Article
Chemistry, Applied
Assia Tafrioucht, Jad Rabah, Krystyna Baczko, Helene Fensterbank, Rachel Meallet-Renault, Gilles Clavier, Francois Couty, Emmanuel Allard, Karen Wright
Summary: An easily synthesized alpha-hydroxy-beta-azidotetrazole scaffold was used to build a three dimensional polychromic system, which exhibited notably efficient energy transfer values.
Review
Chemistry, Physical
Wjatscheslaw Popp, Dominik Brey, Robert Binder, Irene Burghardt
Summary: The study of ultrafast photoinduced energy and charge transfer events in organic multichromophoric systems requires quantum dynamical studies due to the complex interplay of electronic couplings, exciton delocalization, nonadiabatic effects, and vibronic couplings. By combining first-principles lattice Hamiltonians with accurate quantum dynamical simulations, a detailed understanding of the coherent exciton migration, charge transfer exciton creation, and exciton dissociation in organic functional materials can be achieved. Key factors such as coherent transfer, trapping effects from high-frequency phonon modes, and thermal activation from low-frequency soft modes are highlighted in driving diffusive dynamics.
ANNUAL REVIEW OF PHYSICAL CHEMISTRY, VOL 72
(2021)
Article
Chemistry, Multidisciplinary
Yang Zhou, Stephane Maisonneuve, Francois Maurel, Juan Xie, Remi Metivier
Summary: This study reports the experimental and theoretical investigation of compounds with multiple DCM units, evaluating their photophysical properties and revealing the intramolecular energy transfer processes occurring among DCM units.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Physics, Condensed Matter
Edoardo Cignoni, Lorenzo Cupellini, Benedetta Mennucci
Summary: In this study, a method is developed to compute electronic couplings in multichromophoric aggregates without expensive quantum chemical calculations. Transition charge approximation is used to represent the quantum mechanical transition densities of the chromophores, while an atomistic and polarizable classical model is utilized to describe the environment. Additionally, a regression approach is employed to estimate transition charges directly from the chromophore geometry, bypassing the need for quantum mechanical calculations.
JOURNAL OF PHYSICS-CONDENSED MATTER
(2022)
Article
Chemistry, Multidisciplinary
Deepak Badgurjar, Sairaman Seetharaman, Francis D'Souza, Raghu Chitta
Summary: A panchromatic triad composed of benzothiazole (BTZ) and BF2-chelated boron-dipyrromethene (BODIPY) moieties linked to a zinc porphyrin (ZnP) core has been synthesized and characterized. The triad displayed photoinduced energy transfer and subsequent singlet-singlet energy transfer, while the formation of a supramolecular tetrad with electron transfer properties was confirmed. Femtosecond transient absorption studies provided evidence for the sequential occurrence of energy transfer and electron transfer events in the supramolecular tetrad.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Nanoscience & Nanotechnology
Honghong Duan, Fan Cao, Hongxing Hao, Hongtao Bian, Liping Cao
Summary: The study explores the construction of artificial photofunctional systems with energy and electron transfer functions via a host-guest approach using a tetraphenylethene-based octacationic cage and fluorescent dyes. The cage traps various dyes within its hydrophobic cavity to form 1:1 host-guest complexes via CH-pi, pi-pi, and/or electrostatic interactions in solution. Efficient energy transfer and ultrafast photoinduced electron transfer between the cage and dyes are competitive processes in artificial photofunctional systems.
ACS APPLIED MATERIALS & INTERFACES
(2021)
Article
Chemistry, Organic
Cesar Ray, Edurne Avellanal-Zaballa, Monica Munoz-Ubeda, Jessica Colligan, Florencio Moreno, Gilles Mueller, Ivan Lopez-Montero, Jorge Banuelos, Beatriz L. Maroto, Santiago de la Moya
Summary: We report a simple method for the direct post-multifunctionalization of common BODIPYs, which does not interfere with their initial photophysical behavior. This method involves the transformation of an F-BODIPY into an N-BODIPY using a readily available dissimilarly-N,N'-disubstituted bis(sulfonamide). Using this approach, we synthesized a series of unprecedented dissimilar-at-boron N-BODIPYs, which can be used as efficient multichromophoric arrays for light harvesting, specific bioprobes for fluorescent imaging, or efficient chiroptical dyes exhibiting visible circular dichroism and circularly polarized luminescence. Notably, this approach also led to the synthesis of the first CPL-bright chiral-at-boron BODIPYs, a significant novelty in BODIPY chemistry and CPL emitters.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Physical
Bhupendra Kumar Dwivedi, Ambikesh Dhar Dwivedi, Daya Shankar Pandey
Summary: The strategic design, synthesis, and thorough characterizations of a redox-active BODIPY-based tripodal system (tri-BDP) displaying efficient aggregation-induced emission (AIE), great sensitivity toward the viscosity of a medium, ability for triplet photosensitization, singlet oxygen generation, and photooxidation have been described. The photophysical properties of tri-BDP in various solvents and in the solid state have been extensively investigated. It displayed efficient AIE and green (-,520) emission in acetonitrile/ether mixture and red (-,621 nm) emission in the solid state. Detailed viscosity-dependent studies suggested that it can act as a fluorescent molecular rotor. Triplet photosensitization, singlet oxygen generation, and photooxidation studies in the presence of 1,3-diphenylisobenzofuran and 1,5-dihydroxyl naphthalene suggested its high efficiency toward intersystem crossing and singlet oxygen generation. Detailed electrochemical investigations suggested the redox activity of the system. Hence, this system represents multifunctional features and can be applied as a functional material for various applications.
