Article
Chemistry, Inorganic & Nuclear
Jiri Schulz, Jakub Antala, David Rezazgui, Ivana Cisarova, Petr Stepnicka
Summary: This study describes a new ferrocene-based phosphine stibine compound and investigates its properties using experimental and theoretical methods. The compound exhibits donor-acceptor interactions between the phosphine and stibine groups, as well as between the phosphine and oxygen/selenium. The compound also shows good catalytic performance in gold-catalyzed reactions.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Hong-Cheng Li, Xun Tang, Sheng-Yi Yang, Yang-Kun Qu, Zuo-Quan Jiang, Liang-Sheng Liao
Summary: By binding D/A units in space and controlling their interaction, intramolecular charge transfer is achieved which enhances the emission properties of the material. The DM-Me-B material exhibits high external quantum efficiency and low efficiency roll-off.
CHINESE CHEMICAL LETTERS
(2021)
Article
Chemistry, Multidisciplinary
Joshua J. Sutton, Dan Preston, Philipp Traber, Johannes Steinmetzer, Xue Wu, Surajit Kayal, Xue-Z Sun, James D. Crowley, Michael W. George, Stephan Kupfer, Keith C. Gordon
Summary: The optical properties of two Re(CO)(3)(bpy)Cl complexes with different substituents were studied, revealing distinct charge transfer bands in their absorption spectra and two emissive states in their excited-state spectroscopy which are modulated by solvent. Time-resolved infrared spectroscopy identified the nature of the excited states in different solvents, with DFT calculations suggesting that the switching of properties induced by solvent is controlled by spin-orbit coupling.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Shanshan Wang, Yinhui Li, Yu Fu, Xiaoyu Li, Chunhui Tao, Wenxiang Zhang, Heping Ma
Summary: A porous organic framework with well-defined donor-acceptor units, called D-A-POF, has been synthesized successfully. The intramolecular donor-acceptor interactions induce a localized electric field gradient at the pore surface, giving D-A-POF excellent desulfurization capabilities.
ADVANCED FUNCTIONAL MATERIALS
(2023)
Article
Chemistry, Physical
J. Terence Blaskovits, Maria Fumanal, Sergi Vela, Raimon Fabregat, Clemence Corminboeuf
Summary: This study identifies the trade-off between the main requirements of the donor-acceptor strategy for iSF and formulates design rules for tuning them simultaneously in a fragment-based approach. Simple guidelines to build promising novel materials for iSF are established based on a library of 2944 donor-acceptor copolymers. Systems containing benzothiadiazole and thiophene-1,1-dioxide acceptors have been shown to fulfill all criteria for iSF simultaneously when paired with appropriate donors, making them highly promising candidates in the quest for iSF materials.
CHEMISTRY OF MATERIALS
(2021)
Article
Chemistry, Multidisciplinary
Fabian Weber, Hirotoshi Mori
Summary: Following a report on the importance of intramolecular hydrogen bonds in improving NIR-TADF efficiency in CAT-1, a study was conducted to compare the performance of intramolecular doubly hydrogen-bonded base design to singly and non-bonded derivatives. The results showed that the structures with more intramolecular hydrogen bonds have lower internal reorganization energies. Additionally, the proposed base design allows for interlocking of charge transfer donor-, linker- and acceptor-planes through steric gauche-interactions, enabling the trapping of smaller heterocyclic linkers.
