Macrocyclic copper(II) complexes containing diazacyclam-based ligand: spectral, structural and docking studies

Zahra Mardani*, Keyvan Moeini, Majid Darroudi, Cameron Carpenter-Warren, Alexandra M. Z. Slawin, J. Derek Woollins

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

Abstract

The macrocyclic copper complex, [Cu(ACE)(NO3)2] (ACE = 1,3,6,10,12,15-hexaazatricyclo[13.3.1.16,10]eicosane), was synthesized by template condensation from a mixture of N1-(2-aminoethyl)-1,3-diaminopropane, formaldehyde and copper(II) nitrate. Replacement of the nitrate with thiocyanato and azido ligands gives [Cu(ACE)NSC]NSC (2) and the 1D-coordination polymer, [Cu(ACE)(μ-N3)]n[N3]n (3), respectively. Complex 1, [Cu(ACE)(NO3)]NO3, is an intermediate product in which one of the nitrate ions is separated from its parent molecule. The formation of 1 allowed us to conclude that the mechanism of ion exchange in the parent molecule is similar to SN1. These complexes have been characterized by FT-IR spectroscopy and X-ray crystallography. In the crystal structures of 1 and 2, the copper(II) ion has a distorted square pyramidal geometry in which the N4-donor ACE ligand lies on the equatorial plane and other ligand occupies the axial position. The copper(II) ion in 3 has an octahedral geometry, coordinating to one ACE ligand in the equatorial plane and two N-donor bridging azido groups in the axial positions. In all structures, owing to the Jahn-Teller effect, the coordinated bond length of the axial position is longer than the equatorial ones. The ability of the ACE ligand and its complexes 1 and 2, along with their analogues, to interact with 10 selected biomacromolecules (BRAF kinase, CatB, DNA gyrase, HDAC7, rHA, RNR, TrxR, TS, Top II and B-DNA) was investigated by docking calculations and compared with that of doxorubicin.
Original languageEnglish
Pages (from-to)3030-3045
Number of pages16
JournalJournal of Coordination Chemistry
Volume72
Issue number18
DOIs
Publication statusPublished - 6 Nov 2019

Keywords

  • Macrocycle
  • Diazacyclam
  • Copper complex
  • Template synthesis
  • Docking study

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