Article
Chemistry, Applied
Xiaoyu Zhao, Ivan Kurganskii, Ayhan Elmali, Jianzhang Zhao, Ahmet Karatay, Gloria Mazzone, Matvey Fedin
Summary: A series of compact coumarin-anthracene donor-acceptor dyads were synthesized to investigate the relationship between molecular configuration, electronic coupling, and intersystem crossing (ISC) efficiency. The results showed that the orthogonal geometry of the dyads was beneficial to the spin-orbit charge transfer ISC (SOCT-ISC) mechanism. Singlet oxygen quantum yields were solvent polarity-dependent, and the orthogonal dyads exhibited higher yields compared to the coplanar dyad. Transient absorption spectra revealed different localized and delocalized triplet states in the dyads, with varied lifetimes. Time-resolved electron paramagnetic resonance (TREPR) spectra confirmed the involvement of the SOCT-ISC mechanism in orthogonal dyads, while both SOCT-ISC and spin-orbit ISC (SO-ISC) mechanisms contributed to the triplet state formation in the coplanar dyad. The electron spin polarization (ESP) pattern of the triplet states depended on not only the molecular geometry but also the electron donor and acceptor structure.
Article
Chemistry, Multidisciplinary
Maximilian Maylaender, Theresia Quintes, Michael Franz, Xavier Allonas, Andreas Vargas Jentzsch, Sabine Richert
Summary: Photogenerated organic triplet-doublet systems have attracted increasing attention in molecular spintronics due to their versatility and suitability for technological applications. The formation of chromophore triplet states and subsequent quartet states depends on the enhanced intersystem crossing (EISC) and exchange interaction J(TR). Factors influencing the EISC process and quartet state formation were studied using a series of BODIPY-nitroxide dyads, suggesting that dipolar interactions mediate triplet formation and the absolute magnitude of J(TR) affects quartet state formation.
Article
Biochemistry & Molecular Biology
Wenhui Zhu, Yanran Wu, Yiyan Zhang, Andrey A. Sukhanov, Yuqi Chu, Xue Zhang, Jianzhang Zhao, Violeta K. Voronkova
Summary: We synthesized a rhodamine-TEMPO chromophore-radical dyad (RB-TEMPO) to investigate the radical enhanced intersystem crossing (REISC). The covalent connection between the visible light-harvesting chromophore rhodamine and the nitroxide radical TEMPO was established through a C-N bond. The fluorescence of the rhodamine moiety is effectively quenched in RB-TEMPO, attributed to the intramolecular electron spin-spin interaction between the nitroxide radical and the photoexcited rhodamine chromophore. Nanosecond transient absorption spectra confirmed the occurrence of REISC in RB-TEMPO, with the detection of the rhodamine chromophore triplet excited state. The application of RB-TEMPO as a photoinitiator for the photopolymerization of PETA was explored.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Chemistry, Physical
Muhammad Imran, Maria Taddei, Andrey A. Sukhanov, Laura Bussotti, Wenjun Ni, Paolo Foggi, Gagik G. Gurzadyan, Jianzhang Zhao, Mariangela Di Donato, Violeta K. Voronkova
Summary: Attaching stable radicals to organic chromophores is an effective method to enhance the intersystem crossing (ISC) of the chromophores. The study investigated the effect of the radical on the photophysical properties of perylene and observed strong fluorescence quenching due to radical enhanced ISC. The interaction between the radical and the chromophore was found to be ferromagnetic based on DFT computations, with a calculated energy value of 0.05 to 0.10 eV.
Article
Chemistry, Multidisciplinary
Qi Ou, Yihan Shao, Zhigang Shuai
Summary: This study proposes a mechanism for promoting reverse intersystem crossing through light-matter coupling, which can broaden the scope of molecular design and facilitate the development of highly efficient cavity-promoted light-emitting materials.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Physical
Alexander J. Gillett, Anton Pershin, Raj Pandya, Sascha Feldmann, Alexander J. Sneyd, Antonios M. Alvertis, Emrys W. Evans, Tudor H. Thomas, Lin-Song Cui, Bluebell H. Drummond, Gregory D. Scholes, Yoann Olivier, Akshay Rao, Richard H. Friend, David Beljonne
Summary: Thermally activated delayed fluorescence (TADF) materials are influenced by the dielectric environment, especially in materials with higher dipole moments. Environmental reorganization after excitation can decrease the activation energy for reverse intersystem crossing, leading to an increased rate of reverse intersystem crossing.
