Article
Chemistry, Multidisciplinary
Taeyeon Kim, Yuanning Feng, James P. O'Connor, J. Fraser Stoddart, Ryan M. Young, Michael R. Wasielewski
Summary: Designing and controlling charge transfer pathways in organic semiconductors are crucial for solar energy applications. This study investigates the photoinduced charge transfer and relaxation dynamics in host-guest complexes, and demonstrates that the charge transfer pathway can be controlled by subtle chemical modifications of the acceptor host.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Inorganic & Nuclear
Hong-Xiang Nie, Bo Zhang, Yi-Ming Liu, Mei-Hui Yu, Ze Chang
Summary: Fluorescence modulation of host-guest donor-acceptor (D-A) coordination polymer (CP) materials can be achieved through subtle structural engineering, resulting in multifarious emission properties and demonstrating great potential for fluorescence modulation.
INORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Multidisciplinary Sciences
Xiao-Ting Liu, Weijie Hua, Hong-Xiang Nie, Mingxing Chen, Ze Chang, Xian-He Bu
Summary: Thermally activated delayed fluorescence was achieved by spatially separating donor and acceptor molecules in a metal-organic framework host. The resulting material exhibited enhanced emission intensity and high photoluminescence quantum yield, which increased with temperature.
NATIONAL SCIENCE REVIEW
(2022)
Article
Nanoscience & Nanotechnology
Tu Thi Kim Cuc, Pham Quoc Nhien, Trang Manh Khang, Hao-Yu Chen, Chia-Hua Wu, Bui-Thi Buu Hue, Yaw-Kuen Li, Judy Wu, Hong-Cheu Lin
Summary: The novel supramolecular host-guest systems exhibited interesting photoluminescence properties in DMF/H2O solutions, including bifluorophoric behavior after aluminum detection. Notably, Forster resonance energy transfer processes occurred between blue-emissive TPE donors and green-emissive fluorescein acceptors, resulting in strong green emissions. These systems showed high sensitivities and selectivities toward aluminum ions with effective FRET processes, making them promising for aluminum detection applications.
ACS APPLIED MATERIALS & INTERFACES
(2021)
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, Applied
Jian-Jun Liu, Jia-Jia Fu, Teng Liu, Xianfu Shen, Fei-Xiang Cheng
Summary: The rational construction and modulation of charge-transfer based fluorescence materials in host-guest systems remains a challenge. In this study, a well-defined MOF host with electron-deficient properties was successfully used to fabricate host-guest materials with charge-transfer based fluorescence. By selecting guest molecules, the emission color can be tuned over a wide range. This work provides a hopeful strategy for the assembly of various novel charge transfer fluorescent materials.
Article
Chemistry, Multidisciplinary
Alexander Aster, Christopher Rumble, Anna-Bea Bornhof, Hsin-Hua Huang, Naomi Sakai, Tomas Solomek, Stefan Matile, Eric Vauthey
Summary: The study focuses on the charge-transfer dynamics of electron donor-acceptor dyads based on NDI chromophores, demonstrating long-lived charge separation in the triplet state can be achieved by controlling the mutual orientation of the donor-acceptor sub-units.
Article
Chemistry, Inorganic & Nuclear
Hong-Xiang Nie, Bo Zhang, Yi-Ming Liu, Mei-Hui Yu, Ze Chang
Summary: Fluorescence modulation of host-guest donor-acceptor (D-A) coordination polymer (CP) materials can be achieved through subtle structural engineering, resulting in multifarious emission properties and demonstrating great potential in achieving fluorescence modulation.
INORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Physical
Alejandro Benitz, Michael B. Thomas, Imesha de Silva, Vladimir N. Nesterov, Guido F. Verbeck, Francis D'Souza
Summary: The study investigates the photoinduced electron transfer in newly assembled dyads formed via metal-ligand axial coordination of BODIPY(Im)2 and zinc tetrapyrroles in non-coordinating o-dichlorobenzene. Results show that the electron acceptor properties of bis(styryl)BODIPY in donor-acceptor conjugates are significant, with PET being thermodynamically unfavorable in the ZnP-bearing complex but possible in ZnPc- and ZnNc-bearing complexes when selectively exciting the zinc tetrapyrrole. Efficient PET is observed in the latter two dyads based on femtosecond transient absorption studies, with spectroscopic identification of the electron transfer products.
