Review
Chemistry, Organic
Shengmei Wu, Lizhi Gai, Zhikuan Zhou, Hua Lu
Summary: This review highlights the recent progress of zig-zag-fused BODIPYs, focusing on their synthetic approaches, spectroscopic characteristics of intriguing structures, and their multiple applications in biomedicine and material science.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Issei Nishimura, Tomohiro Higashino, Hiroshi Imahori
Summary: The thiophene-fused porphyrin dimers displayed strong electronic communication as effective pi-extended helical chromophores, with red-shifted absorption extending up to 1100 nm. Their racemic inversion barriers can be modulated by central metal ions.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Kazuya Miyagawa, Ichiro Hisaki, Norihito Fukui, Hiroshi Shinokubo
Summary: 3,5-Ethenoporphyrin and its analogues, with unique structure on the ethene unit, provide a new approach towards dynamic redox-active materials. The formation of the cyclobutane ring shows significant stability, holding potential applications in the field of organic material design.
Article
Chemistry, Inorganic & Nuclear
Inderpal Yadav, Muniappan Sankar
Summary: Four new beta-functionalized cobalt corroles were synthesized and characterized. These compounds exhibited panchromatic and near-infrared absorption, enhanced molar absorptivity, and unique spectral features. The appended groups also demonstrated potential applications in electrocatalysis and nonlinear optics.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Akito Nakai, Tomoki Yoneda, Takayuki Tanaka, Atsuhiro Osuka
Summary: Pd-II complexation induced meso-carbon extrusion of N-fused [22]pentaphyrin(1.1.1.1.1), resulting in the formation of 22 pi aromatic compounds [22]sapphyrin. Oxidation of the compound yielded directly C-N linked dimer.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Inorganic & Nuclear
Anil Reddy Marri, Bogdan Marekha, Thomas Penfold, Stefan Haacke, Philippe C. Gros
Summary: A study on iron(ii) complexes with pyridyl N-heterocyclic carbene ligands, using both experimental and theoretical approaches, has been conducted. The focus of this study is to investigate the influence of extending the ligands with different numbers of thiophenes. The results show that these thiophene moieties induce a mixture of the occupied t(2g) and pi HOMO orbitals, leading to a red-shift of the (MLCT)-M-1 transition and an increase in the molar extinction coefficient. Additionally, the introduction of thiophenes prolongs the excited state lifetimes, which can be qualitatively explained by a reduction in the (MLCT)-M-3-(MC)-M-3 energy gap.
INORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Chengyu Liu, Daan van den Bos, Barthold den Hartog, Dennis van der Meij, Ashok Ramakrishnan, Sylvestre Bonnet
Summary: Finding photostable first-row transition metal-based molecular systems for photocatalytic water oxidation is a key step towards sustainable solar fuel production. Nickel(II) hydrophilic porphyrins have been discovered as molecular catalysts for this purpose, showing high turnover frequencies but with issues in the catalytic activity of the electron-poorest Ni-porphyrin.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Mari Irikura, Yusuke Tamaki, Osamu Ishitani
Summary: The heteroleptic osmium(ii) complex demonstrated the ability to absorb the full wavelength range of visible light and function as a panchromatic redox photosensitizer. It was able to catalyze the reduction of CO2 to HCOOH under light irradiation, showcasing its potential for diverse photocatalytic applications.
Article
Chemistry, Organic
Qingjie Pan, Li Liu, Ying Pan, Mingbo Zhou, Ling Xu, Yutao Rao, Bangshao Yin, Jianxin Song, Atsuhiro Osuka
Summary: Fused dimers with red-shifted absorption bands were obtained through simple chemical reactions and showed different structures.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Physical
Bikram Gurung, Sajan Pradhan, Debesh Sharma, Deshaj Bhujel, Siddhant Basel, Shivanand Chettri, Sagarmani Rasaily, Anand Pariyar, Sudarsan Tamang
Summary: This study reports the synthesis of highly stable CsPbBr(3)QD based photocatalysts using dibromoisocyanuric acid (DBI) as a non-toxic bromide precursor. The QDs were used as a visible light photocatalyst for the intramolecular cyclisation reaction, resulting in the formation of enantiopure bioactive heterocycles with high yields. The reaction is simple, scalable, operates at room temperature, and exhibits a high catalytic efficiency and apparent quantum efficiency.
