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Keywords = calculation of triplet energy

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11 pages, 1494 KiB  
Article
Effect of the Number of Phenylcarbazole Units Adorned to the Silicon Atom for High Triplet Energy with High Charge Mobility
by Mina Ahn, Sunhee Lee, Min-Ji Kim, Jeongyoon Kim, Jina Lee, Heejun Nam, Kyung-Ryang Wee and Won-Sik Han
Molecules 2025, 30(3), 454; https://doi.org/10.3390/molecules30030454 - 21 Jan 2025
Abstract
Increasing the number of phenylcarbazole (PC) units attached to the silicon atom in organic solid-state thin films led to a remarkable enhancement in charge mobility. Specifically, the charge mobility values exhibited an increase from 1.32 × 10−4 cm2/Vs for 3PCBP [...] Read more.
Increasing the number of phenylcarbazole (PC) units attached to the silicon atom in organic solid-state thin films led to a remarkable enhancement in charge mobility. Specifically, the charge mobility values exhibited an increase from 1.32 × 10−4 cm2/Vs for 3PCBP to 4.39 × 10–4 cm2/Vs for 2MCBP, ultimately reaching 1.16 × 10–3 cm2/Vs for MCBP. Notably, these enhancements were achieved while maintaining a high triplet energy of 3.01 eV. DFT calculations on the spin density distribution provided insights into the nature of the improved mobility while preserving the triplet energy. The accuracy of the DFT calculations was validated by comparing the results with experimental data from photoemission spectroscopy (PES). Mobility measurements, as contemplated by DFT, allowed for a comprehensive understanding of the factors influencing enhanced mobility while keeping the triplet energy constant. This study suggested that intramolecular charge transfers played a crucial role in reducing reorganization energy, showing an inverse dependence on the number of PCs. Consequently, it was inferred that the manipulation of PC units could effectively optimize charge transfer mechanisms, offering a promising avenue for tailoring organic thin films with improved electronic properties. Full article
(This article belongs to the Section Molecular Structure)
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19 pages, 3538 KiB  
Article
Localized and Excimer Triplet Electronic States of Naphthalene Dimers: A Computational Study
by Lara Martínez-Fernández and Roberto Improta
Molecules 2025, 30(2), 298; https://doi.org/10.3390/molecules30020298 - 13 Jan 2025
Viewed by 357
Abstract
We perform DFT calculations with different hybrid (ωB97X-D and M05-2X) and double hybrid (B2PLYP-D3 and ωB2PLYP) functionals to characterize the lowest energy triplet excited states of naphthalene monomer and dimers in different stacking arrangements and to simulate their absorption spectra. We show that [...] Read more.
We perform DFT calculations with different hybrid (ωB97X-D and M05-2X) and double hybrid (B2PLYP-D3 and ωB2PLYP) functionals to characterize the lowest energy triplet excited states of naphthalene monomer and dimers in different stacking arrangements and to simulate their absorption spectra. We show that both excimer and localized triplet minima exist. In the former, the spin density is delocalized over the two monomers, adopting a face-to-face arrangement with a short inter-molecular distance. In the latter, the spin density is localized on a single naphthalene molecule, and different minima or pseudo-minima are possible, the most stable one corresponding to a slipped parallel arrangement. According to B2PLYP-D3 calculations, excimer minima are the most stable, in line with the indications of ADC(2) studies. However, the relative stability of the minima is reverted when including thermal and vibrational effects. Excimer minima exhibit a very intense absorption spectrum, peaking above 500 nm. The computed absorption spectra of localized minima significantly depend on the stacking geometry and do not coincide with that of isolated naphthalene. Hybrid functionals provide very accurate vibronic absorption spectra for naphthalene monomer, both in the singlet and in the triplet state, but underestimate the stability of the excimer triplet. Full article
(This article belongs to the Section Physical Chemistry)
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13 pages, 2563 KiB  
Article
Fluorescence Properties of Novel Multiresonant Indolocarbazole Derivatives for Deep-Blue OLEDs from Multiscale Computer Modelling
by Nikita O. Dubinets and Andrey Yu. Sosorev
Molecules 2025, 30(2), 255; https://doi.org/10.3390/molecules30020255 - 10 Jan 2025
Viewed by 388
Abstract
Multiresonant fluorophores are a novel class of organic luminophores with a narrow emission spectrum. They can yield organic light-emitting devices, e.g., OLEDs, with high colour purity. In this study, we applied DFT and multiscale modelling to predict the electronic and optical properties of [...] Read more.
