Twelve tricarbonyl rhenium(i) complexes in the '2 + 1' system with the anionic bidentate N,O-donor ligand (deprotonated 8-hydroxyquinoline (HQ) or its 2-methyl (MeHQ) or 5-chloro (ClHQ) derivative) and neutral N-donor diazoles (imidazole (Him), 2-methylimidazole (MeHim), 3,5-dimethylpyrazole (Hdmpz), and 3-phenylpyrazole (HPhpz)) were synthesized: [Re(CO)(L)L] (L = Q, MeQ, ClQ; L = Him, MeHim, Hdmpz, HPhpz). Their crystal structures were determined by the scXRD method, compared with the DFT-calculated ones, and characterized by analytical (EA) and spectroscopic techniques (FT-IR, NMR, and UV-Vis) interpreted with DFT and TD-DFT calculations. Most of the Re(i) complexes did not show relevant antibacterial activity against Gram-negative and Gram-positive bacterial strains. Only [Re(CO)(MeQ)Him] demonstrated significant action 4-fold better against Gram-negative than the free MeHQ ligand. The cytotoxicity of the compounds was estimated using human acute promyelocytic leukemia (HL-60), ovarian (SKOV-3), prostate (PC-3), and breast (MCF-7) cancer, and breast non-cancerous (MCF-10A) cell lines. Only HQ and ClHQ ligands and [Re(CO)(Q)Hdmpz] complex had good selectivity toward MCF-7 cell line. HL-60 cells were sensitive to all complexes (IC = 1.5-14 μM). Still, pure HQ and ClHQ ligands were slightly more active than the complexes.
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http://dx.doi.org/10.1039/d4ra03141e | DOI Listing |
J Inorg Biochem
January 2025
Department of Organic Chemistry, University of Zagreb, Faculty of Chemical Engineering and Technology, Marulićev trg 19, 10000 Zagreb, Croatia. Electronic address:
Novel 6-substituted 2-(trifluoromethyl)quinoline 5a-5e and coumarin 6a-6d ligands with aldoxime ether linked pyridine moiety were synthesized by O-alkylation of quinoline and coumarin with (E)-picolinaldehyde oxime and subsequently with [Re(CO)Cl] gave rhenium(I) tricarbonyl complexes 5a-5e and 6a-6d that were fully characterized by NMR, single-crystal X-ray diffraction, IR and UV-Vis spectroscopy. The results of antiproliferative evaluation of quinoline and coumarin ligands and their rhenium(I) tricarbonyl complexes on various human tumor cell lines, including acute lymphoblastic leukemia (CCRF-CEM), acute monocytic leukemia (THP1), cervical adenocarcinoma (HeLa), colon adenocarcinoma (CaCo-2), T-cell lymphoma (HuT78), and non-tumor human fibroblasts (BJ) showed that the quinoline complexes 5a-5e had higher inhibitory activity than coumarin complexes 6a-6d, particularly against T-cell lymphoma (HuT78) cells. 6-Methoxy-2-(trifluoromethyl)quinoline 5e and 6-methylcoumarin 6d, and their rhenium(I) tricarbonyl complexes 5e and 6d were found to arrest the cell cycle of HuT78 cells by causing a significant accumulation of cells in the G0/G1 phase and a marked decrease in the number of cells in the G2/M phase.
View Article and Find Full Text PDFInorg Chem
September 2024
Centro de Química Estrutural, Institute of Molecular Sciences, Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade de Lisboa, Campo Grande, 1749-016 Lisboa, Portugal.
The catalytic efficacy of a novel mononuclear rhenium(I) complex in CO reduction is remarkable, with a turnover number (TON) of 1517 in 3 h, significantly outperforming previous Re(I) catalysts. This complex, synthesized via a substitution reaction on an aromatic ring to form a bromo-bipyridine derivative, = 2-bromo-6-(1-pyrazol-1-yl)pyridine, and further reacting with [Re(CO)Cl], results in the facial-tricarbonyl complex [ReL1(CO)Cl] (). The light green solid was obtained with an 80% yield and thoroughly characterized using cyclic voltammetry, nuclear magnetic resonance (NMR), Fourier transform infrared (FTIR) spectroscopy, and ultraviolet-visible (UV-vis) spectroscopy.
View Article and Find Full Text PDFChemistry
September 2024
Department of Chemistry, School of Advanced Sciences, Vellore Institute of Technology, Vellore, Tamil Nadu, 632014, India.
We have introduced Re(I) tricarbonyl complexes (ReL1 - ReL6) [Re(CO)(N^N)Cl] where N^N=extensive π conjugated imidazo-[4,5-f][1,10]-phenanthroline derivatives that helps in strong DNA intercalation, enhanced photophysical behavior, increase the π-π* character of T state for PDT and high value of lipophilicity for cell membrane penetration. These complexes exhibited prominent intraligand/ligand-centered (π-π*/LC) absorption bands at λ 260-350 nm and relatively weak metal-to-ligand charge-transfer (MLCT) bands within the λ 350-550 nm range. Among the six synthesized complexes, [(CO)ReCl(K-N,N-2-(4-(1-benzyl-1H-tetrazol-5-yl)phenyl)-1H-imidazo[4,5-f][1,10]phenanthroline] (ReL6) exhibited outstanding potency (IC~6 μM, PI>9) under yellow light irradiation compared to dark conditions.
View Article and Find Full Text PDFACS Appl Mater Interfaces
September 2024
Department of Chemistry, University of Southern California, California, Los Angeles 90089, United States.
The storage of renewable energy through the conversion of CO to CO provides a viable solution for the intermittent nature of these energy sources. The immobilization of rhenium(I) tricarbonyl molecular complexes is presented through the reductive coupling of bis(diazonium) aryl substituents. The heterogenized complex was characterized through ultra-visible, attenuated total reflectance, infrared reflection absorption spectroscopy, and X-ray photoelectron spectroscopy to probe the electronic structure of the immobilized complex.
View Article and Find Full Text PDFTwelve tricarbonyl rhenium(i) complexes in the '2 + 1' system with the anionic bidentate N,O-donor ligand (deprotonated 8-hydroxyquinoline (HQ) or its 2-methyl (MeHQ) or 5-chloro (ClHQ) derivative) and neutral N-donor diazoles (imidazole (Him), 2-methylimidazole (MeHim), 3,5-dimethylpyrazole (Hdmpz), and 3-phenylpyrazole (HPhpz)) were synthesized: [Re(CO)(L)L] (L = Q, MeQ, ClQ; L = Him, MeHim, Hdmpz, HPhpz). Their crystal structures were determined by the scXRD method, compared with the DFT-calculated ones, and characterized by analytical (EA) and spectroscopic techniques (FT-IR, NMR, and UV-Vis) interpreted with DFT and TD-DFT calculations. Most of the Re(i) complexes did not show relevant antibacterial activity against Gram-negative and Gram-positive bacterial strains.
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