievements and progress in areas such as tumor therapy and biosensing.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Physical
Zhiping Qian, Rui Zhang, Yan Xiao, Hongwei Huang, Ying Sun, Yang Chen, Tianyi Ma, Xiaodong Sun
Summary: Benefitting from its ultra-high porosity, large specific surface area, and rich active sites, metal-organic frameworks (MOFs) have become a star material in energy and environmental applications, especially in photocatalysis. This paper provides a comprehensive and systematic review on the self-tuning of MOFs to enhance photocatalytic activity. It summarizes the analysis of MOFs' components, defects, and crystal structure, and discusses their applications in various photocatalytic processes. The opportunities and challenges in the self-tuning of MOFs are also analyzed.
ADVANCED ENERGY MATERIALS
(2023)
Review
Chemistry, Multidisciplinary
Bing Chen, Jiaoran Wang, Linzhuang Peng, Qiang Wang, Yuan Wang, Xiuwen Xu
Summary: Metal-organic frameworks (MOFs) are multifunctional materials with high chemical/structural designability. Radiation-responsive MOFs, which can convert ionizing radiations into electrical charges or visible light, have emerged as promising substitutes for conventional radiation-responsive substances. This review article documents recent advancements in radiation-responsive MOFs and explores their applications in biomedicine and technology. It also highlights future opportunities for expanding the research of radiation-responsive MOFs.
ADVANCED FUNCTIONAL MATERIALS
(2023)
Review
Chemistry, Inorganic & Nuclear
Soumya Mukherjee, Debobroto Sensharma, Omid T. Qazvini, Subhajit Dutta, Lauren K. Macreadie, Sujit K. Ghosh, Ravichandar Babarao
Summary: The chemical industry contributes around 7% of the global GDP, with 40% of its energy consumption coming from separation/purification processes of commodity chemicals. The use of recyclable adsorbents, such as metal-organic framework (MOF) physisorbents, shows promise in reducing this energy footprint, particularly in the separation of C6 cyclic hydrocarbons like benzene and cyclohexane. Despite the potential of MOFs as selective adsorbents, further research is needed to fully explore their capabilities in this niche area.
COORDINATION CHEMISTRY REVIEWS
(2021)
Article
Chemistry, Multidisciplinary
Chun-Hao Su, Meng-Jung Tsai, Wei-Kai Wang, Yi-Yun Li, Jing-Yun Wu
Summary: Through a dual-ligand synthetic approach, five isoreticular primitive cubic (pcu)-type pillared-layer metal-organic frameworks with microporous structures were engineered. The study revealed solvent-dependent fluorescence properties in some frameworks, which could be efficiently quenched by trace amounts of nitrobenzene.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Jacopo Perego, Charl X. Bezuidenhout, Silvia Bracco, Sergio Piva, Giacomo Prando, Cristian Aloisi, Pietro Carretta, Jiri Kaleta, Thi Phuong Le, Piero Sozzani, Andrea Daolio, Angiolina Comotti
Summary: Fluorinated metal-organic frameworks exhibit benchmark mobility of correlated dipolar rotors at low temperatures, with practically zero activation energy. Through various experiments and calculations, the dynamic characteristics and cascade mechanism of dipole configurations have been revealed. It has also been shown that the dipole configurations in the crystal can be changed by chemical stimuli such as CO2.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Jing Du, Yuan-Yuan Ma, Wen-Jing Cui, Si -Meng Zhang, Zhan-Gang Han, Run-Han Li, Xing-Qi Han, Wei Guan, Yong-Hui Wang, Ying-Qi Li, Yang Liu, Fei-Yang Yu, Kai-Qiang Wei, Hua-Qiao Tan, Zhen-Hui Kang, Yang-Guang Li
Summary: In this study, the electron-transfer mechanism in heterogeneous photocatalytic CO2 reduction reaction was investigated using a new type of metal-organic framework as model photocatalysts. The results revealed the significant regulation role of different polyoxometalate units on electron transfer and photocatalytic activities.
APPLIED CATALYSIS B-ENVIRONMENTAL
(2022)
Article
Chemistry, Inorganic & Nuclear
Shimin Zhang, Weiyu Yu, Pengfei Hao, Gaopeng Li, Junju Shen, Yunlong Fu
Summary: Two novel naphthalene diimide coordination polymers (CPs) were designed and synthesized using electron-deficient NicNDI, electron-rich aromatic carboxylic acid ligands, and cadmium ions. The usage of different aromatic carboxylic acid ligands led to the generation of distinct interpenetrated 3D frameworks. The photochromism and weak photoactivity of the CPs were attributed to the introduction of different auxiliary ligands and the formation of distinct interfacial contacts, affecting photoinduced intermolecular electron transfer and photoresponsive behaviors.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Kangho Park, Sukwon Hyeon, Kyoung Min Kang, Kiwon Eum, Jihan Kim, Dae Woo Kim, Hee-Tae Jung
Summary: The study found that on ZIF-8 surfaces, rod-shaped molecules with short alkyl chain lengths are vertically aligned while those with long alkyl chain lengths are randomly oriented. Disk- and column-shaped molecules, on the other hand, exhibit random orientation. Molecular dynamic simulations suggest that the physical anchoring by ZIF-8 micropores contributes to the vertical alignment of rod-shaped molecules.
JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Weisu Kong, Da Zhu, Yong Zhang, Rengan Luo, Jing Ma, Jianping Lei, Huangxian Ju
Summary: To improve the photoelectrochemical performance, an additional electron donor/acceptor is typically needed to suppress electron-hole recombination. However, the enhancement is limited due to long-distance diffusion. In this study, a self-supplying electron strategy is designed by coordinating an electron donor 1.4-diazabicyclo[2.2.2]octane (Dabco) in a metal-organic framework (MOF) to enhance PEC performance. The presence of Dabco effectively inhibits electron-hole recombination and leads to a 23.2-fold enhancement in photocurrent. This work provides a new approach for improving the PEC performance of nanomaterials.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Karolis Norvaisa, Sophie Maguire, Claire Donohoe, John E. O'Brien, Brendan Twamley, Ligia C. Gomes-da-Silva, Mathias O. Senge
Summary: Inspired by 'picket-fence' systems, this study utilized strain to introduce intramolecular tension, leading to selective compound atropisomer conversion and the formation of distinctive supramolecular nanostructures.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Review
Biochemistry & Molecular Biology
Arno Wiehe, Mathias O. Senge
Summary: This review provides an overview of the research, development, and clinical applications of the photosensitizer 5,10,15,20-tetra(m-hydroxyphenyl)chlorin (mTHPC, temoporfin) in photodynamic (cancer) therapy (PDT) and other medical applications. The review covers the chemistry, biochemistry, pharmacology, and clinical applications of temoporfin, including the formulation development such as liposomal formulations. The literature covered spans from 2009 to early 2022 and is connected to a previous extensive review on this photosensitizer, which traces its development, approval, and clinical application.
PHOTOCHEMISTRY AND PHOTOBIOLOGY
(2023)
Article
Chemistry, Organic
Claire Donohoe, Asterios Charisiadis, Sophie Maguire, Brendan Twamley, Fabio A. Schaberle, Ligia C. Gomes-da-Silva, Mathias O. Senge
Summary: The time dependence of atropisomer interconversion has hindered the development of single atropisomer drug candidates. The instability caused by moderate interconversion energy barriers is a concern for drug stability. However, there is a recent focus on developing stable atropisomer drugs with enhanced activity.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Biao Yang, Kaifeng Niu, Nan Cao, Nitika Grover, Wenchao Zhao, Alexander Riss, Jonas Bjoerk, Willi Auwaerter, Johannes V. Barth, Mathias O. Senge
Summary: In this study, the behavior of 1,3-disubstituted BCP moieties on metal surfaces was examined using low-temperature scanning tunneling microscopy/non-contact atomic force microscopy studies and density functional theory modeling. The configuration, supramolecular assembly, and thermally activated dehalogenative coupling reactions of BCP-containing precursors on Au(111) were investigated, resulting in the formation of polymeric chains. These findings provide sub-molecular insights into the behavior of BCP scaffolds on surfaces and expand the potential application of BCP derivatives in custom-designed surface architectures.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Nitika Grover, Maxime Cheveau, Brendan Twamley, Christopher J. Kingsbury, Cornelia M. Mattern, Mathias O. Senge
Summary: We present a two-step method for obtaining versatile bicyclo[1.1.1]pentane (BCP) derivatives using Grignard reagents. This approach allows for the incorporation of BCP units into tetrapyrrolic macrocycles, as well as the synthesis of a novel class of calix[4]pyrrole analogues by replacing bridging methylene groups with BCP units. Moreover, electron-withdrawing substituents at the BCP bridgeheads lead to the formation of a doubly N-confused system. Single-crystal X-ray diffraction analyses and 2D NMR spectroscopy reveal that the pyrrole rings in BCP-containing macrocycles exist in 1,3-alternate or alpha beta alpha beta conformations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Irina Osadchuk, Hanna-Eliisa Luts, Karolis Norvaisa, Victor Borovkov, Mathias O. Senge
Summary: The determination of molecular stereochemistry and absolute configuration is important in chemistry, pharmacology, and biology. Electronic circular dichroism (ECD) is a widely used tool for chirality assignment, but the mechanisms of induced ECD in porphyrin complexes are not fully understood.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Crystallography
Harry C. Sample, Brendan Twamley, Mathias O. Senge
Summary: The crystal structures of three S-(pyridin-2-yl) benzothioesters with different para-phenyl substituents are reported. These compounds are used in the mono-acylation of pyrrolic species to produce multifunctional tetrapyrroles. The dominant interactions in the crystal packing vary from pi-pi stacking in compound 1 to exclusively C-H···O/N interactions in compound 3 as the para-phenyl motif changes from electron withdrawing to electron donating.
