Article
Chemistry, Multidisciplinary
Kristina Martinez, Sydney M. Koehne, Kaitlyn Benson, Jared J. Paul, Russell H. Schmehl
Summary: Bimolecular excited-state proton-coupled electron transfer (PCET*) was observed for the reaction between the triplet MLCT state of [(dpab)2Ru(4,4 '-dhbpy)]2+ and N-methyl-4,4 '-bipyridinium (MQ+) and N-benzyl-4,4 '-bipyridinium (BMQ+). The PCET* products, oxidized and deprotonated Ru complex, and reduced protonated MQ+ can be distinguished from other reaction products based on the difference in their visible absorption spectra. The observed behavior is different from the reaction between the MLCT state of [(bpy)2Ru(4,4 '-dhbpy)]2+ and MQ+, which involves initial electron transfer (ET*) followed by proton transfer (PT*).
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Akshay M. Nair, Indranil Halder, Chandra M. R. Volla
Summary: We report a highly selective cascade reaction for the synthesis of highly functionalized dihydrochromenones. The reaction involves arylsulfonylation, radical cyclization, and selenylation of alkynyl cyclohexadienones. Aryldiazonium salts and DABSO are used as reactants, with DABSO also serving as a benign SO2 source and redox mediator. A visible light mediated protocol using diaryliodonium salts as reactants was also developed.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Liang Hu, Guangrong Meng, Xiangyang Chen, Joseph S. S. Yoon, Jing-Ran Shan, Nikita Chekshin, Daniel A. A. Strassfeld, Tao Sheng, Zhe Zhuang, Rodolphe Jazzar, Guy Bertrand, K. N. Houk, Jin-Quan Yu
Summary: The discovery of a ligand scaffold containing a remote amide motif that can form a favorable hydrogen bonding interaction with the aliphatic acid substrate is reported. This ligand scaffold is used in the development of an unprecedented C(sp(3))-H bromination of α-tertiary and α-quaternary free carboxylic acids, which exhibits high mono-selectivity. The geometric relationship between the NHAc hydrogen bond donor and the coordinating quinoline ligand is crucial for the formation of the macrocyclic-like hydrogen bonding interaction, providing a guideline for future catalyst design using secondary interactions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Zhengwei Ding, Zhi Liu, Zhijun Wang, Tao Yu, Ming Xu, Jingru Wen, Kaiyan Yang, Hailong Zhang, Liang Xu, Pengfei Li
Summary: This study reports an economical reaction using commercial diboron(4) as a catalyst. By designing a catalytic cycle and using a pyridine cocatalyst, boronyl radicals can be generated and transferred reversibly. The reaction features metal-free conditions, inexpensive and stable catalysts, simple operation, and a broad substrate scope compared to transition metal-based catalysts.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Lakshya Daukiya, Joan Teyssandier, Samuel Eyley, Salim El Kazzi, Miriam Candelaria Rodriguez Gonzalez, Bapi Pradhan, Wim Thielemans, Johan Hofkens, Steven De Feyter
Summary: In this study, covalent functionalization of MoS2 was achieved through chemical activation, allowing for high level control over the grafting density and yield on the basal plane. The covalent modification of MoS2 was proven using scanning probe microscopies and X-ray photoelectron spectroscopy.