Article
Chemistry, Physical
Maria Fumanal, Clemence Corminboeuf
Summary: Donor-acceptor (D-A) copolymers have shown potential for intramolecular singlet fission (iSF), but design principles for optimizing these systems are limited. Inducing torsion can bypass the limitations of coplanar approaches, revealing the potential of noncoplanar copolymers with low triplet energies.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2021)
Article
Chemistry, Physical
Chengxi Li, Xue Jin, Jianlei Han, Tonghan Zhao, Pengfei Duan
Summary: This article discusses the circularly polarized luminescence (CPL) activity of chiroptical materials, emphasizing the importance of increasing the dissymmetry factor glum value. Recent studies have shown that amplification of glum value can be achieved in hybrid donor-acceptor systems, providing new insights for the development of highly efficient CPL materials.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2021)
Article
Chemistry, Multidisciplinary
Chao Wu, Weiqiang Liu, Kai Li, Gang Cheng, Jinfan Xiong, Teng Teng, Chi-Ming Che, Chuluo Yang
Summary: Intramolecular through-space charge-transfer (TSCT) excited states are utilized for developing thermally activated delayed fluorescence (TADF) emitters, with a series of precisely controlled TSCT emitters designed through alignment optimization of donor and acceptor segments. By increasing intramolecular pi-pi interactions, radiative decay rate of the lowest singlet excited state (S-1) is progressively enhanced with suppression of nonradiative decay, leading to significantly improved photoluminescence quantum yields of up to 0.99 in doped thin films. A high-efficiency electroluminescence device achieves a maximum external quantum efficiency (EQE) of 23.96% and maintains >20% at a brightness of 1000 cd m(-2), highlighting the importance of conformation control for high-efficiency intramolecular exciplex emitters.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Mina Ahn, Min-Ji Kim, Dae Won Cho, Kyung-Ryang Wee
Summary: A series of Peri-DPA(R) compounds were successfully synthesized to investigate their ICT properties, with steady-state spectroscopy and DFT/TD-DFT calculations confirming the gradual regulation of ICT by different substituents. Comparing D-A and D-A-D systems revealed that the type and direction of ICT are influenced by different substituents and subunit combinations.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Qing Ma, Zhen Cheng, Lei Yang, Wei Du, Yilin Yin, Wenqiang Ma, Guijuan Fan, Jinshan Li
Summary: By conducting domain-related data search and using combinatorial design, we have successfully developed a novel energetic material with excellent energy performance, safety performance, and thermal stability. This research may have significant implications for searching other high-performing energetic materials.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Yang Jiao, Luka Dordevic, Haochuan Mao, Ryan M. Young, Tyler Jaynes, Hongliang Chen, Yunyan Qiu, Kang Cai, Long Zhang, Xiao-Yang Chen, Yuanning Feng, Michael R. Wasielewski, Samuel Stupp, J. Fraser Stoddart
Summary: This study enhances the charge-transfer interactions between donor and acceptor molecules through mechanical interlocking, leading to increased absorption of visible light and good catalytic activity. The [2]catenane demonstrated excellent performance in both photo-reductions and -oxidations, showing potential for solar energy conversion and development of active artificial molecular shuttles, switches, and machines.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Sudip Baguli, Abhishek Kundu, Soumajit Nath, Debashis Adhikari, Debabrata Mukherjee
Summary: Virtually irreversible intramolecular C-H activations are detrimental to aza-carbenes. A picolyl-tethered cyclic(alkyl)(amino)carbene (CAAC) undergoes isomerization into a donor-acceptor cyclopropane, but can be restored as a CAAC through retro-C-H activation in the presence of trapping agents such as Se or CuCl. The same donor-acceptor cyclopropane can be readily hydrolyzed to form a pyrrolidin-2-ol, acting as another precursor of picoCAAC, by undergoing 1,1-dehydration in the presence of Se or CuCl. This chemistry differs from the N-heterocyclic carbene analogue.
