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Kroitor AP, Martynov AG, Gorbunova YG, Tsivadze AY, Sorokin AB. Non-aggregated ruthenium naphthalocyanine enabling homogeneous carbene insertion into N-H bonds at low catalyst loading. Dalton Trans 2025; 54:4018-4024. [PMID: 39937538 DOI: 10.1039/d4dt03263b] [Citation(s) in RCA: 0] [Impact Index Per Article: 0] [Reference Citation Analysis] [Abstract] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Indexed: 02/13/2025]
Abstract
The novel ruthenium octa-n-butoxy-naphthalocyanine complex was shown to retain an essentially monomeric state in dilute solutions. It was successfully applied as a homogeneous catalyst for carbene insertion into N-H bonds of amines with various substitution patterns, providing high yields of glycine derivatives.
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Affiliation(s)
- Andrey P Kroitor
- Institut de Recherches sur la Catalyse et l'Environnement de Lyon IRCELYON, UMR 5256, CNRS - Université Lyon 1, 2 av. A. Einstein, 69626 Villeurbanne, France.
- Frumkin Institute of Physical Chemistry and Electrochemistry Russian Academy of Sciences, 31-4 Leninsky prospect, 119071, Moscow, Russia.
| | - Alexander G Martynov
- Frumkin Institute of Physical Chemistry and Electrochemistry Russian Academy of Sciences, 31-4 Leninsky prospect, 119071, Moscow, Russia.
| | - Yulia G Gorbunova
- Frumkin Institute of Physical Chemistry and Electrochemistry Russian Academy of Sciences, 31-4 Leninsky prospect, 119071, Moscow, Russia.
- Kurnakov Institute of General and Inorganic Chemistry Russian Academy of Sciences, 31 Lenisky prospect, 119991 Moscow, Russia.
| | - Aslan Yu Tsivadze
- Frumkin Institute of Physical Chemistry and Electrochemistry Russian Academy of Sciences, 31-4 Leninsky prospect, 119071, Moscow, Russia.
- Kurnakov Institute of General and Inorganic Chemistry Russian Academy of Sciences, 31 Lenisky prospect, 119991 Moscow, Russia.
| | - Alexander B Sorokin
- Institut de Recherches sur la Catalyse et l'Environnement de Lyon IRCELYON, UMR 5256, CNRS - Université Lyon 1, 2 av. A. Einstein, 69626 Villeurbanne, France.
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Sailaja STN, Maisuls I, Hepp A, Brünink D, Doltsinis NL, Faust A, Hermann S, Strassert CA. Dual Emissive Zn(II) Naphthalocyanines: Synthesis, Structural and Photophysical Characterization with Theory-Supported Insights towards Soluble Coordination Compounds with Visible and Near-Infrared Emission. Int J Mol Sci 2024; 25:2605. [PMID: 38473852 DOI: 10.3390/ijms25052605] [Citation(s) in RCA: 0] [Impact Index Per Article: 0] [Reference Citation Analysis] [Abstract] [Key Words] [Grants] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Received: 12/31/2023] [Revised: 02/09/2024] [Accepted: 02/14/2024] [Indexed: 03/14/2024] Open
Abstract
Metal phthalocyaninates and their higher homologues are recognized as deep-red luminophores emitting from their lowest excited singlet state. Herein, we report on the design, synthesis, and in-depth characterization of a new class of dual-emissive (visible and NIR) metal naphthalocyaninates. A 4-N,N-dimethylaminophen-4-yl-substituted naphthalocyaninato zinc(II) complex (Zn-NMe2Nc) and the derived water-soluble coordination compound (Zn-NMe3Nc) exhibit a near-infrared fluorescence from the lowest ligand-centered state, along with a unique push-pull-supported luminescence in the visible region of the electromagnetic spectrum. An unprecedentedly broad structural (2D-NMR spectroscopy and mass spectrometry) as well as photophysical characterization (steady-state state and time-resolved photoluminescence spectroscopy) is presented. The unique dual emission was assigned to two independent sets of singlet states related to the intrinsic Q-band of the macrocycle and to the push-pull substituents in the molecular periphery, respectively, as predicted by TD-DFT calculations. In general, the elusive chemical aspects of these macrocyclic compounds are addressed, involving both reaction conditions, thorough purification, and in-depth characterization. Besides the fundamental aspects that are investigated herein, the photoacoustic properties were exemplarily examined using phantom gels to assess their tomographic imaging capabilities. Finally, the robust luminescence in the visible range arising from the push-pull character of the peripheral moieties demonstrated a notable independence from aggregation and was exemplarily implemented for optical imaging (FLIM) through time-resolved multiphoton micro(spectro)scopy.