Multiresonant fluorophores are a novel class of organic luminophores with a narrow emission spectrum. They can yield organic light-emitting devices, e.g., OLEDs, with high colour purity. In this study, we applied DFT and multiscale modelling to predict the electronic and optical properties of several novel derivatives of indolocarbazole pSFIAc, which had recently shown a high potential in deep-blue OLEDs. We found that the addition of phenyls to a certain position of the pSFIAc core can considerably increase the fluorescent rate, leaving other properties (HOMO, LUMO, lowest excited singlet and lowest triplet states’ energies) virtually unaffected. This can improve the efficiency and stability of deep-blue organic light-emitting devices; the suggested phenyl-substituted indolocarbazoles have been shown to be compatible with two popular anthracene-based hosts. On the contrary, the addition of phenyls to another positions of the core is detrimental for optoelectronic properties. QM/MM and QM/EFP calculations yielded negligible inhomogeneous broadening of the emission spectrum of the studied luminophores when embedded as dopants in anthracene-based hosts, predicting high colour purity of the corresponding devices. On the basis of the obtained results, we selected one novel multiresonant indolocarbazole derivative that is most promising for organic light-emitting devices. We anticipate the revealed structure-property relationships will facilitate the rational design of efficient materials for organic (opto)electronics. Full article
(This article belongs to the Section Computational and Theoretical Chemistry)
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15 pages, 1634 KiB  
Article
Theoretical Study on Singlet Fission Dynamics and Triplet Migration Process in Symmetric Heterotrimer Models
by Hajime Miyamoto, Kenji Okada, Kohei Tada, Ryohei Kishi and Yasutaka Kitagawa
Molecules 2024, 29(22), 5449; https://doi.org/10.3390/molecules29225449 - 19 Nov 2024
Viewed by 832
Abstract
Singlet fission (SF) is a photophysical process where one singlet exciton splits into two triplet excitons. To construct design guidelines for engineering directional triplet exciton migration, we investigated the SF dynamics in symmetric linear heterotrimer systems consisting of different unsubstituted or 6,13-disubstituted pentacene [...] Read more.
Singlet fission (SF) is a photophysical process where one singlet exciton splits into two triplet excitons. To construct design guidelines for engineering directional triplet exciton migration, we investigated the SF dynamics in symmetric linear heterotrimer systems consisting of different unsubstituted or 6,13-disubstituted pentacene derivatives denoted as X/Y (X, Y: terminal and center monomer species). Time-dependent density functional theory (TDDFT) calculations clarified that the induction effects of the substituents, represented as Hammett’s para-substitution coefficients σp, correlated with both the excitation energies of S1 and T1 states, in addition to the energies of the highest occupied and lowest unoccupied molecular orbitals (HOMO and LUMO). Electronic coupling calculations and quantum dynamics simulations revealed that the selectivity of spatially separated TT states for heterotrimers increased over 70%, superior to that in the homotrimer: an optimal region of the difference in σp between the substituents of X and Y for the increase in SF rate was found. The origin of the rise in SF rate is explained by considering the quantum interference effect: reduction in structural symmetry opens new interaction paths, allowing the S1-TT mixing, which contributes to accelerating the hetero-fission between the terminal and center molecules. Full article
(This article belongs to the Section Computational and Theoretical Chemistry)
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9 pages, 2120 KiB  
Article
Exploring Aromaticity Effects on Electronic Transport in Cyclo[n]carbon Single-Molecule Junctions
by Peiqi Yang, Haoyang Pan, Yudi Wang, Jie Li, Yangyu Dong, Yongfeng Wang and Shimin Hou
Molecules 2024, 29(16), 3827; https://doi.org/10.3390/molecules29163827 - 12 Aug 2024
Viewed by 1224
Abstract
Cyclo[n]carbon (Cn) is one member of the all-carbon allotrope family with potential applications in next-generation electronic devices. By employing first-principles quantum transport calculations, we have investigated the electronic transport properties of single-molecule junctions of Cn, with n = 14, [...] Read more.