CATALYSIS SCIENCE & TECHNOLOGY
(2022)
Article
Chemistry, Organic
Bharti Yadav, Prosenjit Isar, Mangalampalli Ravikanth
Summary: A variety of fused benzo-benzisapphyrins were synthesized by reacting benzodipyrrole-derived diol and para-benzitripyrrane in the presence of TFA and DDQ. The structure and properties of the fused sapphyrins were characterized using HRMS, 1D and 2D NMR spectroscopy.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Jibin Alex Abraham, Shigeki Mori, Masatoshi Ishida, Hiroyuki Furuta
Summary: NFP can form a ring-opened iridium complex and a cod-isomerized iridium complex under oxidative and inert conditions, respectively.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Mariachiara Trapani, Maria Angela Castriciano, Elisabetta Collini, Giovanni Bella, Massimiliano Cordaro
Summary: The study presents a method for preparing supramolecular BODIPY dimers capable of forming triple hydrogen bonds through interactions. Computational and photophysical properties of dimers and monomers show variations in different solvent media. Investigating the effects of interaction geometry on the stability of hydrogen-bonded systems is also emphasized.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Huan Wang, Mahbod Morshedi, Mahesh S. Kodikara, Yovan de Coene, Koen Clays, Chi Zhang, Mark G. Humphrey
Summary: Metal-alkynyl donor/nitro acceptor-functionalized porphyrins are promising candidates for nonlinear optical (NLO) applications, exhibiting exceptional properties such as record quadratic optical nonlinearity, remarkable two-photon absorption, and outstanding three-photon absorption, as well as being the first porphyrins to exhibit four-photon absorption. The absorption peaks for two-, three-, and four-photon absorption correspond to multiples of linear absorption bands associated with porphyrin-localized pi*<-pi transitions and donor-porphyrin to porphyrin-acceptor charge transfer transitions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Qizhao Li, Masatoshi Ishida, Chengjie Li, Glib Baryshnikov, Feng Sha, Bin Zhu, Xinyan Wu, Hans Agren, Hiroyuki Furuta, Yongshu Xie
Summary: This study reports the synthesis of novel dimeric porphyrin analogs through a one-pot oxidation reaction. These compounds exhibit tunable conformations and unique properties, making them potential candidates for organic optoelectronic materials.
Article
Chemistry, Applied
Ekaterina S. Shremzer, Daria A. Polivanovskaia, Kirill P. Birin, Yulia G. Gorbunova, Aslan Yu Tsivadze
Summary: A series of pi-expanded pyrazinoporphyrins were synthesized and tested as sensitizers for the photocatalytic oxidation of sulfides. The structures of the compounds were confirmed by NMR analysis. The absorption bands of the compounds showed a gradual bathochromic shift with the expansion of the macrocycle aromatic system. The photocatalytic activity of the pi-expanded pyrazinoporphyrins increased with the expansion of the pi-system, achieving high conversion and selectivity with low catalyst loading.
Article
Biochemistry & Molecular Biology
Evgeniya A. Safonova, Filipp M. Kolomeychuk, Daniil A. Gvozdev, Aslan Yu. Tsivadze, Yulia G. Gorbunova
Summary: This study demonstrated, for the first time, the efficient singlet oxygen (SO) generation ability of P(V) phthalocyanines (Pcs), specifically unsubstituted and alpha- and beta-octabutoxy-substituted P(V)Pcs. The photophysical and photochemical properties of these compounds can be fine-tuned by varying the substituents in the Pc ring and P(V) axial ligands. The introduction of electron-donating butoxy groups, especially in the alpha-position, increased the photostability of P(V)Pcs. Furthermore, the photostability depended on the nature of axial ligands, with higher stability observed in the order of OPh < OMe < OH for beta-BuO-substituted P(V)Pcs.
