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N^N^C-Cyclometalated rhodium(III) complexes with isomeric pyrimidine-based ligands: unveiling the impact of isomerism on structural motifs, luminescence and cytotoxicity.

Sofia N VorobyevaSof'ya A BautinaNikita A ShekhovtsovElena B NikolaenkovaTaisiya S SukhikhYuliya A GolubevaLyubov S KlyushovaViktor P KrivopalovMarianna I RakhmanovaChristophe GourlaouenMark B Bushuev
Published in: Dalton transactions (Cambridge, England : 2003) (2024)
The impact of isomerism of pyrimidine-based ligands and their rhodium(III) complexes with regard to their structures and properties was investigated. Two isomeric ligands, 4-(3,5-dimethyl-1 H -pyrazol-1-yl)-2,5-diphenylpyrimidine (HL2,5) and 4-(3,5-dimethyl-1 H -pyrazol-1-yl)-2,6-diphenylpyrimidine (HL2,6), were synthesized. The ligands differ by the degree of steric bulk: the molecular structure of HL2,5 is more distorted due to presence of pyrazolyl and phenyl groups in the neighbouring positions 4 and 5 of the pyrimidine ring. The complexation of HL2,5 and HL2,6 with RhCl 3 leads to the sp 2 C-H bond activation, resulting in the isolation of two complexes, [RhL2,5(Solv)Cl2]·nEtOH and [RhL2,6(Solv)Cl2]·nEtOH (Solv = H 2 O, EtOH), with the deprotonated forms of the pyrazolylpyrimidine molecules which coordinate the Rh 3+ ion as N^N^C-tridentate ligands. According to DFT modelling, the mechanism of the deprotonation involves (i) the C-H bond breaking in the 2-phenyl group followed by the coordination of the C atom to the Rh atom, (ii) the protonation of coordinated chlorido ligand, (iii) the ejection of the HCl molecule and (iv) the coordination of the H 2 O molecule. The ligand isomerism has an impact on emission properties and cytotoxicity of the complexes. Although the excited states of the complexes effectively deactivate through S 0 /T 1 and S 0 /S 1 crossings associated with the cleavage of the weak H 2 O ligands upon excitation, the [RhL2,5(Solv)Cl2]·nEtOH complex appeared to be emissive in the solid state, while [RhL2,6(Solv)Cl2]·nEtOH is non-emissive at all. The complexes show significant cytotoxic activity against cancerous HepG2 and Hep2 cell lines, with the [RhL2,6(Solv)Cl2]·nEtOH complex being more active than its isomer [RhL2,5(Solv)Cl2]·nEtOH. On the other hand, noticeable cytotoxicity of the latter against HepG2 is supplemented by its non-toxicity against non-cancerous MRC-5 cells.
Keyphrases
  • solid state
  • high resolution
  • oxidative stress
  • mass spectrometry
  • cell death
  • endoplasmic reticulum stress
  • crystal structure
  • visible light