Article
Chemistry, Inorganic & Nuclear
Miao Li, Yu-Qi Shi, Xinye Gan, Longbin Su, Jialin Liang, Huiqi Wu, Yiting You, Meizi Che, Peiyang Su, Tun Wu, Zhe Zhang, Wei Zhang, Liao-Yuan Yao, Pingshan Wang, Ting-Zheng Xie
Summary: A new type of coordination-driven host combining porphyrin and terpyridine moieties with a long cavity was designed and synthesized in this study. The host can encapsulate bisite or monosite guests through axial coordination binding of porphyrin and aromatic pi interactions of terpyridine. Characterization of the ligands and prismatic complexes was conducted using ESI-MS, TWIM-MS, NMR spectrometry, and single-crystal X-ray diffraction analysis. The encapsulation mechanism of guests was investigated through ESI-MS, NMR spectrometry, and transient absorption spectroscopy analysis. The binding constant and stability were determined by UV-Vis spectrometry and gMS2 techniques. A selectively confined condensation reaction was performed and detected by NMR spectrometry based on the prism. This study provides a new type of host that could be used for the detection of pyridyl- and amine-contained molecules and confined catalysis.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Yuki Oka, Hiroshi Masai, Jun Terao
Summary: In this study, a ligand-controlled switching method for multistate switching of catenanes controlled by complexation with added amine ligands was reported. A [3]catenane with rigid pi-system comprised of cyclic porphyrin dimers was synthesized to verify this method. The relative positions among the cyclic components of the [3]catenane could be precisely controlled by complexation with various amine ligands. Furthermore, ligand-controlled multistate switching affected the optical properties of the [3]catenanes, with emission intensity being tuned by modulating the sizes and coordination numbers of integrated amine ligands. This work demonstrates the utility of using organic ligands for structural switching of catenanes and contributes to the development of multistate switchable mechanically interlocked molecules.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(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
Polymer Science
Qiuyan Song, Kairong Zhao, Tanlong Xue, Shuai Zhao, Di Pei, Jun Nie, Yincheng Chang
Summary: Two novel supramolecular photoinitiators were developed by host-guest complexation of macrocycles with diphenyl-iodonium salt, demonstrating efficient polymerization and extending the initiating wavelength, potentially opening a new route for high-performance photoinitiator design.
Article
Chemistry, Applied
Guozheng Zhao, Wenya Liu, Fang Yuan, Jinjian Liu
Summary: Two host-guest two-dimensional (2D) MOFs based on N,N'-bis(n-hexyl)-4,4'-bipyridinium dibromide were prepared and showed photochromic properties. The electronic structures and matching rules between donors and receptors were explored using density functional theory.
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, Multidisciplinary
Yu Tian, Jie Yang, Zhenjiang Liu, Mingxue Gao, Xiaoning Li, Weilong Che, Manman Fang, Zhen Li
Summary: A new host-guest doping system was developed in this study to achieve turn-on RTP effect through co-crystallization or grinding, creating organic RTP materials with stimulus-responsive characteristics. Multistage stimulus-responsive RTP characteristics were achieved by introducing pyridine group, and anti-counterfeiting printings were realized through various methods, moving RTP materials closer to commercialization.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
O. A. Stasyuk, A. J. Stasyuk, M. Sola, A. A. Voityuk
Summary: The chemistry of hoop-shaped pi-conjugated molecules has developed significantly in recent years. In this study, a computational model of photoinduced electron transfer processes in a series of host-guest complexes of Twin1, Twin2, and Twin3 double nanohoops with C-60 fullerene is presented. The findings suggest that charge transfer from cycloparaphenylene (CPP) fragments to C-60 is energetically favorable and occurs rapidly within a sub-nanosecond time scale. The slow decay of the charge-separated state indicates the potential interest of these complexes for organic photovoltaics.