Article
Chemistry, Analytical
Elizaveta Kozhina, Sergey Bedin, Alexander Martynov, Stepan Andreev, Alexey Piryazev, Yuri Grigoriev, Yulia Gorbunova, Andrey Naumov
Summary: The most relevant technique for portable (on-chip) sensors is Surface Enhanced Raman Scattering (SERS). This strategy fails for large molecules and nano-objects, whose SERS spectra are irreproducible at low concentrations. SERS-mapping is proposed as a solution to this problem. The distributions of SERS parameters for small (malachite green (MG)) and large (phthalocyanine, H2Pc*) molecules are analyzed, showing negligible fluctuations for small MG and noticeable distribution for large H2Pc* due to random arrangement of molecules with respect to hot spot areas.
Article
Chemistry, Analytical
Irina I. Shepeleva, Kirill P. Birin, Daria A. Polivanovskaia, Alexander G. Martynov, Alexander V. Shokurov, Aslan Yu. Tsivadze, Sofiya L. Selektor, Yulia G. Gorbunova
Summary: Detection of nitroaromatic compounds (NAC) is important due to their hazardous nature. A new pyrene-imidazoporphyrin dyad is reported to exhibit an unusual 'turn-on' response to NAC with the appearance of a new band attributed to exciplex emission. The dyad's porphyrin backbone allows for ratiometric detection using its own fluorescence as an internal reference signal. Association constants of the dyad are reported to be in the order of 10(4) M-1.
Article
Chemistry, Inorganic & Nuclear
Maxim A. Faraonov, Alexander G. Martynov, Marina A. Polovkova, Salavat S. Khasanov, Yulia G. Gorbunova, Aslan Yu. Tsivadze, Akihiro Otsuka, Hideki Yamochi, Hiroshi Kitagawa, Dmitri V. Konarev
Summary: Two forms of binuclear heteroleptic triple-decker terbium(III) phthalocyaninate have been synthesized, including a solvent-free powder and a crystal solvate. The crystal structure shows different Tb-N distances and a twist angle between the outer and inner decks. The magnetic properties reveal single-molecule magnet behavior in both forms, but with different dynamic characteristics.
Article
Chemistry, Inorganic & Nuclear
Alexander G. Martynov, Anna E. Ovchenkova, Pavel V. Dorovatovskii, Marina A. Polovkova, Anna E. Ovchenkova, Kirill P. Birin, Gayane A. Kirakosyan, Yulia G. Gorbunova, Aslan Yu. Tsivadze
Summary: The stabilization of different conformers of crown- and butoxy-substituted Tb(III) and Y(III) trisphthalocyaninates by altering the solvation environment has been demonstrated through crystallographic characterization, analysis of intermolecular solvent-solvate interactions, and NMR characterization. Solvation-induced conformational switching can be used to control the magnetic properties of lanthanide trisphthalocyaninates.
INORGANIC CHEMISTRY
(2023)
Article
Biochemistry & Molecular Biology
Alexander G. Martynov, Kirill P. Birin, Gayane A. Kirakosyan, Yulia G. Gorbunova, Aslan Yu. Tsivadze
Summary: We report the synthesis of isomeric heteronuclear terbium and yttrium triple-decker phthalocyaninates, which undergo solvation-induced switching between different conformations. By analyzing the H-1 NMR spectra, we determine that the axial component of the magnetic susceptibility tensor is particularly sensitive to conformational switching when terbium is placed in the switchable M site. This result provides a new tool for controlling the magnetic properties of lanthanide complexes with phthalocyanine ligands.