Cyclo[n]carbon (Cn) is one member of the all-carbon allotrope family with potential applications in next-generation electronic devices. By employing first-principles quantum transport calculations, we have investigated the electronic transport properties of single-molecule junctions of Cn, with n = 14, 16, 18, and 20, connected to two bulk gold electrodes, uncovering notable distinctions arising from the varying aromaticities. For the doubly aromatic C14 and C18 molecules, slightly deformed complexes at the singlet state arise after bonding with one Au atom at each side; in contrast, the reduced energy gaps between the highest occupied and the lowest unoccupied molecular orbitals due to the orbital reordering observed in the doubly anti-aromatic C16 and C20 molecules lead to heavily deformed asymmetric complexes at the triplet state. Consequently, spin-unpolarized transmission functions are obtained for the Au-C14/18-Au junctions, while spin-polarized transmission appears in the Au-C16/20-Au junctions. Furthermore, the asymmetric in-plane π-type hybrid molecular orbitals of the Au-C16/20-Au junctions contribute to two broad but low transmission peaks far away from the Fermi level (Ef), while the out-of-plane π-type hybrid molecular orbitals dominate two sharp transmission peaks that are adjacent to Ef, thus resulting in much lower transmission coefficients at Ef compared to those of the Au-C14/18-Au junctions. Our findings are helpful for the design and application of future cyclo[n]carbon-based molecular electronic devices. Full article
(This article belongs to the Section Nanochemistry)
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25 pages, 5186 KiB  
Article
Kinetic Study and Reaction Mechanism of the Gas-Phase Thermolysis Reaction of Methyl Derivatives of 1,2,4,5-Tetroxane
by Alexander G. Bordón, Mariela I. Profeta, Jorge M. Romero, María J. Jorge, Lilian C. Jorge, Nelly L. Jorge, C. Ignacio Sainz-Díaz, Juliana Cuéllar-Zuquin, Daniel Roca-Sanjuán, César Viseras Iborra, André Grand and Alfonso Hernández-Laguna
Molecules 2024, 29(14), 3274; https://doi.org/10.3390/molecules29143274 - 11 Jul 2024
Viewed by 1138
Abstract
Tetroxane derivatives are interesting drugs for antileishmaniasis and antimalaric treatments. The gas-phase thermal decomposition of 3,6,-dimethyl-1,2,4,5-tetroxane (DMT) and 3,3,6,6,-tetramethyl-1,2,4,5-tetroxane (acetone diperoxide (ACDP)) was studied at 493–543 K by direct gas chromatography by means of a flow reactor. The reaction is produced in the [...] Read more.
Tetroxane derivatives are interesting drugs for antileishmaniasis and antimalaric treatments. The gas-phase thermal decomposition of 3,6,-dimethyl-1,2,4,5-tetroxane (DMT) and 3,3,6,6,-tetramethyl-1,2,4,5-tetroxane (acetone diperoxide (ACDP)) was studied at 493–543 K by direct gas chromatography by means of a flow reactor. The reaction is produced in the injector chamber at different temperatures. The resulting kinetics Arrhenius equations were calculated for both tetroxanes. Including the parent compound of the series 1,2,4,5-tetroxane (formaldehyde diperoxide (FDP)), the activation energy and frequency factors decrease linearly with the number of methyl groups. The reaction mechanisms of ACDP and 3,6,6-trimethyl-1,2,4,5-tetroxane (TMT) decomposition have been studied by means of the DFT method with the BHANDHLYP functional. Our calculations confirm that the concerted mechanism should be discarded and that only the stepwise mechanism occurs. The critical points of the singlet and triplet state potential energy surfaces (S- and T-PES) of the thermolysis reaction of both compounds have been determined. The calculated activation energies of the different steps vary linearly with the number of methyl groups of the methyl-tetroxanes series. The mechanism for the S-PES leads to a diradical O···O open structure, which leads to a C···O dissociation in the second step and the production of the first acetaldehyde/acetone molecule. This last one yields a second C···O dissociation, producing O2 and another acetone/acetaldehyde molecule. The O2 molecule is in the singlet state. A quasi-parallel mechanism for the T-PES from the open diradical to