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Affiliation(s)
- Sidharth Thulaseedharan Nair Sailaja
- Institut für Anorganische und Analytische Chemie, Universität Münster, Corrensstraße 28/30, 48149 Münster, Germany
- CeNTech, CiMIC, SoN, Universität Münster, Heisenbergstraße 11, 48149 Münster, Germany
| | - Iván Maisuls
- Institut für Anorganische und Analytische Chemie, Universität Münster, Corrensstraße 28/30, 48149 Münster, Germany
- CeNTech, CiMIC, SoN, Universität Münster, Heisenbergstraße 11, 48149 Münster, Germany
| | - Alexander Hepp
- Institut für Anorganische und Analytische Chemie, Universität Münster, Corrensstraße 28/30, 48149 Münster, Germany
| | - Dana Brünink
- Institute for Solid State Theory and Center for Multiscale Theory and Computation, Universität Münster, Wilhelm-Klemm-Straße 10, 48149 Münster, Germany
| | - Nikos L Doltsinis
- Institute for Solid State Theory and Center for Multiscale Theory and Computation, Universität Münster, Wilhelm-Klemm-Straße 10, 48149 Münster, Germany
| | - Andreas Faust
- European Institute for Molecular Imaging, Universität Münster, Röntgenstraße 16, 48149 Münster, Germany
- Department of Nuclear Medicine, University Hospital Münster, Albert-Schweitzer-Campus 1, 48149 Münster, Germany
| | - Sven Hermann
- European Institute for Molecular Imaging, Universität Münster, Röntgenstraße 16, 48149 Münster, Germany
- Department of Nuclear Medicine, University Hospital Münster, Albert-Schweitzer-Campus 1, 48149 Münster, Germany
| | - Cristian A Strassert
- Institut für Anorganische und Analytische Chemie, Universität Münster, Corrensstraße 28/30, 48149 Münster, Germany
- CeNTech, CiMIC, SoN, Universität Münster, Heisenbergstraße 11, 48149 Münster, Germany
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Yenilmez HY, Farajzadeh N, Güler Kuşçulu N, Bahar D, Özdemir S, Tollu G, Güllü M, Altuntaş Bayır Z. Effect of Axial Ligand Length on Biological and Anticancer Properties of Axially Disubstituted Silicon Phthalocyanines. Chem Biodivers 2023; 20:e202201167. [PMID: 36912724 DOI: 10.1002/cbdv.202201167] [Citation(s) in RCA: 2] [Impact Index Per Article: 1.0] [Reference Citation Analysis] [Abstract] [Key Words] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Received: 12/09/2022] [Accepted: 02/21/2023] [Indexed: 03/14/2023]
Abstract
In this study, three new axially disubstituted silicon phthalocyanines (SiPc1-3) and their quaternized phthalocyanine derivatives (QSiPc1-3) were prepared and characterized. The biological properties (antioxidant, antimicrobial, antibiofilm, and microbial cell viability activities) of the water-soluble silicon phthalocyanines were examined, as well. A 1 % DMSO diluted with pure water was used as a solvent in biological activity studies. All the compounds exhibited high antioxidant activity. They displayed efficient antimicrobial and antimicrobial photodynamic therapeutic properties against various microorganisms, especially Gram (+) bacteria. Additionally, they demonstrated high antibiofilm activities against S. aureus and P. aeruginosa. In addition, 100 % bacterial reduction was obtained for all the studied phthalocyanines against E. coli viable cells. Besides, the DNA cleavage and binding features of compounds (QSiPc1-3) were studied using pBR322 DNA and CT-DNA, respectively. Furthermore, the human topoisomerase I enzyme inhibition activities of compounds QSiPc1-3 were studied. Anticancer properties of the water-soluble compounds were investigated using cell proliferation MTT assay. They exhibited anticarcinogenic activity against the human colon cancer cell line (DLD-1). Compounds QSiPc1 and QSiPc3 displayed a high anticarcinogenic effect on the DLD-1 cell line. The obtained results indicated that all the studied compounds may be effective biological agents and anticancer drugs after further investigations.
