Article
Chemistry, Multidisciplinary
Qiang Chen, Amber L. Thompson, Kirsten E. Christensen, Peter N. Horton, Simon J. Coles, Harry L. Anderson
Summary: This study reported the synthesis of unprecedented β,β-directly linked cyclic zinc porphyrin oligomers, the trimer (CP3) and tetramer (CP4), through Yamamoto coupling of a 2,3-dibromoporphyrin precursor. The three-dimensional structures of CP3 and CP4 were confirmed by various analytical techniques. CP3 exhibited a propeller shape while CP4 had a saddle shape, resulting in different photophysical and electrochemical properties. CP4 also showed affinity for fullerenes, forming complexes with C70 and C60 in toluene solution.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Qiang Chen, Amber L. Thompson, Kirsten E. Christensen, Peter N. Horton, Simon J. Coles, Harry L. Anderson
Summary: In this study, unprecedented β,β-directly linked cyclic zinc porphyrin oligomers, the trimer (CP3) and tetramer (CP4), were synthesized and their three-dimensional structures were confirmed. The different geometries of CP3 and CP4 result in distinct photophysical and electrochemical properties. CP4, with its saddle-shaped structure, serves as a ditopic receptor for fullerenes.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Correction
Chemistry, Multidisciplinary
Davide Ranieri, Fabio Santanni, Alberto Privitera, Andrea Albino, Enrico Salvadori, Mario Chiesa, Federico Totti, Lorenzo Sorace, Roberta Sessoli
Summary: This correction article discusses the application of vanadyl porphyrin dimer in quantum information processing. The authors address some issues and errors in previous works and provide a more accurate understanding of the vanadyl porphyrin dimer.
Article
Chemistry, Organic
Vinoth Kumar Veeran, Gayathri Prakasam, Arunamaheswari Chakravarthy, Bhavana Purushothaman, Prasath Rangaraj
Summary: Imine-bridged meso-meso and beta-meso unsymmetrical thien-2-yl porphyrin dyads were synthesized and their structural and photophysical properties were investigated. The two porphyrin units interact through the near coplanar thien-2-yl linker.
POLYCYCLIC AROMATIC COMPOUNDS
(2023)
Article
Chemistry, Multidisciplinary
Chuanyong Wang, Kesheng Huang, Jie Ye, Wei-Liang Duan
Summary: The first highly enantioselective catalytic synthesis of P-stereogenic secondary phosphine-boranes was achieved using a newly developed unsymmetric bisphosphine pincer-nickel complex. Various P-stereogenic secondary phosphine-boranes were obtained in good yields with high enantioselectivity and diastereoselectivity. Subsequent alkylation upon P-C bond formation provided a practical way to access P-chiral compounds with diverse functional groups.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Applied
Elmira Payami, Saeed Neshad, Alireza Aghaiepour, Reza Teimuri-Mofrad
Summary: This paper focuses on the synthesis of novel ferrocene-appended porphyrin architectures and their zinc metal complexes. Tetraferrocenylporphyrins were successfully synthesized via a direct tetramerization reaction, and related zinc complexes were prepared through a metalation reaction. The structures of the new organometallic compounds were confirmed, and their redox-active properties were characterized.
APPLIED ORGANOMETALLIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Ningchao Liu, Hirofumi Morimoto, Fan Wu, Xiaojuan Lv, Bentian Xiao, Daiki Kuzuhara, Jianming Pan, Fengxian Qiu, Naoki Aratani, Zhen Shen, Hiroko Yamada, Songlin Xue
Summary: In this study, a one-pot synthesis method was used to successfully obtain 24 pi antiaromatic and 26 pi aromatic meso-aryl rosarins from beta-free bipyrrole for the first time. The planarity of the beta-free pristine rosarin backbones was confirmed by X-ray crystallography. Optical measurements showed interconversion between 24 pi antiaromatic and 26 pi aromatic beta-free pristine rosarin via redox reactions, which was not observed in distorted beta-dodecamethyl rosarin.
Article
Chemistry, Multidisciplinary
Tian-Xiang Luan, Jia-Rui Wang, Keyu Li, Hailian Li, Fuchun Nan, William W. Yu, Pei-Zhou Li
Summary: By embedding metal ions into a robust photosensitive covalent organic framework, effective photocatalysts for CO2 conversion are designed and constructed. The metallized COFs show significantly enhanced photochemical properties, with the Co-metallized COF achieving a high CO production rate and selectivity, and the Ni-metallized COF tandem catalyzing the generated CO to CH4. The remarkable performance enhancement is attributed to the incorporated metal sites in the COF skeleton, promoting CO2 adsorption and activation, CO desorption, and reducing the reaction energy barrier for intermediate formation.