Article
Chemistry, Organic
Jiabin Shen, Jun Xu, Qing Zhu, Pengfei Zhang
Summary: This study presents a rapid three-component cascade reaction for the synthesis of unsymmetric azo compounds using a radical activation strategy. Various aryldiazonium salts and unactivated alkenes are compatible, providing the corresponding products in good to excellent yields. The proposed free radical pathway mechanism offers an efficient and practical solution for the synthesis of unsymmetric azo compounds with two C-N bond formation.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Organic
Fengkai Qiu, Yu Cao, Linghui Zeng, Chong Zhang, Liping Fu, Jiankang Zhang, Huajian Zhu, Jiaan Shao
Summary: A novel divergent domino annulation reactions of sulfur ylides with aryldiazonium tetrafluoroborates have been developed, producing various tetra- and trisubstituted pyrazole derivatives in moderate to good yields. In these one-pot reactions, three molecules of sulfur ylides were used as C-1 synthon to construct complex products with five new chemical bonds formed.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Denis A. B. Therien, Danielle M. McRae, Claire Mangeney, Nordin Felidj, Francois Lagugne-Labarthet
Summary: This study investigates surface plasmon-mediated chemical reactions using a crosshair-like nanostructure to induce local enhancement of the electromagnetic field at specific wavelengths. The resulting grafting shows polarization and wavelength-dependent growth patterns at the nanoscale, supported by scanning electron microscopy observations and finite domain time domain modelling.
NANOSCALE ADVANCES
(2021)
Article
Chemistry, Multidisciplinary
Shuo Lu, Tianyu Zheng, Jiawei Ma, Zhangming Deng, Shengmeng Qin, Yu Chen, Yong Liang
Summary: In this study, a new ionic ligand is developed and successfully used for the para-selective functionalization of aromatic salts. The reaction shows great potential in gram-scale transformation, late-stage elaboration for drug molecules, and diversification of products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Xinhua Wang, Qiuping Ding, Chenxi Yang, Jianguo Yang, Jie Wu
Summary: This study reports a catalytic asymmetric three-component reaction for the synthesis of sulfonyl-containing axially chiral styrenes. By using a photocatalyst under visible light irradiation, 4-substituted Hantzsch esters, NaHSO3, and 1-(arylethynyl)naphthalen-2-ols were used as reactants to undergo a mild radical process, leading to high yields of axially chiral (S,E)-1-(1-(alkylsulfonyl)-2-arylvinyl)naphthalen-2-ols with excellent enantioselectivity. The reaction also demonstrated excellent regioselectivity and chemoselectivity. Sodium hydrogen sulfite was utilized as a surrogate for sulfur dioxide in this organocatalytic enantioselective radical sulfonylation under photoinduced conditions.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Physical
Soraya Rahpeima, Anton Le Brun, Colin L. Raston, Nadim Darwish
Summary: Electrochemical reduction of diazonium salts on silicon electrodes of different crystal orientations has been studied. The kinetics of surface reaction and reduction potential were found to be dependent on Si crystal facets. The potential of zero charge (PZC) of each crystal orientation was found to control the adsorption of diazonium cations and influence the formation of compact films. The findings contribute to the understanding of the electro-polymerization reaction of diazonium salts on Si and its potential applications in integrated molecular and Si electronics technology.
JOURNAL OF COLLOID AND INTERFACE SCIENCE
(2022)
Article
Chemistry, Organic
Gangqi Peng, Hao Cheng, Xiya Cheng, Yang He, Yuanyuan An, Jie Wu, Danqing Zheng
Summary: A reductive Sandmeyer-type sulfinylation reaction of aryldiazonium salts with sodium sulfinates was developed, which proceeds under photocatalysis and generates various sulfoxides of significant value via radical substitution pathway. The in situ diazotization of aromatic amines in a one-pot, two-step process also allows for the conversion to corresponding sulfoxides. The successful late-stage sulfinylation of drug-based amines further demonstrates the practicality of this method.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Junhyuk Jo, Seonyul Kim, Jun-Ho Choi, Won-Jin Chung
Summary: A convenient pyridine-boryl radical-mediated pinacol coupling of diaryl ketones has been developed, using a stable diboron reagent and pyridine Lewis base catalyst to generate ketyl radicals. This new method allows for the efficient production of diols with up to 99% yield within 1 hour, demonstrating the superior reactivity of diaryl ketones over monoaryl carbonyl compounds. DFT calculations suggest that the presence of two aromatic rings is necessary for maximum stabilization of the transition states.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Physical
Giovanna Angelica Vazquez-Hernandez, Roxana Delgado-Cruz, Maria-Elena Sanchez-Vergara, Lioudmila Fomina, Virginia Gomez-Vidales, Beatriz de la Mora, Alonso Acosta, Citlalli Rios, Roberto Salcedo
Summary: New derivatives of the 2,5-aromatic disubstituted pyrrole were prepared in this work, with fullerene and ferrocene as substituent fragments. These compounds exhibit semiconductor behavior by withdrawing electronic charge from the aromatic ring, with the fullerene compound identified as a low band gap semiconductor through Kubelka-Munk method analysis.
