Synthesis, characterisation and biological evaluation of monometallic Re(<scp>i</scp>) and heterobimetallic Re(<scp>i</scp>)/Fe(<scp>ii</scp>) complexes with a 1,2,3-triazolyl pyridine chelating moiety

Jakopec, Silvio; Gourdon, Lisa; Čipor, Ivona; Meščić, Andrijana; Perić, Berislav; Piantanida, Ivo; Cariou, Kevin; Gasser, Gilles; Kirin, Srećko I.; Raić‐Malić, Silvana

doi:10.1039/d3dt01070h

Cited by 5 publications

(4 citation statements)

References 86 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In contrast, a recent report of ferrocene conjugates of Re(I) tricarbonyl complexes by Jakopec et al . has not presented any emission due to complete emission quenching by the ferrocene moiety . However, the observed weak emission of ReFctp might be useful in determining its in-cell localization.…”

Section: Results and Discussionmentioning

confidence: 95%

“…48 In contrast, a recent report of ferrocene conjugates of Re(I) tricarbonyl complexes by Jakopec et al has not presented any emission due to complete emission quenching by the ferrocene moiety. 49 However, the observed weak emission of ReFctp might be useful in determining its incell localization. Retp and ReFctp displayed good stability in the DMSO/DMEM (2:98, v/v) solution under both dark and light conditions, as observed by time-dependent UV−vis.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

See 1 more Smart Citation

Visible and Red Light-Triggered Anticancer Profile of a Ferrocene-Re(I)-Tricarbonyl Conjugate: Experimental and Theoretical Studies

Kushwaha,

Upadhyay,

Peters

et al. 2024

Langmuir

View full text Add to dashboard Cite

We have red-shifted the light absorbance property of a Re(I)-tricarbonyl complex via distant conjugation of a ferrocene moiety and developed a novel complex ReFctp, [Re(Fctp)(CO) 3 Cl], where Fctp = 4′-ferrocenyl-2,2′:6′,2″-terpyridine. ReFctp showed green to red light absorption ability and blue emission, indicating its potential for photodynamic therapy (PDT) application. The conjugation of ferrocene introduced ferrocenebased transitions, which lie at a higher wavelength within the PDT therapeutic window. The time-dependent density functional theory and excited state calculations revealed an efficient intersystem crossing for ReFctp, which is helpful for PDT. ReFctp elicited both PDT type I and type II pathways for reactive oxygen species (ROS) generation and facilitated NADH (1,4-dihydro-nicotinamide adenine dinucleotide) oxidation upon exposure to visible light. Importantly, ReFctp showed effective penetration through the layers of clinically relevant 3D multicellular tumor spheroids and localized primarily in mitochondria (Pearson's correlation coefficient, PCC = 0.65) of A549 cancer cells. ReFctp produced more than 20 times higher phototoxicity (IC 50 ∼1.5 μM) by inducing ROS generation and altering mitochondrial membrane potential in A549 cancer cells than the nonferrocene analogue Retp, [Re(CO) 3 (tp)Cl], where tp = 2,2′:6′,2″-terpyridine. ReFctp induced apoptotic mode of cell death with a notable photocytotoxicity index (PI, PI = IC 50dark /IC 50light ) and selectivity index (SI, SI = normal cell's IC 50dark /cancer cell's IC 50light ) in the range of 25−33.

show abstract

Section: Results and Discussionmentioning

confidence: 95%

Section: ■ Experimental Sectionmentioning

confidence: 99%

Visible and Red Light-Triggered Anticancer Profile of a Ferrocene-Re(I)-Tricarbonyl Conjugate: Experimental and Theoretical Studies

Kushwaha,

Upadhyay,

Peters

et al. 2024

Langmuir

View full text Add to dashboard Cite

show abstract

“…In continuation of our research on ferrocene‐based heterobimetallic complexes, 20 and having in mind the stereochemistry of flexible tridentate ligands, herein, we have studied structurally more flexible analogs of previously described 2,2′‐dipyridylamine–ferrocene conjugates 14 . The presented work describes coordination chemistry, electron transfer properties and effect on cell viability of ferrocene derivatives in which the metallocene core is linked directly or via an ethylenediamine linker to a bis(2‐picolyl)amine (bpa), iminodiacetamide (imda), and bis‐1,2,3‐triazole (bta) coordinating group.…”

Section: Introductionmentioning

confidence: 87%

Late transition metal complexes of ferrocene‐containing nitrogen ligands: Coordination chemistry, electron transfer properties, and tumor cell viability