products is also found. Most of the critical points of both PES are linear with the number of methyl groups. Reaction in the triplet state is much more exothermic than the singlet state mechanism. Transitions from the singlet ground state, S0 and low-lying singlet states S1–3, to the low-lying triplet excited states, T1–4, (chemical excitation) in the family of methyl tetroxanes are also studied at the CASSCF/CASPT2 level. Two possible mechanisms are possible here: (i) from S0 to T3 by strong spin orbit coupling (SOC) and subsequent fast internal conversion to the excited T1 state and (ii) from S0 to S2 from internal conversion and subsequent S2 to T1 by SOC. From these experimental and theoretical results, the additivity effect of the methyl groups in the thermolysis reaction of the methyl tetroxane derivatives is clearly highlighted. This information will have a great impact for controlling these processes in the laboratory and chemical industries. Full article
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12 pages, 2246 KiB  
Article
Blue Phosphorescent Pt(II) Compound Based on Tetradentate Carbazole/2,3′-Bipyridine Ligand and Its Application in Organic Light-Emitting Diodes
by Hakjo Kim, Chan-Hee Ryu, Miso Hong, Kang Mun Lee, Unhyeok Jo and Youngjin Kang
Molecules 2024, 29(12), 2929; https://doi.org/10.3390/molecules29122929 - 20 Jun 2024
Cited by 1 | Viewed by 1269
Abstract
The tetradentate ligand, merging a carbazole unit with high triplet energy and dimethoxy bipyridine, renowned for its exceptional quantum efficiency in coordination with metals like Pt, is expected to demonstrate remarkable luminescent properties. However, instances of tetradentate ligands such as bipyridine-based pyridylcarbazole derivatives [...] Read more.
The tetradentate ligand, merging a carbazole unit with high triplet energy and dimethoxy bipyridine, renowned for its exceptional quantum efficiency in coordination with metals like Pt, is expected to demonstrate remarkable luminescent properties. However, instances of tetradentate ligands such as bipyridine-based pyridylcarbazole derivatives remain exceptionally scarce in the current literature. In this study, we developed a tetradentate ligand based on carbazole and 2,3′-bipyridine and successfully complexed it with Pt(II) ions. This novel compound (1) serves as a sky-blue phosphorescent material for use in light-emitting diodes. Based on single-crystal X-ray analysis, compound 1 has a distorted square-planar geometry with a 5/6/6 backbone around the Pt(II) core. Bright sky-blue emissions were observed at 488 and 516 nm with photoluminescent quantum yields of 34% and a luminescent lifetime of 2.6 μs. TD-DFT calculations for 1 revealed that the electronic transition was mostly attributed to the ligand-centered (LC) charge transfer transition with a small contribution from the metal-to-ligand charge transfer transition (MLCT, ~14%). A phosphorescent organic light-emitting device was successfully fabricated using this material as a dopant, along with 3′-di(9H-carbazol-9-yl)-1,1′-biphenyl (mCBP) and 9-(3′-carbazol-9-yl-5-cyano-biphenyl-3-yl)-9H-carbazole-3-carbonitrile (CNmCBPCN) as mixed hosts. A maximum quantum efficiency of 5.2% and a current efficiency of 15.5 cd/A were obtained at a doping level of 5%. Full article
(This article belongs to the Special Issue Structure, Spectroscopic Characterization and Application of Crystals)
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16 pages, 4369 KiB  
Article
Structural Characteristics and Improved Thermal Stability of HDPE/Calcium Pimelate Nanocomposites
by Christina Samiotaki, Evangelia Tarani, Dimitra Karavasili, Alexandra Zamboulis, Konstantinos Chrissafis and Dimitrios N. Bikiaris
Macromol 2024, 4(1), 42-57; https://doi.org/10.3390/macromol4010003 - 5 Feb 2024
Cited by 1 | Viewed by 1589
Abstract
In the present research work, calcium pimelate (CaPim) was synthesized and investigated as an additive for high-density polyethylene (HDPE). HDPE/CaPim nanocomposites were prepared by melt-mixing, with CaPim content ranging from 0.1% to 1%, affording white homogeneous materials. The chemical structure of the nanocomposites [...] Read more.