JOURNAL OF MOLECULAR STRUCTURE
(2021)
Review
Chemistry, Multidisciplinary
Guglielmo A. Coppola, Serena Pillitteri, Erik V. Van der Eycken, Shu-Li You, Upendra K. Sharma
Summary: Visible-light photoredox catalysis and organic electrochemistry are important tools in organic synthesis, providing alternative routes with higher selectivity and broader applicability. These two fields have great research value and are making continuous progress.
CHEMICAL SOCIETY REVIEWS
(2022)
Article
Chemistry, Multidisciplinary
Subeesh Madayanad Suresh, Le Zhang, David Hall, Changfeng Si, Gaetano Ricci, Tomas Matulaitis, Alexandra M. Z. Slawin, Stuart Warriner, Yoann Olivier, Ifor D. W. Samuel, Eli Zysman-Colman
Summary: NOBNacene is a rare example of a p- and n-doped nonacene compound with linearly extended ladder-type multiresonant thermally activated delayed fluorescence (MR-TADF) emission. It exhibits efficient narrow deep blue emission with a PL wavelength of 410 nm, FWHM of 38 nm, PL quantum yield of 71%, and delayed lifetime of 1.18 ms. The OLED using NOBNacene as the emitter shows a comparable electroluminescence spectrum with a peak at 409 nm and a maximum external quantum efficiency (EQE(max)) of 8.5% at CIE coordinates of (0.173, 0.055). The EQE(max) is increased to 11.2% with 3 wt% doping of the emitter in the emissive layer, resulting in a slightly broadened electroluminescence spectrum with CIE coordinates of (0.176, 0.068).
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Crystallography
Fatin Nur Ain Abdul Rashid, Muhamad Zulfaqar Bacho, Alexandra M. Z. Slawin, Mohd Abdul Fatah Abdul Manan, Saiful Azmi Johari, Mohd Fazli Mohammat
Summary: The substance is triclinic with space group P (1) over bar (no. 2). The cell parameters are a = 7.9179(7) angstrom, b = 10.1982(9) angstrom, c = 10.4144(8) angstrom, alpha = 76.184(7) degrees, beta = 87.090 (7) degrees, gamma = 73.500(8) degrees. The volume of the unit cell is 782.86(12) angstrom(3), and there are 2 molecules in the lattice. The R-gt(F) value is 0.0458, and the wR(ref)(F-2) value is 0.1333. The temperature is 93 K.
ZEITSCHRIFT FUR KRISTALLOGRAPHIE-NEW CRYSTAL STRUCTURES
(2023)
Article
Crystallography
R. Alan Aitken, Alexander J. B. Nelson, Alexandra M. Z. Slawin, Dheirya K. Sonecha
Summary: Thirteen new crystal structures of cyclic NH carboximides have been determined and compared based on their intermolecular hydrogen bonding patterns. The structures include a new cyclobutane-fused succinimide, seven new simple bi- and tricyclic succinimides derived from Diels-Alder reactions, three methylated glutarimides, a morpholinedione and adipimide, and the first seven-membered ring NH carboximide to be characterized. The compounds were found to adopt ribbon structures, centrosymmetric dimers, and bonding between NH and a remote bridging ether oxygen. Halogen bonding was also observed in one case.