JOURNAL OF PHYSICAL CHEMISTRY B
(2022)
Article
Chemistry, Physical
Genwang Wei, Xinyue Zhang, Jianan Li, Wenjun Bai, Caichao Ye, Wenqing Zhang
Summary: 2,2'-Bithiazolothienyl-4,4',10,10'-tetracarboxydiimide (DTzTI) is a novel imide-functionalized thiazole that serves as an excellent building block for constructing all-acceptor homopolymers. The conjugation length of the homopolymer molecules significantly affects the recombination energy, delocalization of frontier molecular orbitals, and electron-transfer efficiency. The substitution of fluorine or selenium can lower the LUMO level and improve the environmental stability.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Multidisciplinary
Steven C. Boggess, Shivaani S. Gandhi, Brittany R. Benlian, Evan W. Miller
Summary: Improvements in the fluorene molecular wire scaffold by adding a single vinyl spacer led to enhanced voltage sensitivity and reduced phototoxicity, enabling successful monitoring of action potential kinetics in various cell types.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Fei-Fei Yan, Wen-Jing Jiang, Nian-Tao Yao, Pan-Dong Mao, Liang Zhao, Hui-Ying Sun, Yin-Shan Meng, Tao Liu
Summary: Manipulating fluorescence by photo-switched spin-state conversions is an attractive prospect for applications in smart magneto-optical materials and devices. In this work, a spin crossover (SCO) Fe-II-based fluorophore was embedded into a metal-organic framework (MOF) to tune the energy transfer paths. This work represents a new prototype compound showing bidirectional photo-switched fluorescence by manipulating the spin states of iron(II).
Article
Chemistry, Multidisciplinary
Kaiya Wang, Krishnasamy Velmurugan, Bin Li, Xiao-Yu Hu
Summary: This review highlights the current research status and potential applications of light-harvesting systems, focusing on the use of macrocycles as supramolecular hosts for constructing LHSs and their applications in photocatalysis, sensing, and imaging. Challenges and developing trends in photochemical solar energy conversion are also discussed.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Lina M. Aguirre-Diaz, Marcelo Echeverri, Katherine Paredes-Gil, Natalia Snejko, Berta Gomez-Lor, Enrique Gutierrez-Puebla, M. Angeles Monge
Summary: Three new cadmium-based coordination polymers, CdPF-1, CdPF-2, and CdPF-3, were synthesized hydrothermally using different nitrogenated auxiliary linkers. Among them, CdPF-2 and CdPF-3 showed excellent sensing capabilities for explosive nitro aromatic compounds.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Optics
Xilong Liang, Chengbing Qin, Zhixing Qiao, Wenhui Kang, Hualong Yin, Shuai Dong, Xiangdong Li, Shen Wang, Xingliang Su, Guofeng Zhang, Ruiyun Chen, Jianyong Hu, Liantuan Xiao, Suotang Jia
Summary: This study demonstrates that the optical interference effect between quantum dots (QD) and 2D materials can dramatically enhance and modulate the photoluminescence (PL) intensity of QD films in hybrid structures. Experimental measurements confirm the theoretical predictions and show the potential of the optical interference effect in controlling the PL properties in different QD-2D hybrid structures.