JOURNAL OF NANOSTRUCTURE IN CHEMISTRY
(2022)
Review
Chemistry, Multidisciplinary
Siamak Javanbakht, Sima Darvishi, Faeze Dorchei, Maryam Hosseini-Ghalehno, Marjan Dehghani, Malihe Pooresmaeil, Yota Suzuki, Qurat Ul Ain, Leire Ruiz Rubio, Ahmad Shaabani, Takashi Hayashita, Hassan Namazi, Abolfazl Heydari
Summary: Diabetes mellitus is a prevalent chronic health condition, and monitoring blood glucose levels is crucial in diabetes management. However, developing noninvasive, rapid, accurate, sensitive, selective, and stable systems for continuous monitoring remains a challenge. Cyclodextrins can be instrumental in addressing these challenges and improving the performance and stability of glucose monitoring systems.
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
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, Organic
Ruth Mariam Ipe, Athira Parammal, Probal Nag, Shigeki Mori, Sivaranjana Reddy Vennapusa, Sabapathi Gokulnath
Summary: We synthesized and characterized two porphyrin arrays, C6F5-PyZnDP and Mes-PyZnDP, linked by a pyrene moiety with different substituents at their meso-positions. The key precursor bis-dipyrromethane linked with a pyrene bridge was prepared. C6F5-PyZnDP was synthesized through two different routes, with one being more efficient, and both the free base and metalated diporphyrins showed bathochromically shifted absorption and intense red emission.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Sergey Titov, Vitaly G. Avakyan
Summary: The method of molecular dynamics was used to model crystal structures based on dimers and trimers of beta-cyclodextrin containing luminescent complexes. A novel technique was developed to construct these crystals. The obtained structures are stable and allow for the explanation of the observable luminescence properties. This technique is promising for the prediction of new crystal structures and obtaining important supramolecular crystals.
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, Multidisciplinary
G. George, O. A. Stasyuk, A. A. Voityuk, A. J. Stasyuk, M. Sola
Summary: Pi-conjugated organic molecules have a wide range of exciting applications in batteries, solar cells, and light-emitting diodes. Among these, antiaromatic compounds are of particular interest due to their smaller energy gap, which facilitates charge transfer. This study explores the ground and excited-state properties of two nitrogen-doped nanohoops and their complexes with C-60 fullerene, showing different behavior depending on aromaticity. The results suggest that antiaromatic compounds have a longer charge transfer state lifetime compared to aromatic compounds.
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
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
Biochemistry & Molecular Biology
Pritam Mondal, Garrett B. Tolbert, Gayan B. Wijeratne
Summary: This study investigates the low temperature reactivities of high-valent heme intermediates with nitric oxide (NO), revealing two different reaction pathways. The findings highlight the potential of high-valent heme species in catalyzing efficient NOx interconversions, shedding light on unexplored territory central to human physiology and therapeutics.
JOURNAL OF INORGANIC BIOCHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Pritam Mondal, Shanuk Rajapakse, Gayan B. Wijeratne
Summary: Recent interest in direct conversion pathways from indoles to oxindoles has shed light on various pathogenic processes in humans and highlighted the therapeutic potential of oxindoles. Heme enzymes play a crucial role in this conversion, offering promising therapeutic targets, yet a comprehensive mechanistic understanding is still needed. The development of synthetic heme models for indole monooxygenation could provide insights into drug design targeting heme enzymes and pave the way for the future development of better synthetic protocols for the generation of 2-oxindole motifs.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(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, Multidisciplinary
Pritam Mondal, Izumi Ishigami, Syun-Ru Yeh, Gayan B. Wijeratne
Summary: This study investigates the mechanism of action of mammalian nitric oxide synthase (NOS) through a NOS model system. The findings provide evidence that heme peroxo intermediates play a crucial role in the oxidation of oximes, leading to the formation of ketones and nitroxyl anions. The results are consistent with previous studies and are supported by recent enzymatic research.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
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)
Article
Chemistry, Multidisciplinary
Pritam Mondal, Izumi Ishigami, Emilie F. Gerard, Chaeeun Lim, Syun-Ru Yeh, Sam P. de Visser, Gayan B. Wijeratne
Summary: Heme superoxides are versatile metallo-intermediates in biology, facilitating a wide range of oxidation and oxygenation reactions involving O-2(g). The electronic factors of heme center modulate the feasibility of proton-coupled electron transfer (PCET) processes, influencing both thermodynamic and kinetic parameters. Understanding these electronic effects is pivotal in biological heme systems and alternative energy applications.