Article
Chemistry, Physical
Inna A. Abdulaeva, Kirill P. Birin, Remi Chassagnon, Alla Bessmertnykh-Lemeune
Summary: Heterogenized metalloporphyrin catalysts were immobilized on hydrated mesoporous titanium dioxide through carboxylate or phosphonate anchoring groups. The element composition of the obtained mesoporous materials was investigated and the integrity of the immobilized complexes was confirmed. The catalytic efficiency of the more stable material Mn(TMPIP)/TiO2 with the phosphonate anchor was evaluated in the selective oxidation of sulfides to sulfoxides, showing excellent catalytic activity.
Article
Biochemistry & Molecular Biology
Stepan M. M. Korobkov, Kirill P. P. Birin, Anatole N. N. Khodan, Oleg Yu. Grafov, Yulia G. G. Gorbunova, Aslan Yu. Tsivadze
Summary: A method for successfully grafting unsymmetrical A(2)BC-type 5,15-bis(4-butoxyphenyl)-10-(4-carboxyphenyl)-20-(phenanthrenoimidazolyl)-porphyrin onto the surface of nanostructured aluminum oxyhydroxide modified with a single SiO2 layer (NAOM) has been developed. This method allows for the preparation of a new porphyrin-containing hybrid material through a straightforward surface modification procedure of NAOM. The 3D heterostructure obtained was extensively characterized using XPS, TEM, and diffuse reflectance spectroscopy, and the stability of the material against leaching as well as the porphyrin immobilization ratio of approximately 14% by weight were revealed.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Chemistry, Multidisciplinary
Elena E. Bardina, Eugeniya V. Makotchenko, Kirill P. Birin, Iraida A. Baidina, Taisiya S. Sukhikh, Alexander S. Novikov, Yulia G. Gorbunova, Aslan Yu. Tsivadze, Artem L. Gushchin
Summary: In this study, a new gold(iii) complex [Au(TBPP)][AuCl4] (1) was synthesized and characterized. The crystal structure of 1 and two other crystalline phases were analyzed, revealing weak intermolecular interactions between the [Au(TBPP)](+) cationic complex and [AuCl4](-) anions, HOAc molecules, and neighboring [Au(TBPP)](+) cations. Density functional theory calculations confirmed the noncovalent nature of these interactions.
Article
Chemistry, Inorganic & Nuclear
Ekaterina A. Zhigileva, Yulia Yu. Enakieva, Anna A. Sinelshchikova, Vladimir V. Chernyshev, Ivan N. Senchikhin, Konstantin A. Kovalenko, Irina A. Stenina, Andrey B. Yaroslavtsev, Yulia G. Gorbunova, Aslan Yu. Tsivadze
Summary: Herein, a novel anionic hydrogen-bonded organic framework (HOF-IPCE-1Pd) based on a new complex of palladium(ii) with meso-tetrakis(4-(phosphonatophenyl))porphyrin is reported. The framework shows high crystallinity, simple synthetic procedure, and is easily regenerated. The directed structural transformation of the framework and the absorption of ammonia and water molecules led to the formation of a more hydrolytically stable structure (HOF-IPCE-1Pd-NH3) with a proton conductivity of 1.27 x 10(-3) S cm(-1) at 85 degrees C and 85% RH, which is one of the highest among all known porphyrin-based HOFs. It is noteworthy that the reversible absorbance of water/ammonia molecules preserves the crystal structure of HOF-IPCE-1Pd-NH3.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Marina V. Volostnykh, Gayane A. Kirakosyan, Anna A. Sinelshchikova, Polina A. Loboda, Pavel V. Dorovatovskii, Maxim A. Mikhaylov, Aslan Yu. Tsivadze, Maxim N. Sokolov, Yulia G. Gorbunova
Summary: This study reports the coordinated design and synthesis of stable supramolecular cluster-porphyrin (CP) hybrids based on an octahedral molybdenum(ii) iodide cluster and a ruthenium porphyrin. The supramolecular assembly of the cluster with the porphyrin has been studied, and the formation of discrete cluster-porphyrin adducts with different numbers of coordinated porphyrins has been observed. The coordination-based supramolecular approach provides new stable cluster-multiporphyrin arrays, which can be promising for the design of photoactive materials.
DALTON TRANSACTIONS
(2023)