Article
Chemistry, Applied
Chao-Qun Ma, Ning Han, Ying Wang, Rong-Zhou Wang, Shengsheng Yu, Yue-Bo Wang, Ling-Bao Xing
Summary: In this study, an efficient artificial light-harvesting system was constructed using a polyelectrolyte material sodium carboxymethyl cellulose (CMC) and an AIE molecule cyano-substituted amphiphilic hydroquinone derivative (PPTA) in an aqueous solution. The energy harvested by fluorescent dyes EY and SR101 from the supramolecular assembly PPTA-CMC was utilized for photochemical catalysis reactions in the aqueous medium, including dehalogenation, cross dehydrogenation coupling, and alkylation.
Article
Chemistry, Organic
Xiaofei Chen, Quentin Duez, Guilherme L. Tripodi, Pieter J. Gilissen, Dimitrios Piperoudis, Paul Tinnemans, Johannes A. A. W. Elemans, Jana Roithova, Roeland J. M. Nolte
Summary: In this study, the mechanistic process of alkene epoxidation mediated by achiral and chiral manganese(V)oxo porphyrin cage complexes was investigated using ion mobility mass spectrometry. The results show that the oxo ligand on the outside of the cage reacts faster with the substrate than the oxo ligand on the inside, indicating how the catalytic activity of the macrocyclic porphyrin complex can be tuned.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Multidisciplinary Sciences
Anne Swartjes, Paul B. White, Jeroen P. J. Bruekers, Johannes A. A. W. Elemans, Roeland J. M. Nolte
Summary: The study shows that metallohost-guest systems can be studied using the paramagnetic relaxation enhancement effect. Mn(III) porphyrin cage compounds can bind and thread low molecular weight and polymeric guests through this effect.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Chris E. Finlayson, Giselle Rosetta, John J. Tomes
Summary: The method of spectroscopic ellipsometry is used to investigate complex periodic nanomaterials with intense resonant structural color. A multilayer optical quasi-model is developed to understand the correlation between ellipsometric parameters and shear-induced crystallinity. These approaches provide reliable means for in-line tracking of sample quality in large scale processing and applications of such materials.
APPLIED SCIENCES-BASEL
(2022)
Article
Materials Science, Multidisciplinary
Tao Wang, Tianshi Ye, Liang Qiao, Weiyu Kong, Fang Zeng, Yao Zhang, Ruitian Sun, Lin Zhang, Han Chen, Rongkun Zheng, Xudong Yang
Summary: In this study, we report a feasible multifunctional additive strategy using cesium stearate to passivate defects in perovskite films, effectively suppressing nonradiative recombination losses and improving the photovoltaic performance and stability of perovskite solar cells. The power conversion efficiency of the pin structured PSC is boosted to 23.41%, and the device shows good stability in ambient air without encapsulation, maintaining 91.6% of the initial efficiency after 720 hours.
SCIENCE CHINA-MATERIALS
(2022)
Article
Chemistry, Multidisciplinary
Pieter J. Gilissen, Xiaofei Chen, Joep De Graaf, Paul Tinnemans, Ben L. Feringa, Johannes A. A. W. Elemans, Roeland J. M. Nolte
Summary: We report a photoswitchable iron(III) salen phosphate catalyst for enantiodivergent oxidation of prochiral aryl alkyl sulfides to chiral aryl alkyl sulfoxides. The stable (S)-axial isomer of the catalyst produced enantioenriched sulfoxides with (R)-configuration up to 75% e.e., while the photoisomerized metastable (R)-axial isomer favored the formation of (S)-sulfoxides up to 43% e.e. The maximum Delta e.e. value obtained in enantiodivergent sulfoxidation was 118%, identical to that observed in the enantiodivergent epoxidation of alkenes by a related Mn1 catalyst. This iron-based catalyst expands the range of photoswitchable enantiodivergent catalysts and shows potential for development of a catalytic system capable of writing digital information on a polymer chain in the form of chiral sulfoxide functions.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Electrochemistry
Mark E. Orazem, Burak Ulgut
Summary: The effectiveness of drift correction in measuring electrochemical impedance spectra is examined. Numerical simulations and experimental data on batteries and capacitors demonstrate that drift correction cannot generate Kramers-Kronig consistent data for nonstationary systems. While drift correction improves the quality of spectra obtained for stationary systems, it does not fully recover the original spectrum unaffected by drift.
ELECTROCHIMICA ACTA
(2023)
Article
Education, Scientific Disciplines
Bethany Walker, Chris E. Finlayson
Summary: The advanced simulation software with convenient graphical user-interfaces provides a powerful tool for teaching quantum chemistry methods and other applications of quantum mechanics. In this student project, a series of semiconducting chalcogenophenes with varying polymer chain lengths were simulated using density functional theory. The results showed that increasing the chain length led to a narrowing and convergence of the bandgap, with hexa-tellurophene having significantly favorable electronic properties compared to the other analogues.