Article
Chemistry, Multidisciplinary
Maximilian Maylaender, Oliver Nolden, Michael Franz, Su Chen, Laura Bancroft, Yunfan Qiu, Michael R. Wasielewski, Peter Gilch, Sabine Richert
Summary: In this study, radical-enhanced intersystem crossing (EISC) was used to successfully generate the PDI triplet state, and strong magnetic exchange coupling between the PDI triplet state and TEMPO was demonstrated through femtosecond UV-vis transient absorption and transient electron paramagnetic resonance spectroscopies. Significant differences were observed in the deactivation rate constants of the S-1 state and triplet yields for compounds bearing PDI moieties with different core substitution patterns.
Article
Chemistry, Multidisciplinary
Noreen Rehmat, Ivan Kurganskii, Zafar Mahmood, Qing Lin Guan, Jianzhang Zhao, Yong Heng Xing, Gagik G. Gurzadyan, Matvey Fedin
Summary: The study investigated the impact of spin-orbit charge transfer intersystem crossing on PBI-AN donor-acceptor dyads/triad, revealing that molecular conformation, electronic coupling, and dihedral angle between donor and acceptor significantly affect photophysical properties. The dyad PBI-9-AN with orthogonal geometry showed low ground-state coupling and efficient intersystem crossing, while the more coplanar PBI-2-AN exhibited weaker performance in these aspects.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Xi Chen, Noreen Rehmat, Ivan V. Kurganskii, Partha Maity, Ayhan Elmali, Jianzhang Zhao, Ahmet Karatay, Omar F. Mohammed, Matvey V. Fedin
Summary: Bodipy (BDP)-perylenebisimide (PBI) donor-acceptor dyads/triad were synthesized to investigate the spin-orbit charge-transfer intersystem crossing (SOCT-ISC). Different quantum yields of singlet oxygen were observed for the dyads/triad, and various processes including FRET, CS, CR, and TTET were observed in the excited state dynamics. Time-resolved electron paramagnetic resonance spectroscopy revealed the involvement of both radical pair ISC and SOCT-ISC in the intersystem crossing. The triad BDP-PBI-2 showed an unusual electron spin polarization pattern of (e, e, e, e, e, e) in the triplet state formed via the RP ISC mechanism.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Physical
Bin Zhang, Zhigang Shuai
Summary: Through the investigation of the reverse intersystem crossing process in cavity devices, we found that changing the detuning energy can significantly increase the rate of this process. At the same time, the incident angle and doping concentration also affect the rate. This theory provides a solid foundation for the design of highly efficient cavity-promoted light-emitting materials.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Chemistry, Multidisciplinary
Kepeng Chen, Ivan V. Kurganskii, Xue Zhang, Ayhan Elmali, Jianzhang Zhao, Ahmet Karatay, Matvey V. Fedin
Summary: Compact electron donor-acceptor dyads of anthracene-naphthalimide (An-NI) were prepared with varying orientation and distance between the subunits by direct connection or with an intervening phenyl linker. Efficient spin-orbit charge transfer was observed for both directly connected dyads and those with an intervening phenyl linker, with implications for photochemical reactions.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Multidisciplinary Sciences
Yi Yu, Suman Mallick, Mao Wang, Karl Borjesson
Summary: Strong light-matter coupling can challenge traditional chemistry rules, leading to the inversion of singlet and triplet excited states and enabling higher quantum efficiency. Manipulating energy flow in molecular systems through strong light-matter coupling may promote the development of organic optoelectronics devices.