In the present research work, calcium pimelate (CaPim) was synthesized and investigated as an additive for high-density polyethylene (HDPE). HDPE/CaPim nanocomposites were prepared by melt-mixing, with CaPim content ranging from 0.1% to 1%, affording white homogeneous materials. The chemical structure of the nanocomposites and the incorporation of CaPim was confirmed by infrared spectroscopy. The surficial morphology and the additive distribution were examined by scanning electron microscopy. Differential scanning calorimetry and X-ray diffraction measurements showed that the thermal transitions and crystal structure of HDPE are not affected by the incorporation of CaPim, while the mechanical properties are retained overall. This study focuses on the thermal degradation of HDPE nanocomposites, investigating the degradation mechanism and kinetic parameters through various analytical methods. Isoconversional techniques, including the Friedman method, Vyazovkin analysis, and Ozawa Flynn Wall analysis, were employed to calculate activation energies (Eα). The degradation mechanism and kinetic triplet were determined based on a multivariate non-linear regression method (model-fitting). Finally, the presence of a CaPim additive was shown to increase the Eα of thermal degradation, consistent with the calculated dependence of Eα on the degree of conversion and the improved thermal stability of the HDPE matrix. Full article
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16 pages, 26008 KiB  
Article
Theoretical Investigation of Iridium Complex with Aggregation-Induced Emission Properties
by Piotr Lodowski and Maria Jaworska
Molecules 2024, 29(3), 580; https://doi.org/10.3390/molecules29030580 - 24 Jan 2024
Viewed by 1222
Abstract
The mechanism of aggregation-induced emission (AIE) for the bis(1-(2,4-difluorophenyl)-1H-pyrazole)(2-(20-hydroxyphenyl)-2-oxazoline)iridium(III) complex, denoted as Ir(dfppz)2(oz), was investigated with use DFT and the TD-DFT level of theory. The mechanism of radiationless deactivation of the triplet state was elucidated. Such a mechanism requires an additional, [...] Read more.
The mechanism of aggregation-induced emission (AIE) for the bis(1-(2,4-difluorophenyl)-1H-pyrazole)(2-(20-hydroxyphenyl)-2-oxazoline)iridium(III) complex, denoted as Ir(dfppz)2(oz), was investigated with use DFT and the TD-DFT level of theory. The mechanism of radiationless deactivation of the triplet state was elucidated. Such a mechanism requires an additional, photophysical triplet channel of the internal conversion (IC) type, which is activated as a result of intramolecular motion deforming the structure of the oz ligand and distorting the iridium coordination sphere. Formally, the rotational movement of the oxazoline relative to the C–C bond in the oz ligand is the main active coordinate that leads to the opening of the triplet channel. The rotation of the oxazoline group and the elongation of the Ir-Nox bond cause a transition between the luminescent, low-lying triplet state with a d/ππ* characteristic (T1(eq)), and the radiationless dd triplet state (T1(Ir)). This transition is made possible by the low energy barrier, which, based on calculations, was estimated at approximately 8.5 kcal/mol. Dimerization, or generally aggregation of the complex molecules, blocks the intramolecular movement in the ligand and is responsible for a strong increase in the energy barrier for the T1(eq) conversion of triplet states. Thus, the aggregation phenomenon blocks the nonradiative deactivation channel of the excited states and, consequently, contributes to directing the photophysical process toward phosphorescence. The mechanism involved in locking the nonradiative triplet path can be called restricted access to singlet–triplet crossing (RASTC). Full article
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15 pages, 3694 KiB  
Article
Tropospheric Photochemistry of 2-Butenedial: Role of the Triplet States, CO and Acrolein Formation, and the Experimentally Unidentified Carbonyl Compound—Theoretical Study
by Andrea Maranzana and Glauco Tonachini
Molecules 2024, 29(3), 575; https://doi.org/10.3390/molecules29030575 - 24 Jan 2024
Viewed by 1076
Abstract
Solar irradiation of 2-butenedial in the lower troposphere mainly produces isomeric ketene-enol (a key intermediate product), furanones, and maleic anhydride, the formation pathways of which were investigated in a previous study. The other main products were carbon monoxide and an experimentally unidentified carbonyl [...] Read more.