Article
Chemistry, Multidisciplinary
Maria Fumanal
Summary: The design of a functional 2D-COF with intramolecular singlet fission capabilities is achieved through the investigation and application of the donor-acceptor copolymer strategy.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Xin Qian, Feihong Chu, Wencai Zhou, Zilong Zheng, Xiaoqing Chen, Yi Zhao
Summary: By balancing the conversion of triplet excitons into singlet excitons and the radiative process from a low-lying excited state to the ground state, we studied the impact of the donor-acceptor dihedral angle (.D-A) on TADF molecules. Through first-principles calculations and molecular dynamics simulations, we investigated the effect of .D-A on the energy splitting and spin-orbit coupling between singlet and triplet excitons, as well as the transition dipole moment for carbazole benzonitrile (CzBN) derivatives. The proposed ideal .D-A of 77 degrees achieved a potential highest exciton utilization efficiency (94.4%) for blue light CzBN derivatives.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Organic
Angeliki Giannoulis, Katrin Ackermann, Alexey Bogdanov, David B. B. Cordes, Catherine Higgins, Joshua Ward, Alexandra M. Z. Slawin, James E. E. Taylor, Bela E. E. Bode
Summary: Nitroxides, a unique class of persistent radicals, have a wide range of applications, from spin probes to polarizing agents. This study focuses on the synthesis of pyrroline-based nitroxide radicals and compares two possible synthetic routes for forming two key intermediates. The synthesized compounds were characterized using X-ray crystallography and their electronic communication was quantified using Continuous Wave Electron Paramagnetic Resonance (CW-EPR). This research expands the repertoire of mono- and bis-nitroxides and paves the way for studying quantum coherence effects and using them as polarizing agents.
ORGANIC & BIOMOLECULAR CHEMISTRY
(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
Chemistry, Physical
Lin-jie Yang, Wenye Xuan, David Webster, Lethy Krishnan Jagadamma, Teng Li, David N. Miller, David B. Cordes, Alexandra M. Z. Slawin, Graham A. Turnbull, Ifor D. W. Samuel, Hsin-Yi Tiffany Chen, Philip Lightfoot, Matthew S. Dyer, Julia L. Payne
Summary: One of the advantages of organic-inorganic metal halides is their highly tuneable structures and properties, which are important for optimizing materials for photovoltaics and optoelectronic devices. In this study, bromine was included in a layered perovskite to induce a decrease in band gap and a structural transition. The inclusion of bromine also resulted in the formation of a new band in the electronic structure and a significant increase in mobility and/or carrier concentration. This work highlights the potential of molecular inclusion as a tool to tune the electronic properties of layered organic-inorganic perovskites.
CHEMISTRY OF MATERIALS
(2023)
Article
Chemistry, Physical
Eimantas Duda, Subeesh Madayanad Suresh, David Hall, Sergey Bagnich, Rishabh Saxena, David B. Cordes, Alexandra M. Z. Slawin, David Beljonne, Yoann Olivier, Anna Koehler, Eli Zysman-Colman
Summary: This study introduces a molecular design that gradually increases the number of quasi-degenerate states to enhance the efficiency of thermally activated delayed fluorescence (TADF) using the oligomer approach. By selecting and arranging benzonitrile (BN) acceptors and amine donors, connected together via repetitive donor-acceptor units, the number of quasi-degenerate states is gradually increased. It is found that increasing the size of the oligomer enhances the rates of intersystem crossing and reverse intersystem crossing.
CHEMISTRY OF MATERIALS
(2023)
Article
Chemistry, Inorganic & Nuclear
Hang Liu, Hassan Hafeez, David B. Cordes, Alexandra M. Z. Slawin, Gavin Peters, Stephen L. Lee, Ifor D. W. Samuel, Finlay D. Morrison
Summary: In this work, a novel inorganic halide Cs10MnSb6Cl30 with a distinctive 10H perovskite polytype structure is reported. The Cs10MnSb6Cl30 has 30% B-site vacancies ordered at both corner-and face-sharing sites, resulting in a reduction of octahedral connectivity to 1D and enhanced photoluminescence. This study demonstrates the existence of the 10H perovskite structure in halides and the potential of vacancy rearrangements to tune the optical properties of perovskite polytypes.