ACTA CRYSTALLOGRAPHICA SECTION E-CRYSTALLOGRAPHIC COMMUNICATIONS
(2023)
Article
Crystallography
Harry C. Sample, Brendan Twamley, Mathias O. Senge
Summary: The crystal structure of compound 1 (C26H24Br2N4O8S2) is presented in this study. Compound 1 was obtained as a by-product in the synthesis of geminal-dimethyl hydrodipyrrins. Unexpected enantiomeric resolution was observed in both the bulk sample and crystal of 1, with distinct C-H···O (C-methyl-H···O-nitro, C-sp3-H···O-sulfonyl) interactions present in the enantiomers, along with other interactions, forming a polymer along the c-axis direction. Little data is available on the 1,3-dinitrobutane scaffold, unlike the well-documented pyrrolic fragments.
ACTA CRYSTALLOGRAPHICA SECTION E-CRYSTALLOGRAPHIC COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Davide Ranieri, Alberto Privitera, Fabio Santanni, Karolina Urbanska, Grant J. Strachan, Brendan Twamley, Enrico Salvadori, Yu-Kai Liao, Mario Chiesa, Mathias O. Senge, Federico Totti, Lorenzo Sorace, Roberta Sessoli
Summary: By synthesizing and studying a VIVO-CuII porphyrin dimer, we observed measurable exchange coupling and good spin coherence, making it suitable for operating two-qubit molecular spin-based quantum gates under various conditions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Irina Osadchuk, Hanna-Eliisa Luts, Karolis Norvaisa, Victor Borovkov
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Editorial Material
Chemistry, Multidisciplinary
Irina Osadchuk, Hanna-Eliisa Luts, Karolis Norvaisa, Victor Borovkov, Mathias O. Senge
Summary: This article features the groups of Irina Osadchuk at Tallinn University of Technology and Mathias Senge at Trinity College Dublin. The image illustrates the measurement and simulation of ECD and UV-Vis spectra of a porphyrin molecule with two guest molecules (R)-camphor sulfonic acid under UV-visible light irradiation. Read the full text of the article at 10.1002/chem.202301408.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Nan Cao, Jonas Bjoerk, Eduardo Corral-Rascon, Zhi Chen, Mario Ruben, Mathias O. Senge, Johannes V. Barth, Alexander Riss
Summary: This study investigates how aromaticity affects the reactivity of alkyne-substituted porphyrin molecules on a Au(111) surface. The experiments show that carbon atoms stabilized by aromaticity display lower reactivity, which is consistent with density functional theory calculations.
Review
Chemistry, Multidisciplinary
Tomoya Ishizuka, Nitika Grover, Christopher J. Kingsbury, Hiroaki Kotani, Mathias O. Senge, Takahiko Kojima
Summary: This article summarizes the synthetic methods and design aspects of nonplanar porphyrin formation, the key properties and functionality of the nonplanar aromatic framework, and the scope and utility of this emerging class in addressing important scientific, industrial, and environmental issues.
CHEMICAL SOCIETY REVIEWS
(2022)
Article
Chemistry, Multidisciplinary
Karolis Norvaisa, John E. O'Brien, Irina Osadchuk, Brendan Twamley, Victor Borovkov, Mathias O. Senge
Summary: In this study, we investigated the activity and symmetry of porphyrin-based supramolecular receptors in a chiral environment through NMR analysis of atropisomeric receptors. By exploiting the hydrogen bond abilities of the exposed porphyrin inner core, we found that N-H signals in a previously underutilized region of the spectrum can detect enantiomeric compositions with three times higher sensitivity than previously reported systems.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Robby Buechner, Vinicius Vaz da Cruz, Nitika Grover, Asterios Charisiadis, Mattis Fondell, Robert Haverkamp, Mathias O. Senge, Alexander Foehlisch
Summary: Free base porphyrins, such as 5,10,15,20-tetrakis(4-carboxylatophenyl)porphyrin, are powerful photosensitizers for singlet oxygen generation and light-harvesting. The atomic level selectivity of dynamic UV pump - N K-edge probe X-ray absorption spectroscopy, combined with TD-DFT theory, provides insight into the excited molecular states within an unusual relaxation pathway. The efficient intersystem crossing is confirmed to be the result of long singlet excited state lifetime and thermal effects.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)