NATURE COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Arpita Mukherjee, Johannes Feist, Karl Borjesson
Summary: Strong interactions between excitons and photons lead to the formation of exciton-polaritons. The relaxation of polaritonic states enables a new kind of energy transfer event. The rate of intersystem crossing from the polariton to the triplet states depends on the energy alignment of the excited polaritonic states. In the strong coupling regime, the rate of intersystem crossing can be substantially enhanced, which has potential applications in molecular photophysics/chemistry and organic electronics.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Arpita Mukherjee, Johannes Feist, Karl Borjesson
Summary: Strong interactions between excitons and photons lead to the formation of exciton-polaritons, which possess completely different properties compared to their constituents. The rate of intersystem crossing from the polariton to the triplet states depends on the energy alignment of the excited polaritonic states. In the strong coupling regime, the rate of intersystem crossing can be substantially enhanced to the point where it approaches the rate of the radiative decay of the polariton.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Huaiman Cao, Andrey A. Sukhanov, Marcel M. Bakirov, Yuri E. Kandrashkin, Jianzhang Zhao, Violeta K. Voronkova
Summary: Two Bodipy dimers were prepared, and it was found that the triplet excited state of the first dimer depopulates fast to the ground state, while the metastable triplet state is well-detected in the second dimer. With two iodine atoms attached, BDP-BDP-I2 exhibited a high singlet oxygen quantum yield and long intrinsic triplet state lifetime, similar to diiodoBodipy monomer. Phosphorescence experiments showed that the T1-state of BDP-BDP-I2 predominantly localizes on the diiodo Bodipy subunit and a little on the diphenyl Bodipy subunit. The presence of energy and electron transfer pathways between the two moieties of the studied dimers was implied by the observed properties.
JOURNAL OF PHYSICAL CHEMISTRY C
(2022)
Review
Chemistry, Multidisciplinary
Xi Chen, Xue Zhang, Xiao Xiao, Zhijia Wang, Jianzhang Zhao
Summary: Charge transfer is crucial in molecular electron donor-acceptor systems for artificial photosynthesis, photocatalysis, photovoltaics, and fundamental photochemistry. We summarized recent developments in the study of charge transfer and discussed its application in thermally activated delayed fluorescence (TADF) emitters.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Omar Elkhatib, Yun Xie, Abdelhalim Mohamed, Maziar Arshadi, Mohammad Piri, Lamia Goual
Summary: In this study, the in situ change in oil flow behavior inside propped fractures due to wettability alteration of proppant grains and fracture surfaces was thoroughly investigated. The experiments showed that proppant wettability changed toward an intermediate-wet state while that of fracture surfaces became strongly oil-wet during the initial production. Chemical treatment of the proppant and surfactant injection had an impact on wettability, resulting in a smaller fracture oil layer. Re-introducing oil into the fracture instantaneously re-instated the initial wettability state of proppant grains. The study revealed the importance of monitoring the wettability of the proppant pack for enhancing oil production through hydraulic fractures.
Article
Chemistry, Multidisciplinary
Haiqing Wang, Andrey A. Sukhanov, Alessandro Iagatti, Laura Bussotti, Xiaoyu Zhao, Jianzhang Zhao, Violeta K. Voronkova, Mariangela Di Donato
Summary: To obtain long-lived charge separated (CS) states in electron donor-acceptor dyads, a series of AQ-PTZ dyads with adamantane as the linker were synthesized. UV-vis absorption spectra showed no electronic interaction between AQ and PTZ units at the ground state, but CT emission bands were observed. Nanosecond transient absorption showed the population of (3)AQ and formation of (CS)-C-3 states in different solvents. Similarly, femtosecond transient absorption spectra demonstrated the formation of (3)AQ and (CS)-C-3 states with varying lifetimes. Time-resolved electron paramagnetic resonance (TREPR) spectra revealed the presence of radical ion pairs in AQ-PTZ and AQ-PTZ-M, while only (3)AQ state was observed in dyads with the oxidized PTZ unit.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Applied
Xiaoyu Zhao, Ivan Kurganskii, Ayhan Elmali, Jianzhang Zhao, Ahmet Karatay, Gloria Mazzone, Matvey Fedin
Summary: A series of compact coumarin-anthracene donor-acceptor dyads were synthesized to investigate the relationship between molecular configuration, electronic coupling, and intersystem crossing (ISC) efficiency. The results showed that the orthogonal geometry of the dyads was beneficial to the spin-orbit charge transfer ISC (SOCT-ISC) mechanism. Singlet oxygen quantum yields were solvent polarity-dependent, and the orthogonal dyads exhibited higher yields compared to the coplanar dyad. Transient absorption spectra revealed different localized and delocalized triplet states in the dyads, with varied lifetimes. Time-resolved electron paramagnetic resonance (TREPR) spectra confirmed the involvement of the SOCT-ISC mechanism in orthogonal dyads, while both SOCT-ISC and spin-orbit ISC (SO-ISC) mechanisms contributed to the triplet state formation in the coplanar dyad. The electron spin polarization (ESP) pattern of the triplet states depended on not only the molecular geometry but also the electron donor and acceptor structure.