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Affiliation(s)
- H Yasemin Yenilmez
- Department of Chemistry, Istanbul Technical University, TR-34469, Istanbul, Turkey
| | - Nazli Farajzadeh
- Department of Chemistry, Istanbul Technical University, TR-34469, Istanbul, Turkey
| | - Nilgün Güler Kuşçulu
- Department of Chemistry Technology, Mustafa Çıkrıkçıoğlu Vocational School, Kayseri University, TR-38280, Kayseri, Turkey
| | - Dilek Bahar
- Genome & Stem Cell Center (GENKOK), Erciyes University, TR-38039, Kayseri, Turkey
| | - Sadin Özdemir
- Food Processing Programme, Technical Science Vocational School, Mersin University, TR-33343 Yenisehir, Mersin, Turkey
| | - Gülşah Tollu
- Department of Laboratory and Veterinary Health, Technical Science Vocational School, Mersin University, TR-33343 Yenisehir, Mersin, Turkey
| | - Mithat Güllü
- Department of Biology, Faculty of Science, Erciyes University, TR-38039, Kayseri, Turkey
| | - Zehra Altuntaş Bayır
- Department of Chemistry, Istanbul Technical University, TR-34469, Istanbul, Turkey
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Yalazan H, Maden YE, Koca A, Kantekin H. Multi-step syntheses, electrochemistry and spectroelectrochemistry of peripheral CoII, CuII and MnIIICl phthalocyanines bearing pyrazoline. J Mol Struct 2022. [DOI: 10.1016/j.molstruc.2022.133788] [Citation(s) in RCA: 0] [Impact Index Per Article: 0] [Reference Citation Analysis] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Indexed: 10/16/2022]
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Biyiklioglu Z, Keleş T, Sahin H. Synthesis and acetylcholinesterase enzyme inhibition properties of axially disubstituted silicon phthalocyanines and their quaternized derivatives. J Organomet Chem 2022. [DOI: 10.1016/j.jorganchem.2022.122468] [Citation(s) in RCA: 0] [Impact Index Per Article: 0] [Reference Citation Analysis] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Indexed: 11/26/2022]
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Biyiklioglu Z, Baş H, Sahin H. Non‐aggregated and water soluble axially disubstituted silicon phthalocyanines: Synthesis and inhibitory effect on acetylcholinesterase enzyme. Appl Organomet Chem 2022. [DOI: 10.1002/aoc.6668] [Citation(s) in RCA: 1] [Impact Index Per Article: 0.3] [Reference Citation Analysis] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Indexed: 11/09/2022]
Affiliation(s)
- Zekeriya Biyiklioglu
- Karadeniz Technical University, Faculty of Science, Department of Chemistry Trabzon Turkey
| | - Huseyin Baş
- Karadeniz Technical University, Faculty of Science, Department of Chemistry Trabzon Turkey
| | - Huseyin Sahin
- Giresun University, Espiye Vocational School Giresun Turkey
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Synthesis of 29H,31H-phthalocyanine and chloro (29H,31H-phthalocyaninato) aluminum derivatives showed anti-cancer and anti-bacterial actions. JOURNAL OF SAUDI CHEMICAL SOCIETY 2022. [DOI: 10.1016/j.jscs.2022.101436] [Citation(s) in RCA: 0] [Impact Index Per Article: 0] [Reference Citation Analysis] [Track Full Text] [Subscribe] [Scholar Register] [Indexed: 11/20/2022]
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Kantekin H, Yalazan H, Barut B, Güngör Ö, Ünlüer D, Demirbaş Ü, Özel A, Durmuş M. Dual-purpose both peripheral and non-peripheral triazole substituted ZnII, MgII and PbII phthalocyanines: Synthesis, characterization, photophysicochemical and acetylcholinesterase inhibitory properties. Polyhedron 2021. [DOI: 10.1016/j.poly.2021.115416] [Citation(s) in RCA: 3] [Impact Index Per Article: 0.8] [Reference Citation Analysis] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Indexed: 01/17/2023]
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