Article
Chemistry, Physical
Zimu Wei, Sushil Sharma, Abbey M. Philip, Sanchita Sengupta, Ferdinand C. Grozema
Summary: Donor-bridge-acceptor systems based on BODIPY show potential for bio-imaging and sensing applications, with their photophysical behavior depending on solvent polarity. Factors such as donor-acceptor distance and restricted rotational motion play key roles in tuning the excited state photophysics.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2021)
Article
Chemistry, Physical
Courtney A. DelPo, Saeed-Uz-Zaman Khan, Kyu Hyung Park, Bryan Kudisch, Barry P. Rand, Gregory D. Scholes
Summary: Enhanced delocalization is beneficial for absorbing molecules in organic solar cells, and polaritons offer exceptional delocalization that can improve the efficiency of bilayer organic photovoltaics by aiding in exciton delivery to the donor-acceptor interface. The decay of polaritons in bilayer cavities shows an additional pathway through charge transfer, indicating that the charge transfer from the polariton is fast enough to outcompete decay to the ground state.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2021)
Article
Chemistry, Multidisciplinary
Han Deng, Zilong Guo, Yaxin Wang, Ke Li, Qin Zhou, Chang Ge, Zhanqiang Xu, Sota Sato, Xiaonan Ma, Zhe Sun
Summary: This study presents a modular synthetic approach for the preparation of carbon nanohoops with donor-acceptor or donor-acceptor-donor structures. The properties of these nanohoops, including host-guest complexation with fullerene, optical properties, and charge transfer dynamics, were systematically investigated. The findings revealed intriguing physical properties associated with the donor-acceptor motifs.
Article
Chemistry, Physical
Thomas P. P. Fay, David T. T. Limmer
Summary: In this paper, a physically motivated framework is proposed to describe spin-selective recombination processes in chiral systems. Spin-selective reaction operators for recombination reactions of donor-bridge-acceptor molecules are derived based on chirality and spin-orbit coupling. It is found that spin polarization selectivity only arises in hopping-mediated electron transfer. The framework presented here can be extended to describe spin-selective recombination processes in more complex systems.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Fenghua Zhang, Yujiao Yan, Mandi Li, Tao Lin, Denghui Xu, Xiong Li
Summary: In this study, a nonfullerene acceptor was introduced into the active layer of indoor photovoltaic devices, creating a ternary system specifically designed for indoor light conditions. By optimizing the acceptor ratio, a photovoltaic device suitable for low light intensity and commonly used indoor light sources was prepared, achieving significantly higher efficiency compared to traditional binary devices.
ACS APPLIED ENERGY MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Rebecca L. Spicer, Helen M. O'Connor, Yael Ben-Tal, Hang Zhou, Patrick J. Boaler, Fraser C. Milne, Euan K. Brechin, Guy. C. Lloyd-Jones, Paul J. Lusby
Summary: Coordination cage catalysis is a strategy that utilizes a cage as an exogenous catalyst, rather than relying on the endogenous binding of substrates. The cage alters the properties of a cofactor guest, which then transfers reactivity to the bulk-phase to catalyze reactions.
Article
Chemistry, Multidisciplinary
Amit Kumar, Sarnali Sanfui, Giuseppe Sciortino, Jean-Didier Marechal, Eugenio Garribba, Sankar Prasad Rath
CHEMISTRY-A EUROPEAN JOURNAL
(2020)
Article
Chemistry, Inorganic & Nuclear
Bapan Saha, Sk Asif Ikbal, Sankar Prasad Rath
INORGANIC CHEMISTRY
(2020)
Article
Chemistry, Multidisciplinary
Akhil Kumar Singh, Sankar Prasad Rath
CHEMISTRY-A EUROPEAN JOURNAL
(2020)
Article
Chemistry, Multidisciplinary
Amit Kumar, Mohammad Usman, Deepannita Samanta, Sankar Prasad Rath
Summary: The study indicates that there are significant differences in spectral characteristics and oxidative properties between copper(II)-iron(III) and copper(II)-manganese(III) heterobimetallic porphyrin dimers compared to their corresponding homobimetallic analogs. Analysis of various spectroscopic studies reveals that ring-centered oxidation occurs during the 2e-oxidation process of the heterobimetallic complexes.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Inorganic & Nuclear
Firoz Shah Tuglak Khan, Deepannita Samanta, Dolly Chandel, Syed Jehanger Shah, Sankar Prasad Rath
Summary: Diheme cytochromes play significant roles in enzymatic catalysis and electron transfer, with unique coordination structures and low-spin states that can be influenced by the ligands, leading to changes in the redox potential.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Akhil Kumar Singh, Mohammad Usman, Sabyasachi Sarkar, Giuseppe Sciortino, Devesh Kumar, Eugenio Garribba, Sankar Prasad Rath
Summary: Three different oxidovanadium(IV) porphyrin dimers were synthesized with different spatial arrangements of the two rings by changing the bridge between the porphyrin macrocycles. The electronic and magnetic properties of these dimers were characterized using various analytical techniques, revealing unusual ferromagnetic interactions between the vanadium(IV) and porphyrin pi-cation radicals.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Bapan Saha, Dolly Chandel, Sankar Prasad Rath