Article
Chemistry, Inorganic & Nuclear
Kaiyue Ye, Peili Wang, Minjie Li, Yuqi Hou, Jianzhang Zhao, Yan Wan
Summary: We synthesized a N boolean AND N Pt(II) bisacetylide complex with strong absorption of visible light (molar absorption coefficients epsilon=6.7x10(4) M-1 cm(-1) at 570 nm) and high singlet oxygen quantum yield (phi(Delta) = 78% ). The complex exhibits an intersystem crossing (ISC) of 81.8 ps and a triplet excited state lifetime of 7.6 μs. Density functional theory (DFT) calculations revealed that the S-1 and T-1 states are mainly localized on the perylenemonoimide (PMI) ligands, with noticeable involvement of the Pt(II) center. The complex acts as a triplet photosensitizer to generate delayed fluorescence with perylenebisimide (PBI) via triplet-triplet energy transfer (TTET) and triplet-triplet annihilation (TTA), resulting in a delayed fluorescence lifetime of 52.5 μs under the experimental conditions.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Editorial Material
Chemistry, Inorganic & Nuclear
Xinwen Guo, Jianzhang Zhao
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Muhammad Imran, Huaiman Cao, Jianzhang Zhao, Gloria Mazzone
Summary: In this study, the photophysical properties of a heavy atom-free organic chromophore with near-IR absorption and intersystem crossing ability were investigated. The compound consisting of naphthalenediimide and pentacyclic1,8-diazabicyclo[5.4.0]-undec-7-ene showed strong charge-transfer absorption in the near-IR region, but had poor intersystem crossing efficiency despite its twisted molecular structure.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Physical
Zhibin Yu, Andrey A. Sukhanov, Xiao Xiao, Alessandro Iagatti, Sandra Doria, Valeria Butera, Jianzhang Zhao, Violeta K. Voronkova, Mariangela Di Donato, Gloria Mazzone
Summary: A series of PTZ-AQ dyads with different linkers were prepared to study the relationship between molecular structures and charge transfer and intersystem crossing. The results showed that conformation restriction on the linker led to the observation of thermally activated delayed fluorescence. The presence of charge-separated and locally excited states with similar energy was found to be essential for the occurrence of TADF.
JOURNAL OF PHYSICAL CHEMISTRY B
(2023)
Review
Biochemistry & Molecular Biology
Xiao Xiao, Xiaoyu Zhao, Xi Chen, Jianzhang Zhao
Summary: Photodynamic therapy (PDT) is a promising treatment for cancer due to its low toxicity, non-drug-resistant nature, and targeting capability. However, the current PDT reagents face challenges in their synthesis, purification, and derivatization. This article summarizes recent developments in heavy atom-free triplet photosensitizers (PSs) from a photophysical perspective, including methods such as radical-enhanced intersystem crossing (REISC), twisted pi-conjugation system-induced ISC, and the use of fullerene C-60 as an electron spin converter. The potential application of these compounds in PDT is also briefly discussed.