Solar irradiation of 2-butenedial in the lower troposphere mainly produces isomeric ketene-enol (a key intermediate product), furanones, and maleic anhydride, the formation pathways of which were investigated in a previous study. The other main products were carbon monoxide and an experimentally unidentified carbonyl compound. This was the subject of the present study. The oxidative reaction mechanisms were studied using DFT calculations. Water intervention is found essential. Its addition and subsequent water-assisted isomerizations (an ene-gem-diol/enol and a carboxylic acid/enol form), followed by cyclization, lead to an interesting cyclic carbonyl compound, but this pathway appears to be rather energy demanding. An alternative implies water cooperation in a ketene-enol + carboxylic acid/enol addition that gives the relevant anhydride. The anhydride is proposed as a candidate for the experimentally unidentified carbonyl product. Regarding CO and acrolein formation, the role of the triplet states, as defined by the probability of intersystem crossing from the excited singlet state S1 to T2 and T1, is discussed. The T1 photolysis pathway connecting butenedial to propenal + CO was then defined. Full article
(This article belongs to the Special Issue Interplay between Computational and Experimental Photochemistry)
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17 pages, 5022 KiB  
Article
Electronic Properties of Graphene Nano-Parallelograms: A Thermally Assisted Occupation DFT Computational Study
by Sonai Seenithurai and Jeng-Da Chai
Molecules 2024, 29(2), 349; https://doi.org/10.3390/molecules29020349 - 10 Jan 2024
Cited by 1 | Viewed by 1727
Abstract
In this computational study, we investigate the electronic properties of zigzag graphene nano-parallelograms (GNPs), which are parallelogram-shaped graphene nanoribbons of various widths and lengths, using thermally assisted occupation density functional theory (TAO-DFT). Our calculations revealed a monotonic decrease in the singlet–triplet energy gap [...] Read more.
In this computational study, we investigate the electronic properties of zigzag graphene nano-parallelograms (GNPs), which are parallelogram-shaped graphene nanoribbons of various widths and lengths, using thermally assisted occupation density functional theory (TAO-DFT). Our calculations revealed a monotonic decrease in the singlet–triplet energy gap as the GNP length increased. The GNPs possessed singlet ground states for all the cases examined. With the increase of GNP length, the vertical ionization potential and fundamental gap decreased monotonically, while the vertical electron affinity increased monotonically. Some of the GNPs studied were found to possess fundamental gaps in the range of 1–3 eV, lying in the ideal region relevant to solar energy applications. Besides, as the GNP length increased, the symmetrized von Neumann entropy increased monotonically, denoting an increase in the degree of the multi-reference character associated with the ground state GNPs. The occupation numbers and real-space representation of active orbitals indicated that there was a transition from the nonradical nature of the shorter GNPs to the increasing polyradical nature of the longer GNPs. In addition, the edge/corner localization of the active orbitals was found for the wider and longer GNPs. Full article
(This article belongs to the Special Issue Multiconfigurational and DFT Methods Applied to Chemical Systems)
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15 pages, 361 KiB  
Article
Hadronic Isospin Helicity and the Consequent SU(4) Gauge Theory
by Eckart Marsch and Yasuhito Narita
Symmetry 2023, 15(10), 1953; https://doi.org/10.3390/sym15101953 - 23 Oct 2023
Cited by 1 | Viewed by 827
Abstract
A new approach to the Dirac equation and the associated hadronic symmetries is proposed. In this approach, we linearize the second Casimir operator of the Lorentz Group, which is defined by the energy–momentum four-vector and the fermion spin, thereby using the spinor-helicity representation [...] Read more.
