Two water soluble Re(I) tricarbonyl diimine complexes containing cationic 2,2'-bipyridyl ligands [Re(L1)(CO)(3)(AN)](2+) (1) and [Re(L2)(CO)(3)(AN)](3+) (2) (L1 and L2: a cationic 2,2'-bipyridyl ligand, AN: acetonitrile) were synthesized and characterized. Their photophysical, electrochemical and electrochemiluminescent properties were investigated. The crystal structures of the two complexes have also been determined. Electrochemiluminescence (ECL) of the two complexes 1 and 2 have been studied in aqueous buffer solution in the presence of co-reactant tri-n-propylamine (TPrA) or 2-(dibutylamino)ethanol (DBAE) at a Au working electrode. The ECL behavior of the complexes was also studied in the presence of several surfactants such as Triton X-100 and Zonyl FSN. The ECL signals of the rhenium(I) complex were enhanced about 190-fold and 70-fold at a Au electrode in the presence of Triton X-100 for the [Re(L1)(CO)(3)(AN)](2+)/TPrA and [Re(L1)(CO)(3)(AN)](2+)/DBAE systems, respectively.
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http://dx.doi.org/10.1039/c2dt30074e | DOI Listing |
Inorg 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 PDFDalton Trans
August 2024
Department of Chemistry, Indian Institute of Technology (BHU), Varanasi, Uttar Pradesh, 221005, India.
Here, we have synthesized and characterized three visible light responsive terpyridine based-Re(I)-tricarbonyl complexes; [Re(CO)(ph-tpy)Cl] (Retp1), [Re(CO)(an-tpy)Cl] (Retp2), and [Re(CO)(py-tpy)Cl] (Retp3) where ph-tpy = 4'-phenyl-2,2':6',2″-terpyridine; an-tpy = 4'-anthracenyl-2,2':6',2″-terpyridine, py-tpy = 4'-pyrenyl-2,2':6',2″-terpyridine. The structures of Retp1 and Retp2 were confirmed from the SC-XRD data, indicating distorted octahedral structures. Unlike traditional PDT agents, these complexes generated reactive oxygen species (ROS) type I and type II pathways and oxidized redox crucial NADH (reduced nicotinamide adenine dinucleotide) upon visible light exposure.
View Article and Find Full Text PDFDalton Trans
August 2024
University of Applied Sciences of Western Switzerland, HES-SO, HEIA-FR, Pérolles 80, CH-1705 Fribourg, Switzerland.
Cancer is a leading cause of death worldwide, accounting for about one among six deaths, so the quest for new and improved therapies is of crucial importance. The discovery of cisplatin as an anticancer agent has paved the way for the development of other metal-based therapeutic agents and Re(I)-based candidates have been recently found to show promising results. It is known as well that chirality plays a central role in the interactions of metal-based drugs with intrinsically chiral biomolecules such as membrane transport proteins or DNA.
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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