Article
Chemistry, Organic
Liyuan Cao, Xi Liu, Xue Zhang, Jianzhang Zhao, Fabiao Yu, Yan Wan
Summary: A series of electron donor-acceptor dyads were prepared to study the TADF properties. The photophysical properties of the dyads were tuned by changing the electron-donating and the electron-withdrawing capability of the PTZ and NI moieties. TADF was observed for the dyads containing the native PTZ unit, and the prompt and delayed fluorescence lifetimes changed with different aryl substituents on the imide part.
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Xi Chen, Noreen Rehmat, Ivan V. Kurganskii, Partha Maity, Ayhan Elmali, Jianzhang Zhao, Ahmet Karatay, Omar F. Mohammed, Matvey V. Fedin
Summary: Bodipy (BDP)-perylenebisimide (PBI) donor-acceptor dyads/triad were synthesized to investigate the spin-orbit charge-transfer intersystem crossing (SOCT-ISC). Different quantum yields of singlet oxygen were observed for the dyads/triad, and various processes including FRET, CS, CR, and TTET were observed in the excited state dynamics. Time-resolved electron paramagnetic resonance spectroscopy revealed the involvement of both radical pair ISC and SOCT-ISC in the intersystem crossing. The triad BDP-PBI-2 showed an unusual electron spin polarization pattern of (e, e, e, e, e, e) in the triplet state formed via the RP ISC mechanism.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Physical
Xiao Xiao, Yuxin Yan, Andrey A. Sukhanov, Sandra Doria, Alessandro Iagatti, Laura Bussotti, Jianzhang Zhao, Mariangela Di Donato, Violeta K. Voronkova
Summary: In this study, a series of dyads based on naphthalimide (NI) and phenothiazine (PTZ) were prepared to prolong the charge separation (CS) state lifetime by exploiting the electron spin control effect. The electron coupling magnitude was tuned by conformational restriction exerted by the methyl groups on the phenyl linker. Unlike previously reported analogues, these dyads exhibited a significant CS emission band and thermally activated delayed fluorescence (TADF). Nanosecond transient absorption spectroscopy revealed different states in different solvents, confirming the spin-vibronic coupling theoretical model. Femtosecond transient absorption spectroscopy indicated charge separation in both nonpolar and polar solvents, with varying time constants. Time-resolved electron paramagnetic resonance (TREPR) spectra supported the existence of (NI)-N-3* and CS states in the dyads upon photoexcitation. The electron spin-spin dipole interaction magnitude suggested the contribution of electron spin control to the long CS-state lifetime.
JOURNAL OF PHYSICAL CHEMISTRY B
(2023)
Article
Chemistry, Multidisciplinary
Xue Zhang, Andrey A. Sukhanov, Xi Liu, Maria Taddei, Jianzhang Zhao, Anthony Harriman, Violeta K. Voronkova, Yan Wan, Bernhard Dick, Mariangela Di Donato
Summary: To investigate the relationship between twisted pi-conjugation framework and efficacy of intersystem crossing (ISC), a study on a distorted N,N,O,O-boron-chelated Bodipy derivative was conducted. Surprisingly, this chromophore exhibited high fluorescence and inefficient ISC. It was attributed to a large singlet-triplet energy gap. The introduction of an anthryl unit increased ISC yield, possibly due to the presence of a T2 state with similar energy to the S1 state.
Article
Chemistry, Multidisciplinary
Jieyu Tang, Xi Liu, Xue Zhang, Jianzhang Zhao, Yan Wan
Summary: In this study, the effect of the relative energy order of charge transfer (CT) state and locally excited (3LE) state on the photophysical properties of electron donor-acceptor dyads, specifically their thermally activated delayed fluorescence (TADF) property, was investigated. It was found that the presence of the 3LE state sharing a similar energy with the CT states is critical for the occurrence of TADF.
NEW JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Physical
Xiao Xiao, Tong Mu, Andrey A. Sukhanov, Yihang Zhou, Peiran Yu, Fabiao Yu, Ayhan Elmali, Jianzhang Zhao, Ahmet Karatay, Violeta K. Voronkova
Summary: A long-lived charge transfer state was obtained in a compact rhodamine-thionated naphthalimide electron donor-acceptor dyad through electron spin control, and the solvent polarity affected its energy level and lifetime.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)