Article
Chemistry, Inorganic & Nuclear
Nami Fukui, Kanako Ueno, Masahiko Hada, Hiroshi Fujii
Summary: The study compared the reactivity of meso-tetramesitylporphyrin and 2,7,12,17-tetramethyl-3,8,13,18-tetramesitylporphyrin for different reactions, revealing that the former is more reactive under non-sterically bulky substrate conditions, but the reactivity becomes similar when the substrate becomes sterically hindered. Density functional theory calculations showed differences in the orbital energies of the Fe=O moiety between the two porphyrins.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Tian-Xiang Luan, Lehan Du, Jia-Rui Wang, Keyu Li, Quan Zhang, Pei-Zhou Li, Yanli Zhao
Summary: This study presents a new covalent organic framework (COF) named PyPor-COF, which is a highly efficient photosensitizer. The COF combines photoactive porphyrin moieties through in situ-formed imidazole groups and exhibits high crystallinity, permanent porosity, robust stability, and semiconductive photo response activity. It can effectively initiate the generation of singlet oxygen (1O2) under visible-light irradiation, surpassing the efficiency of other porphyrin-based reactants and commercially available photosensitizing agents. The COF also shows potential in triggering 1O2 production in a physiological environment, making it a promising candidate for photodynamic therapy.
Article
Chemistry, Organic
Burcu Topaloglu Aksoy, Ahmet Senocak, Ismail Erol, Mehmet F. Saglam, Hakan Kandemir, Ibrahim F. Sengul, Bunyemin Cosut
Summary: In this study, a BODIPY compound (4) bearing a carbazole ring system was successfully synthesized and further used as a building block to construct a new class of bis-BODIPYs (5 and 6) via Suzuki and Stille coupling reactions. The photophysical properties of the targeted BODIPYs were investigated, showing important transitions controlled by solvent polarity. Electrochemical and in situ spectroelectrochemical properties were also studied, revealing the electropolymerizable and electrochromic potentials of the synthesized compounds. These findings suggest the potential applications of compounds 5 and 6 in various electrochemical research areas.
Article
Chemistry, Physical
Jessica S. O'Neill, Nicola M. Boyle, Thayse Marques Passos, Katharina Heintz, Wesley R. Browne, Brid Quilty, Mary T. Pryce
Summary: A series of novel porphyrins with tetra-meso-thien-2-yl groups were synthesized, and their photophysical properties were studied. Various techniques were used to investigate the electronic communication between the central Zn(II) porphyrin ring and different meso-substituent groups. The effect of the position and number of thienyl rings on the properties of these porphyrins was compared to zinc tetraphenylporphyrin (ZnTPP). The photochemically-driven antimicrobial activity of zinc(II)-5,10,15,20-tetra(thien-2 '-yl)porphyrin (ZnThPP) as a coating against both Gram-positive and Gram-negative bacteria was determined and compared to ZnTPP. Visible irradiation resulted in significant antimicrobial response.
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY
(2023)
Article
Multidisciplinary Sciences
Hao-Wen Kang, Yu-Chiao Liu, Wei-Kai Shao, Yu-Chen Wei, Chi-Tien Hsieh, Bo-Han Chen, Chih-Hsuan Lu, Shang-Da Yang, Mu-Jeng Cheng, Pi-Tai Chou, Ming-Hsi Chiang, Yao-Ting Wu
Summary: The synthesis, structures, and properties of highly twisted alkenes were investigated. The rotation of the central C = C bonds in these compounds is as facile as the rotation of aryl-aryl bonds in 2-fluorobiphenyl. The compounds exhibit broad photoabsorption range, reduced HOMO-LUMO gap, and small singlet-triplet energy gap.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Applied
Seda Cinar, Pinar Seyitdanlioglu, Canan Unaleroglu
Summary: Novel porphyrin-BODIPY dyads linked by alkyl chains of different lengths were synthesized and their intramolecular energy transfer properties were investigated. The results showed that alkyl chain shortening led to an increase in energy transfer. Calculations and experiments were performed to evaluate the optical and electronic behaviors of the dyads.
Article
Engineering, Environmental
Shuming Wu, Yanwei Li, Tinghong Wang, Hao Li, Xinna Wang, Lijuan Ma, Nazhen Zhang, Penghan Yue, Yanhui Li
Summary: In this study, a 2D porphyrin-based covalent organic framework (Por-PD-COF) with amide bonds was designed and synthesized for the selective adsorption and removal of methylene blue (MB) from aqueous solution. Por-PD-COF exhibited a large adsorption capacity for MB and showed selectivity towards MB over other organic dyes. Moreover, Por-PD-COF functioned as an efficient photocatalyst for MB degradation under visible light irradiation, and could be reused multiple times without significant loss in its adsorption and photocatalytic capacity. The findings suggest that Por-PD-COF has great potential for application in organic molecule separation and organic waste removal.
CHEMICAL ENGINEERING JOURNAL
(2023)
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.
Article
Chemistry, Multidisciplinary
Shaimaa Fayez, Torsten Bruhn, Doris Feineis, Laurent Ake Assi, Prem Prakash Kushwaha, Shashank Kumar, Gerhard Bringmann
Summary: The West African liana Ancistrocladus abbreviatus is a rich source of diverse naphthylisoquinoline alkaloids. Four novel compounds, named ancistrobrevolines A-D (14-17), have been isolated from its roots, showing an unprecedented heterocyclic ring system. Two of these compounds exhibit moderate cytotoxic effects and reduce the formation of mammospheres in breast cancer cells.
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)