Article
Crystallography
R. Alan Aitken, Alexandra M. Z. Slawin, Dheirya K. Sonecha
Summary: This paper reports the crystal structures of 2,5-dihydrothiophene 1,1-dioxide and 2,3-dihydrothiophene 1,1-dioxide, which show perfectly planar rings with expected bond lengths and angles. In contrast, the halogenated derivatives 3,3,4,4-tetrachlorotetrahydrothiophene 1,1-dioxide and 2,3-dibromotetrahydrothiophene 1,1-dioxide exhibit twisted conformations. The degree of planarity is compared with similar 5-membered ring cyclic sulfones, and the C-H...O hydrogen bonding patterns are discussed.
JOURNAL OF CHEMICAL CRYSTALLOGRAPHY
(2023)
Article
Chemistry, Organic
Yihong Wang, Claire M. M. Young, David B. B. Cordes, Alexandra M. Z. Slawin, Andrew D. D. Smith
Summary: The isothiourea-catalyzed formal [2+ 2] cycloaddition of C(1)-alkyl and C(1)-unsubstituted ammonium enolates with beta- and alpha,beta-substituted trifluoromethylenones has been developed. The reaction exhibited preferential [2 + 2]-cycloaddition over the alternative [4 + 2]-cycloaddition, resulting in beta-lactones with excellent diastereo- and enantioselectivity. The regioselectivity of the reaction was determined by the substituents on both reactants.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Biochemistry & Molecular Biology
R. Alan Aitken, Lynn A. A. Power, Alexandra M. Z. Slawin
Summary: (2S,5S)-5-Phenyl-2-t-butyl-1,3-dioxolan-4-one, derived from mandelic acid, can undergo Michael addition reactions with butenolide and 4-methoxy-beta-nitrostyrene, with the absolute configuration of the products confirmed by X-ray diffraction. Thermal fragmentation of the dioxolanone in these reactions results in the formation of phenyl ketone and chiral epoxy ketone, demonstrating its role as a chiral benzoyl anion equivalent and chiral ketene equivalent, respectively. Additionally, the Diels-Alder cycloaddition chemistry of (2S)-5-methylene-2-t-butyl-1,3-dioxolan-4-one, derived from lactic acid, has been studied, and the X-ray structures of four adducts have been determined, providing insights into the mechanism of dioxolanone fragmentation.
Article
Chemistry, Organic
Jan U. Bergsch, Alexandra M. Z. Slawin, Petr Kilian, Brian A. Chalmers
Summary: Researchers successfully synthesized two new types of Sb(III) and Sb(V) peri-substituted acenaphthene phosphorus-antimony compounds. The Sb(III) compound, 1, was prepared by reacting the organolithium precursor with dichloro(p-tolyl)stibine, and 2 was prepared by chlorination of 1. Both compounds were characterized by multinuclear (H-1, C-13, and P-31) NMR spectroscopy and their molecular structures were resolved by single-crystal X-ray diffraction. Both compounds exhibit a dative P-Sb interaction with antimony serving as the Lewis acidic acceptor group.
Article
Chemistry, Organic
Zachary H. Davis, Cameron L. Carpenter-Warren, Laurence J. Taylor, Alexandra M. Z. Slawin, Petr Kilian, Brian A. Chalmers
Summary: A binuclear tungsten(0) complex with an asymmetric bridging 1,2-diphosphole ligand was synthesized by the photolysis of tungsten hexacarbonyl in the presence of 1-isopropyl-2-phenyl-1,2,5,6-tetrahydroacenaphtho [5,6-cd][1,2]diphosphole. The tungsten complex 1 was characterized by high resolution mass spectrometry, multinuclear NMR spectroscopy (H-1, C-13, P-31), and elemental microanalysis. The structure of the trans isomer was resolved by single crystal X-ray diffraction, showing a slight elongation of the P-P bond upon coordination to the W(CO)(5) groups.
Article
Chemistry, Physical
Suman Mandal, Mitali Sarkar, Shanku Denrah, Arka Bagchi, Arunima Biswas, David B. Cordes, Alexandra M. Z. Slawin, Nitis Chandra Saha
Summary: A new pyrazole Schiff-base ligand and its two Ni(II) complexes have been synthesized and characterized. The complexes show promising catalytic and anticancer activities.