INORGANIC CHEMISTRY
(2023)
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, Multidisciplinary
Tomas Matulaitis, Paloma L. dos Santos, Youichi Tsuchiya, David B. Cordes, Alexandra M. Z. Slawin, Chihaya Adachi, Ifor D. W. Samuel, Eli Zysman-Colman
Summary: Three new derivatives of 1,2,4,5-tetraphenylimidazole were synthesized and characterized. DMAC-TPI and PXZ-TPI showed low oscillator strength and low photoluminescence quantum yields, while PTZ-TPI exhibited room temperature phosphorescence by connecting a donor group to the N1 position.
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, Inorganic & Nuclear
Lutao Zhang, Francesca A. Christie, Anna E. Tarcza, Helena G. Lancaster, Laurence J. Taylor, Michael Buhl, Olga L. Malkina, J. Derek Woollins, Cameron L. Carpenter-Warren, David B. Cordes, Alexandra M. Z. Slawin, Brian A. Chalmers, Petr Kilian
Summary: A series of peri-substituted acenaphthene-based phosphine selenoether bidentate ligands were synthesized and their properties in coordination with metals were investigated. The rigid ligands exhibited strong coupling effects and the coordination atoms were bridged by Lewis acidic motifs in the solid-state structures. Analysis of the NMR and X-ray diffraction data of the synthesized metal complexes provided insights into the interaction between the ligands and metals.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Stuart Burnett, Rochelle Ferns, David B. Cordes, Alexandra M. Z. Slawin, Tanja van Mourik, Andreas Stasch
Summary: This article reports on the different complexes obtained from the reactions of [(iPrDip)NacNac)Mg}(2)] with different reactants and reveals the structural characteristics of these complexes through experimental and computational studies.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Daniel J. Davidson, Fei Lu, Laura Faas, Daniel M. Dawson, Geoffrey P. Warren, Isabella Panovic, James R. D. Montgomery, Xiaoyan Ma, Boris G. Bosilkov, Alexandra M. Z. Slawin, Tomas Lebl, Afroditi Chatzifragkou, Steve Robinson, Sharon E. Ashbrook, Liz J. Shaw, Smilja Lambert, Isabella Van Damme, Leonardo D. Gomez, Dimitris Charalampopoulos, Nicholas J. Westwood
Summary: Cocoa pod husks, an underutilized resource in chocolate manufacturing, contain lignin with potential applications. An optimized extraction method led to high-quality lignin, allowing for further investigation of its structure and chemical transformation abilities. Preliminary analysis of other product streams from the husks was also conducted.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2023)
Article
Crystallography
Saied M. Soliman, Ayman El-Faham, Assem Barakat, Alexandra M. Z. Slawin, John Derek Woollins, Morsy A. M. Abu-Youssef
Summary: Through X-ray crystallography, we synthesized and elucidated the structures of two IIB group complexes [Cd(DMPT)Cl-2] (6) and [Zn(DMPT)Cl-2] (7). Both complexes crystallized in the monoclinic crystal system, with different lattice parameters. Complex 6 exhibited a square pyramidal coordination environment, while complex 7 showed an intermediate between trigonal bipyramidal and square pyramidal coordination. Hirshfeld calculations revealed that hydrogen bonding interactions played a significant role in the supramolecular structure of both complexes.
Article
Chemistry, Multidisciplinary
Pagidi Sudhakar, Alexandra Slawin, Eli Zysman-Colman
Summary: This article reports the synthesis and optoelectronic characterization of several luminescent materials, and explains the changes in their luminescent properties in polymer films, revealing that some of these materials exhibit delayed fluorescence and reversible photoluminescent response.
FRONTIERS IN CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Alastair J. Nimmo, Jacqueline Bitai, Claire M. Young, Calum McLaughlin, Alexandra M. Z. Slawin, David B. Cordes, Andrew D. Smith
Summary: This study demonstrates an unusual reversible Michael addition reaction, using an isothiourea as a Lewis base catalyst, which produces stereoselective products. The basicity of the reaction conditions and the reactivity of the catalyst affect the selectivity of the products. By combining the reversible Michael addition with a crystallisation-induced diastereomer transformation, high yields and stereocontrol of the products can be achieved.
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)
