Abstract

Two new organic-inorganic hybrid compounds containing dicarboxylic pyridine acids have been obtained and characterized. Both compounds are potassium oxidodiperoxidomolybdates with 2,6-dicarboxylicpyridine acid or 3,5-dicarboxylicpyridine acid moieties, respectively. The chemical formula for the first one is C14H7K3Mo2N2O18 denoted as K26dcpa, the second C7H4K1Mo1N1O11.5—K35dcpa. Their crystal structures were determined using single crystal (K26dcpa) or XRPD—X-ray powder diffraction techniques (K35dcpa). The purity of the compounds was confirmed by elemental analysis. Their thermal stability was determined with the use of non-ambient XRPD. In addition, they were examined by IR spectroscopy methods and catalytic activity studies were performed for them. Catalytic tests in the Baeyer–Villiger reaction and biological activity have been performed for eight compounds: K26dcpa, K35dcpa, and six peroxidomolybdates previously obtained by our group. The anti-proliferative activity of peroxidomolybdenum compounds after 24 h of incubation was studied in vitro against three selected human tumor cell lines (SW620, LoVo, HEP G2) and normal human cells (fibroblasts). The data were expressed as IC50 values. The structure of the investigated oxodiperoxomolybdenum compounds was shown to have influence on the biological activity and catalytic properties. It has been shown that the newly-obtained compound, K35dcpa, is a very efficient catalyst in the Baeyer–Villiger reaction. The best biological activity results were obtained for Na-picO (previously obtained by us), which is a very effective anti-cancer agent towards SW 620 colorectal adenocarcinoma cells.

Highlights

  • Polyoxometalates (POMs) are a wide group of compounds containing peroxidocompounds as a subgroup

  • The structures of POMs are based on clusters containing transition metal atoms [1,2], surrounded by oxygen atoms

  • The inorganic parts of each compound contain the molybdenum atom surrounded by seven oxygen atoms

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Summary

Introduction

Polyoxometalates (POMs) are a wide group of compounds containing peroxidocompounds as a subgroup. Single metal center containing clusters of peroxido compounds can be classified as mono-, di-, tri-, and even tetra- peroxido metalates depending on the number of O22− groups These groups contain relatively weak O-O bonds, and the formal oxidation state of oxygen atoms is −1 [3]. The carboxylic acids used in the reaction differ only in the relative position of two carboxylic COO- groups with respect to the N-atoms in the pyridine rings This factor directly influences the crystal structures of obtained compounds and is interesting from a crystal engineering point of view. This report highlights the crystal structures and physicochemical properties of the new compounds Their catalytic properties are studied in the cyclooctane oxidation reaction as well as in the Baeyer–Villiger reaction (oxidation of cyclohexanone) and were compared against six previously described compounds. All eight listed peroxidocompounds were tested with regard to their biological activity

Syntheses
IR Measurements
X-ray Thermal Decomposition
MTT Assay
Baeyer–Villiger Reaction
Crystal Structure Data
IR Spectra
Thermal Decomposition
Biological Activity
Catalytic Activity
II IIII IIIIII
Discussion & Conclusions
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