JOURNAL OF MOLECULAR STRUCTURE
(2023)
Article
Chemistry, Organic
R. Alan Aitken, Lynn A. Power, Alexandra M. Z. Slawin
Summary: X-ray diffraction analysis confirmed that the product formed by base-induced dimerization matches the described compound structure, rather than the previously proposed isomeric structure. Additionally, a similar compound derived from a different substrate was obtained and characterized.
Article
Chemistry, Organic
R. Alan Aitken, Alexandra H. Campbell, Chloe E. Fletcher, Alexandra M. Z. Slawin
Article
Chemistry, Inorganic & Nuclear
Hessa H. Al-Rasheed, Sarah A. AL-khamis, Ayman El-Faham, Assem Barakat, Alexandra M. Z. Slawin, John Derek Woollins, Saied M. Soliman
Summary: The unexpected tetranuclear [Cu-4(DPPT)(2)Cl-6] complex was obtained through self-assembly, and it showed good antifungal and antibacterial activity against Gram-positive bacteria.
Article
Materials Science, Multidisciplinary
Ettore Crovini, Rama Dhali, Dianming Sun, Tomas Matulaitis, Thomas Comerford, Alexandra M. Z. Slawin, Cristina Sissa, Francesco Azzolin, Francesco Di Maiolo, Anna Painelli, Eli Zysman-Colman
Summary: We have studied the synthesis, optoelectronic properties, and theoretical analysis of DMAC-py-TRZ, a novel TADF emitter. The structural difference between DMAC-py-TRZ and DMAC-TRZ leads to significant changes in their steric interactions and photophysics. While the bent structure of DMAC-py-TRZ hinders TADF, emission can be observed from a relaxed orthogonal excited-state geometry. The presence of both conformers in amorphous matrices contributes to the efficiency of DMAC-py-TRZ devices through efficient energy transfer.
JOURNAL OF MATERIALS CHEMISTRY C
(2023)
Article
Materials Science, Multidisciplinary
John Marques dos Santos, Chin-Yiu Chan, Shi Tang, David Hall, Tomas Matulaitis, David B. Cordes, Alexandra M. Z. Slawin, Youichi Tsuchiya, Ludvig Edman, Chihaya Adachi, Yoann Olivier, Eli Zysman-Colman
Summary: Two novel p-extended amine/carbonyl-based multi-resonance thermally activated delayed fluorescence (MR-TADF) emitters have been designed and synthesized. The two emitters are isomeric, composed of nine fused rings and show green-yellow emission. Sym-DiDiKTa and Asym-DiDiKTa possess tert-butyl groups distributed in a symmetrical and asymmetrical fashion, respectively, which significantly impact the single-crystal packing structure. The devices with Sym-DiDiKTa and Asym-DiDiKTa displayed electroluminescence maxima of 543 and 544 nm, and maximum external quantum efficiencies (EQE(max)) of 9.8% and 10.5%, respectively. The maximum EQE was further improved to 19.9% by employing a hyperfluorescence strategy. The LEC with Sym-DiDiKTa as the emitter showed a ?(EL) at 551 nm and FWHM of 60 nm with luminance of 300 cd m(-2) and a fast turn-on time of less than 2 s to 100 cd m(-2).
JOURNAL OF MATERIALS CHEMISTRY C
(2023)
Article
Materials Science, Multidisciplinary
Dongyang Chen, Le Zhang, Tomas Matulaitis, David B. Cordes, Alexandra M. Z. Slawin, Xiao-Hong Zhang, Ifor D. W. Samuel, Eli Zysman-Colman
Summary: By judicious molecular engineering, the efficiency of the triplet exciton harvesting mechanisms in OLEDs can be modulated, leading to improved device efficiency.
JOURNAL OF MATERIALS CHEMISTRY C
(2023)