A new approach to the Dirac equation and the associated hadronic symmetries is proposed. In this approach, we linearize the second Casimir operator of the Lorentz Group, which is defined by the energy–momentum four-vector and the fermion spin, thereby using the spinor-helicity representation instead of the three-vector representation of the particle momentum and spin vector. We then expand the so-obtained standard Dirac equation by employing an inner abstract “hadronic” isospin, initially describing a SU(2) fermion doublet. Application of the spin-helicity representation of that isospin leads to the occurrence of a quadruplet of inner states, revealing the SU(4) symmetry via the isospin helicity operator. This further leads to two independent fermion state spaces, specifically, singlet and triplet states, which we interpret as U(1) symmetry of the leptons and SU(3) symmetry of the three quarks, respectively. These results indicate the genuinely very different physical nature of the strong SU(4) symmetry in comparison to the chiral SU(2) symmetry. While our approach does not require the a priori concept of grand unification, such a notion arises naturally from the formulation with the isospin helicity. We then apply the powerful procedures developed for the electroweak interactions in the SM, in order to break the SU(4) symmetry by means of the Higgs mechanism involving a scalar Higgs field as an SU(4) quadruplet. Its finite vacuum creates the masses of the three vector bosons involved, which can change the three quarks into a lepton and vice versa. Finally, we consider a toy model for calculation of the strong coupling constant of a Yukawa potential. Full article
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24 pages, 3540 KiB  
Article
Marcus Cross-Relationship Probed by Time-Resolved CIDNP
by Maksim P. Geniman, Olga B. Morozova, Nikita N. Lukzen, Günter Grampp and Alexandra V. Yurkovskaya
Int. J. Mol. Sci. 2023, 24(18), 13860; https://doi.org/10.3390/ijms241813860 - 8 Sep 2023
Viewed by 1048
Abstract
The time-resolved CIDNP method can provide information about degenerate exchange reactions (DEEs) involving short-lived radicals. In the temperature range from 8 to 65 °C, the DEE reactions of the guanosine-5′-monophosphate anion GMP(-H) with the neutral radical GMP(-H), of the N-acetyl [...] Read more.
The time-resolved CIDNP method can provide information about degenerate exchange reactions (DEEs) involving short-lived radicals. In the temperature range from 8 to 65 °C, the DEE reactions of the guanosine-5′-monophosphate anion GMP(-H) with the neutral radical GMP(-H), of the N-acetyl tyrosine anion N-AcTyrO with a neutral radical N-AcTyrO, and of the tyrosine anion TyrO with a neutral radical TyrO were studied. In all the studied cases, the radicals were formed in the reaction of quenching triplet 2,2′-dipyridyl. The reorganization energies were obtained from Arrhenius plots. The rate constant of the reductive electron transfer reaction in the pair GMP(-H)/TyrO was determined at T = 25 °C. Rate constants of the GMP(-H) radical reduction reactions with TyrO and N-AcTyrO anions calculated by the Marcus cross-relation differ from the experimental ones by two orders of magnitude. The rate constants of several other electron transfer reactions involving GMP(-H)/GMP(-H), N-AcTyrO/N-AcTyrO, and TyrO/TyrO pairs calculated by cross-relation agree well with the experimental values. The rate of nuclear paramagnetic relaxation was found for the 3,5 and β-protons of TyrO and N-AcTyrO, the 8-proton of GMP(-H), and the 3,4-protons of DPH at each temperature. In all cases, the dependences of the rate of nuclear paramagnetic relaxation on temperature are described by the Arrhenius dependence. Full article
(This article belongs to the Special Issue Recent Advances in Free Radicals, Radical Ions and Radical Pairs)
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11 pages, 2433 KiB  
Article
Unraveling the Pivotal Roles of Various Metal Ion Centers in the Catalysis of Quercetin 2,4-Dioxygenases
by Xueyuan Yan, Han Xiao, Jinshuai Song and Chunsen Li
Molecules 2023, 28(17), 6238; https://doi.org/10.3390/molecules28176238 - 25 Aug 2023
Cited by 2 | Viewed by 1503
Abstract
Quercetin 2,4-dioxygenase (QueD) with various transition metal ion co-factors shows great differences, but the internal reasons have not been illustrated in detail. In order to explore the effects of metal ion centers on the catalytic reactivity of QueD, we calculated and compared the [...] Read more.
