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Rhenium Tricarbonyl Complexes of Azodicarboxylate Ligands.

ABSTRACT: The excellent π-accepting azodicarboxylic esters adcOR (R = Et, iPr, tBu, Bn (CH2-C6H5) and Ph) and the piperidinyl amide derivative adcpip were used as bridging chelate ligands in dinuclear Re(CO)3 complexes [{Re(CO)3Cl}2(µ-adcOR)] and [{Re(CO)3Cl}2(µ-adcpip)]. From the adcpip ligand the mononuclear derivatives [Re(CO)3Cl(adcpip)] and [Re(CO)3(PPh3)(µ-adcpip)]Cl were also obtained. Optimised geometries from density functional theory (DFT) calculations show syn and anti isomers for the dinuclear fac-Re(CO)3 complexes at slightly different energies but they were not distinguishable from experimental IR or UV-Vis absorption spectroscopy. The electrochemistry of the adc complexes showed reduction potentials slightly below 0.0 V vs. the ferrocene/ferrocenium couple. Attempts to generate the radicals [{Re(CO)3Cl}2(µ-adcOR)]•- failed as they are inherently unstable, losing very probably first the Cl- coligand and then rapidly cleaving one [Re(CO)3] fragment. Consequently, we found signals in EPR very probably due to mononuclear radical complexes [Re(CO)3(solv)(adc)]•. The underlying Cl-→solvent exchange was modelled for the mononuclear [Re(CO)3Cl(adcpip)] using DFT calculations and showed a markedly enhanced Re-Cl labilisation for the reduced compared with the neutral complex. Both the easy reduction with potentials ranging roughly from -0.2 to -0.1 V for the adc ligands and the low-energy NIR absorptions in the 700 to 850 nm range place the adc ligands with their lowest-lying π* orbital being localised on the azo function, amongst comparable bridging chelate N^N coordinating ligands with low-lying π* orbitals of central azo, tetrazine or pyrazine functions. Comparative (TD)DFT-calculations on the Re(CO)3Cl complexes of the adcpip ligand using the quite established basis set and functionals M06-2X/def2TZVP/LANL2DZ/CPCM(THF) and the more advanced TPSSh/def2-TZVP(+def2-ECP for Re)/CPCMC(THF) for single-point calculations with BP86/def2-TZVP(+def2-ECP for Re)/CPCMC(THF) optimised geometries showed a markedly better agreement of the latter with the experimental XRD, IR and UV-Vis absorption data.

SUBMITTER: Jordan R

PROVIDER: S-EPMC9740152 | biostudies-literature | 2022 Nov

REPOSITORIES: biostudies-literature

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Rhenium Tricarbonyl Complexes of Azodicarboxylate Ligands.

Jordan Rose R Niazi Maryam M Schäfer Sascha S Kaim Wolfgang W Klein Axel A

Molecules (Basel, Switzerland) 20221123 23

The excellent π-accepting azodicarboxylic esters adcOR (R = Et, iPr, tBu, Bn (CH2-C6H5) and Ph) and the piperidinyl amide derivative adcpip were used as bridging chelate ligands in dinuclear Re(CO)3 complexes [{Re(CO)3Cl}2(µ-adcOR)] and [{Re(CO)3Cl}2(µ-adcpip)]. From the adcpip ligand the mononuclear derivatives [Re(CO)3Cl(adcpip)] and [Re(CO)3(PPh3)(µ-adcpip)]Cl ...[more]

PMID: 36500250

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Project description:Seven rhenium(I) complexes of the general formula fac-[Re(CO)3(NN)(OH2)]+ where NN = 2,2'-bipyridine (8), 4,4'-dimethyl-2,2'-bipyridine (9), 4,4'-dimethoxy-2,2'-bipyridine (10), dimethyl 2,2'-bipyridine-4,4'-dicarboxylate (11), 1,10-phenanthroline (12), 2,9-dimethyl-1,10-phenanthroline (13), or 4,7-diphenyl-1,10-phenanthroline (14), were synthesized and characterized by 1H NMR spectroscopy, IR spectroscopy, mass spectrometry, and X-ray crystallography. With the exception of 11, all complexes exhibited 50% growth inhibitory concentration (IC50) values that were less than 20 μM in HeLa cells, indicating that these compounds represent a new potential class of anticancer agents. Complexes 9, 10, and 13 were as effective in cisplatin-resistant cells as wild-type cells, signifying that they circumvent cisplatin resistance. The mechanism of action of the most potent complex, 13, was explored further by leveraging its intrinsic luminescence properties to determine its intracellular localization. These studies indicated that 13 induces cytoplasmic vacuolization that is lysosomal in nature. Additional in vitro assays indicated that 13 induces cell death without causing an increase in intracellular reactive oxygen species or depolarization of the mitochondrial membrane potential. Further studies revealed that the mode of cell death does not fall into one of the canonical categories such as apoptosis, necrosis, paraptosis, and autophagy, suggesting that a novel mode of action may be operative for this class of rhenium compounds. The in vivo biodistribution and metabolism of complex 13 and its 99mTc analogue 13* were also evaluated in naı̈ve mice. Complexes 13 and 13* exhibited comparable biodistribution profiles with both hepatic and renal excretion. High-performance liquid chromatography inductively coupled plasma mass-spectrometry (HPLC-ICP-MS) analysis of mouse blood plasma and urine postadministration showed considerable metabolic stability of 13, rendering this potent complex suitable for in vivo applications. These studies have shown the biological properties of this class of compounds and demonstrated their potential as promising theranostic anticancer agents that can circumvent cisplatin resistance.

Project description:Over the last few years, luminescent Re(i) tricarbonyl complexes have been increasingly proposed as fluorophores suitable for fluorescence microscopy to visualize biological structures and cells. In this sense, incorporating an asymmetrical pyridine Schiff base (PSB) as the ancillary ligand strongly modifies the staining and luminescent properties of Re(i) tricarbonyl complexes. In this work, we analyzed two series of Re(i) tricarbonyl complexes with their respective PSB ligands: (1) fac-[Re(CO)3(2,2'-bpy)(PSB)]1+ and (2) fac-[Re(CO)3(4,4'-bis(ethoxycarbonyl)-2,2'-bpy)(PSB)]1+, where the PSB exhibits substitutions at positions 4 or 6 in the phenolic ring with methyl or halogen substituents. Thus, we performed computational relativistic DFT and TDDFT studies to determine their optical properties. The ten complexes analyzed showed absorption in the visible light range. Furthermore, our analyses, including zero-field splitting (ZFS), allowed us to determine that the low-lying excited state locates below the 3LLCT states. Interestingly, seven of the ten analyzed complexes, whose corresponding PSB harbors an intramolecular hydrogen bond (IHB), exhibited luminescent emission that could be suitable for biological purposes: large Stokes shift, emission in the range 600-700 nm and τ in the order of 10-2 to 10-3 s. Conversely, the three complexes lacking the IHB due to two halogen substituents in the corresponding PSB showed a predicted emission with the lowest triplet excited state energy entering the NIR region. The main differences in the complexes' photophysical behavior have been explained by the energy gap law and time-resolved luminescence. These results emphasize the importance of choosing suitable substituents at the 4 and 6 positions in the phenolic ring of the PSB, which determine the presence of the IHB since they modulate the luminescence properties of the Re(i) core. Therefore, this study could predict Re(i) tricarbonyl complexes' properties, considering the desired emission features for biological and other applications.

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Rhenium Tricarbonyl Complexes of Azodicarboxylate Ligands.

Publications

Rhenium Tricarbonyl Complexes of Azodicarboxylate Ligands.

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