Jakopec,

Pantalon Juraj,

Jadreško

et al. 2024

Applied Organom Chemis

Self Cite

View full text Add to dashboard Cite

Bis(2‐picolyl)amine (bpa), iminodiacetamide (imda), and bis‐1,2,3‐triazole (bta) ferrocene ligands (L) with and without an aliphatic linker were prepared by multi‐step synthesis. The cis‐fac, trans‐fac, or mer stereochemistry of their ML2 complexes with Ni(II), Cu(II), Cd(II), and Zn(II) was studied in the solid state (infrared [IR] and single‐crystal X‐ray diffraction [SC‐XRD]), in solution (nuclear magnetic resonance [NMR] and cyclic voltammetry [CV]) and by density functional theory (DFT) calculations. Crystal structures were determined for bpa ligand 7, and complexes [Ni(1)2](NO3)2 (1Ni), [Cu(8)2]OTf2 (8Cu), [Ni(10b)2](NO3)2 (10bNi), and [Cu(10b)2]OTf2 (10bCu). The bond strength of the central metal ion to the ligand amine nitrogen atom was studied by NMR, electrochemistry, and DFT. The information on redox‐active centers, electron transfer properties of ferrocene ligands (L), and their in situ complexation with zinc(II) and nickel(II) ions were obtained by voltammetric analysis. In addition, DFT calculations showed that the electron ionization in ML2 complexes occurs from one of the ferrocene units, leaving the electronic structure of the other ligand intact, while some of the expelled electron density is recovered by the adjacent amine through resonance. This effect is more pronounced in the free ligands, because the eventual amine resonance in ML2 needs to balance its Zn(II) coordination participation, which justifies why they show higher ionization energies over free ligands. Moreover, due to lower steric hindrance, the N(amino)–Zn(II) coordination is additionally stronger in 1:1 ML complexes, which makes their electron depletion further more demanding. If compared with the clinical drug cisplatin, complexes of bpa 1Ni and imda 2Ni showed a better effect on the viability of different tumor cell lines and better selectivity towards normal cells. Treatment with 1Ni and 2Ni causes an increase of cells in the S phase of the cell cycle and leads to the accumulation of cells in G0/G1. A decrease in the expression level of anti‐apoptotic marker Bcl‐2 upon treatment with both compounds together with increased amount of Annexin V‐FITC positive cells implied apoptosis as the mode of cell death.

show abstract

“…Coppercatalyzed dipolar cycloaddition was utilized for the preparation of the triazolic L7. [20] The quaternary ammonium salt analogues (L3, L6, L8) were obtained by stirring in acetonitrile with benzyl chloride and potassium iodide with high yields.…”

Section: Synthesis and Characterizationmentioning

confidence: 99%

Towards Platinum(II) Complexes forin celluloApplications: Synthesis, Characterization, Biological and Catalytic Evaluation

Gourdon‐Grünewaldt,

Bakija,

Wild

et al. 2023

Helvetica Chimica Acta

Self Cite

View full text Add to dashboard Cite

With the aim of achieving bioorthogonal intracellular catalysis, a library of platinum(II) complexes was synthesized. Their non‐toxicity to living cells was demonstrated and their catalytic activity was evaluated on a cyclization reaction leading to a highly fluorescent coumarin. None of the platinum complexes showed any catalytic activity for coumarin synthesis. Still, we demonstrated that the silver salt AgSbF6 commonly used to ‘activate’ metal catalysts by removing a chloride is a very efficient catalyst for the studied intramolecular cyclization reaction.

show abstract

Synthesis, characterisation and biological evaluation of monometallic Re(i) and heterobimetallic Re(i)/Fe(ii) complexes with a 1,2,3-triazolyl pyridine chelating moiety

Abstract: Bioorganometallic complexes have attracted considerable interest and have shown promise for potential application in the treatment and diagnosis of cancer, as well as bioimaging agents, some acting as theranostic agents....

Cited by 5 publications

References 86 publications

Visible and Red Light-Triggered Anticancer Profile of a Ferrocene-Re(I)-Tricarbonyl Conjugate: Experimental and Theoretical Studies

Visible and Red Light-Triggered Anticancer Profile of a Ferrocene-Re(I)-Tricarbonyl Conjugate: Experimental and Theoretical Studies

Late transition metal complexes of ferrocene‐containing nitrogen ligands: Coordination chemistry, electron transfer properties, and tumor cell viability

Towards Platinum(II) Complexes forin celluloApplications: Synthesis, Characterization, Biological and Catalytic Evaluation

Contact Info

Product

Resources

About