Quercetin 2,4-dioxygenase (QueD) with various transition metal ion co-factors shows great differences, but the internal reasons have not been illustrated in detail. In order to explore the effects of metal ion centers on the catalytic reactivity of QueD, we calculated and compared the minimum energy crossing point (MECP) of dioxygen from the relatively stable triplet state to the active singlet state under different conditions by using the DFT method. It was found that the metal ions play a more important role in the activation of dioxygen compared with the substrate and the protein environment. Simultaneously, the catalytic reactions of the bacterial QueDs containing six different transition metal ions were studied by the QM/MM approach, and we finally obtained the reactivity sequence of metal ions, Ni2+ > Co2+ > Zn2+ > Mn2+ > Fe2+ > Cu2+, which is basically consistent with the previous experimental results. Our calculation results indicate that metal ions act as Lewis acids in the reaction to stabilize the substrate anion and the subsequent superoxo and peroxo species in the reaction, and promote the proton coupled electron transfer (PCET) process. Furthermore, the coordination tendencies of transition metal ion centers also have important effects on the catalytic cycle. These findings have general implications on metalloenzymes, which can expand our understanding on how various metal ions play their key role in modulating catalytic reactivity. Full article
(This article belongs to the Topic Advances in Enzymes and Protein Engineering)
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14 pages, 3072 KiB  
Article
Redox-Regulated Magnetic Conversions between Ferro- and Antiferromagnetism in Organic Nitroxide Diradicals
by Fengying Zhang, Zijun Zhang, Yali Zhao, Chao Du, Yong Li, Jiaqi Gao, Xiaobo Ren, Teng Ma, Boqiong Li and Yuxiang Bu
Molecules 2023, 28(17), 6232; https://doi.org/10.3390/molecules28176232 - 24 Aug 2023
Viewed by 1095
Abstract
Redox-induced magnetic transformation in organic diradicals is an appealing phenomenon. In this study, we theoretically designed twelve couples of diradicals in which two nitroxide (NO) radical groups are connected to the redox-active couplers including p-benzoquinonyl, 1,4-naphthoquinyl, 9,10-anthraquinonyl, naphthacene-5,12-dione, pentacene-6,13-dione, hexacene-6,15-dione, pyrazinyl, quinoxalinyl, phenazinyl, [...] Read more.
Redox-induced magnetic transformation in organic diradicals is an appealing phenomenon. In this study, we theoretically designed twelve couples of diradicals in which two nitroxide (NO) radical groups are connected to the redox-active couplers including p-benzoquinonyl, 1,4-naphthoquinyl, 9,10-anthraquinonyl, naphthacene-5,12-dione, pentacene-6,13-dione, hexacene-6,15-dione, pyrazinyl, quinoxalinyl, phenazinyl, 5,12-diazanaphthacene, 6,13-diazapentacene, and 6,15-diazahexacene. As evidenced at both the B3LYP and M06-2X levels of theory, the calculations reveal that the magnetic reversal can take place from ferromagnetism to antiferromagnetism, or vice versa, by means of redox method in these designed organic magnetic molecules. It was observed that p-benzoquinonyl, 1,4-naphthoquinyl, 9,10-anthraquinonyl, naphthacene-5,12-dione, pentacene-6,13-dione, and hexacene-6,15-dione-bridged NO diradicals produce antiferromagnetism while their dihydrogenated counterparts exhibit ferromagnetism. Similarly, pyrazinyl, quinoxalinyl, phenazinyl, 5,12-diazanaphthacene, 6,13-diazapentacene, and 6,15-diazahexacene-bridged NO diradicals present ferromagnetism while their dihydrogenated counterparts show antiferromagnetism. The differences in the magnetic behaviors and magnetic magnitudes of each of the twelve couples of diradicals could be attributed to their distinctly different spin-interacting pathways. It was found that the nature of the coupler and the length of the coupling path are important factors in controlling the magnitude of the magnetic exchange coupling constant J. Specifically, smaller HOMO-LUMO (HOMO: highest occupied molecular orbital, LUMO: lowest unoccupied molecular orbital) gaps of the couplers and shorter coupler lengths, as well as shorter linking bond lengths, can attain stronger magnetic interactions. In addition, a diradical with an extensively π-conjugated structure is beneficial to spin transport and can effectively promote magnetic coupling, yielding a large |J| accordingly. That is, a larger spin polarization can give rise to a stronger magnetic interaction. The sign of J for these studied diradicals can be predicted from the spin alternation rule, the shape of the singly occupied molecular orbitals (SOMOs), and the SOMO-SOMO energy gaps of the triplet state. This study paves the way for the rational design of magnetic molecular switches. Full article
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Figure 1

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