Summary: The rationalization for chirality transfer mechanism in supramolecular host-guest assemblies has been reported for the first time. The cyclic dimer displays a large bisignate CD couplet, while the monomeric complexes exhibit negligible CD intensity. Crystallographic characterizations demonstrate that the strong intermolecular H bonding in cyclic dimers is responsible for their stability over the linear chain.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Sarnali Sanfui, Mohammad Usman, Sabyasachi Sarkar, Subhadip Pramanik, Eugenio Garribba, Sankar Prasad Rath
Summary: This study reveals the crucial role of the nature of the bridge in long-range electronic communication through the construction of a cobalt porphyrin dimer.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Younis Ahmad Pandit, Syed Jehanger Shah, Mohammad Usman, Sabyasachi Sarkar, Eugenio Garribba, Sankar Prasad Rath
Summary: Dinickel(II) and dicopper(II) porphyrin dimers with a long unconjugated dipyrrole bridge were synthesized. The bridge can be oxidized to form a fully pi-conjugated structure, leading to one- and two-electron-oxidized species with long-range charge/radical delocalization. This results in intense absorptions in the near-infrared region and electron paramagnetic resonance signals of a triplet state. Despite the large physical separation, the two metal centers behave as a single unit and efficiently share electrons between them.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Sabyasachi Sarkar, Pallavi Sarkar, Deepannita Samanta, Swapan K. Pati, Sankar Prasad Rath
Summary: A dual iron porphyrin catalyst has been developed for the oxa-Diels-Alder reaction of aldehydes with 1,3-dienes. This catalyst shows high functional group tolerance and the metal ion plays a key role in the reaction mechanism with the counteranions. The use of this catalyst allows for excellent yields with lower catalyst loading.
Article
Chemistry, Inorganic & Nuclear
Younis Ahmad Pandit, Mohammad Usman, Anindya Sarkar, Syed Jehanger Shah, Sankar Prasad Rath
Summary: In this study, a dinickel(ii)porphyrin dimer was used with a redox-active pyrrole-moiety placed between two Ni(ii)porphyrin centers. The two metal centers were physically separated with almost no communication between them. Upon oxidation, the dimer converted into an indolizinium-fused chlorin-porphyrin heterodimer. Furthermore, oxidations of the dimer using certain oxidants resulted in the formation of a dication diradical complex.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Syed Jehanger Shah, Younis Ahmad Pandit, Eugenio Garribba, Masatoshi Ishida, Sankar Prasad Rath
Summary: We report an unexpected rearrangement that leads to the formation of stable dinickel/dicopper chlorin-porphyrin dication diradical heterodimers. The bridge in these diradicals undergoes a nucleophilic attack at the beta-carbon of the porphyrin pi-cation radical, initiating the rearrangement process.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Dipankar Sahoo, Rakesh Mazumdar, Subhadip Pramanik, Sayantani Banerjee, Ranjan Patra, Sankar Prasad Rath
Summary: This study reports a series of five- and six-coordinated Fe-porphyrins and investigates the effects of non-covalent interactions on the out-of-plane displacement and spin states of iron, as well as the orientation of axial ligands. The results show that weak hydrogen bonding interactions result in elongation of Fe-O bonds and stabilization of the mixed spin state of iron. Additionally, the movement of axial ligands is restricted by strong pi-interactions. This study provides important insights into the functioning of hemoproteins such as hemoglobin.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Avinash Dhamija, Dolly Chandel, Sankar Prasad Rath
Summary: Here, we demonstrate the chiral guest-induced contraction, extension, and twisting motions in a flexible and nano-sized achiral trizinc(ii)porphyrin trimer host. The formation of 1:1, 1:2, and 1:4 host-guest supramolecular complexes leads to the induction, inversion, and amplification, as well as reduction, of porphyrin CD responses in a single molecular framework. The opposite CD signs observed in R and S substrates suggest that chirality is solely determined by the stereographic projection of the chiral center. Additionally, the trisignate CD signals generated by long-range electronic communications between the three porphyrin rings provide further insights into molecular structures.
Article
Chemistry, Inorganic & Nuclear
Dolly Chandel, Chandrani Pal, Bapan Saha, Sk Asif Ikbal, Sankar Prasad Rath
Summary: A highly flexible pyrrole-bridged Zn(ii)porphyrin dimer has been used as an efficient host to accurately determine the absolute configuration of a large number of chiral amino alcohols and 1,2-diols. The addition of substrates leads to the formation of 1:1 and 1:2 host-guest complexes, with the endo-endo conformation being stabilized by strong interligand H-bonds. Spectroscopic and structural studies have provided a systematic understanding of the optical activity and allowed for the determination of absolute stereochemistry in a variety of chiral substrates.
DALTON TRANSACTIONS
(2022)