EUROPEAN JOURNAL OF PHYSICS
(2023)
Article
Chemistry, Physical
Yuhang Liang, Xiangyuan Cui, Feng Li, Catherine Stampfl, Simon P. Ringer, Xudong Yang, Jun Huang, Rongkun Zheng
Summary: Oxygen ingression has been shown to decrease the carrier lifetime of Sn-based perovskites, and our calculations reveal that oxygen tends to form substitutional OI, which remarkably increases the recombination rate of native I vacancies (VI). This explains the observed decline of carrier lifetime in perovskites exposed to air. The enhanced carrier recombination is due to a smaller electron capture barrier of OI, resulting from lattice strengthening and suppressed structural relaxation upon electron capture. These insights offer a route to improve device performance in Sn-based perovskite optoelectronics operating in ambient air.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Crystallography
Giselle Rosetta, John J. Tomes, Mike Butters, Matthew Gunn, Chris E. Finlayson
Summary: This study presents three-dimensional goniometric measurements of structural color from melt-sheared polymer nanoparticle composites, revealing high-angle features resulting from Bragg scattering. The spectroscopic and angular properties of these scattering spots are depicted through 'scattering cones' obtained from full 180 degrees hemispherical scans. The Miller indices of the responsible photonic crystal planes are identified, and observations are made regarding the appearance of scattering in quasi-ordered systems. The report contributes to the understanding of Bragg scattering and structural color in disordered structures, with implications for practical applications in sensing.
Article
Chemistry, Analytical
Gozde Karaoglu, Ezgi Kutbay, Suleyman Ince, Burak Ulgut, Sefik Suzer
Summary: X-ray photoelectron spectroscopy (XPS) was used to investigate the effects of direct and alternating current bias on the potential development in an ionic liquid capacitor. The variations in binding energy positions of atomic core levels were used to extract local information before and after the insertion of additional resistors. This non-invasive and direct method provides valuable insights into the electrochemical properties of the system.
ANALYTICAL CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Isil Ulu, Burak Ulgut, Omer Dag
Summary: A synthetic method has been developed to fabricate spherical mesoporous metal pyrophosphate particles and graphite rod-coated electrodes, which are important for energy storage. The composition and structure of the materials have an impact on the charge capacity and specific capacitance of the electrodes.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Eylul Calikyilmaz, Gozde Karaoglu, Mete Demir, Onur Sahin, Burak Ulgut, Akin Akdag, Yunus Emre Turkmen
Summary: The new scaffold demonstrates efficient intramolecular through-space charge transfer, with electron-rich benzofuran and electron-deficient ynone groups strategically placed in proximity via a naphthalene spacer. The charge transfer is supported by distinct CT bands in the visible region (>500 nm) in their UV-vis absorption and emission spectra.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Isil Ulu, Burak Ulgut, Omer Dag
Summary: The development of high-energy-density electrodes is crucial for the advancement of renewable and clean energy storage materials. In this study, mesoporous Ni2P2O7 (m-NiPP) electrodes with a decent charge capacity were synthesized using a novel method. The electrodes, composed of spherical mesoporous NiPP particles, remained amorphous over a wide temperature range and exhibited a substantial charge capacity when undergoing a chemical conversion in an alkaline medium.
JOURNAL OF MATERIALS CHEMISTRY A
(2023)
Article
Chemistry, Multidisciplinary
Pieter J. Gilissen, Quentin Duez, Guilherme L. Tripodi, Magda M. J. Dekker, Jiangkun Ouyang, Kais Dhbaibi, Nicolas Vanthuyne, Jeanne Crassous, Jana Roithova, Johannes A. A. W. Elemans, Roeland J. M. Nolte
Summary: The kinetic enantio-recognition of chiral viologen guests by planar-chiral porphyrin cage compounds is determined by the planar chirality of the host and influenced by its size, but not the chirality of its substituents.
CHEMICAL COMMUNICATIONS
(2023)
Article
Polymer Science
Giselle Rosetta, Line Macaire, Mike Butters, Chris E. Finlayson
Summary: The emulsion polymerization process allows for control over the size and monodispersity of core-interlayer-shell polymer nanoparticles. By optimizing key experimental parameters, such as temperature, reactant purity, and agitation rate, composite particles with shear-orderable properties can be created. These findings have implications for the industrial-scale fabrication of polymeric photonic materials.