The effect of solvent molecules on crystallisation of heterotrinuclear MII-TbIII-MII complexes with tripodal nonadentate ligands

Kazuma Takahara, Yuki Horino, Koki Wada, Hiromu Sakata, Daichi Tomita, Yukinari Sunatsuki, Hiroshi Isobe, Masaaki Kojima, Takayoshi Suzuki

Research output: Contribution to journalArticlepeer-review

Abstract

The crystal structures and crystallisation behaviours of MII-TbIII-MII heterotrinuclear complexes, [(L)MTbM(L)]NO3 (M = Mn and Zn; L3- stands for a conjugated base of H3L = 1,1,1-tris[(3-methoxysalicylideneamino)methyl]ethane), obtained from various organic solvents (MeOH, EtOH, CH2Cl2 and CHCl3) were investigated. The trinuclear complex cation has two asymmetric centres (? or ?) at two MII sites as a result of the twisted tripodal arms of L3-. Single-crystal X-ray diffraction analysis revealed that all the analysed Zn-Tb-Zn complexes had homochiral structures (?,?- or ?,?-enantiomers) in each single crystal; however, the type of crystallisation behaviour showed clear differences depending on the type of solvent molecule. Specifically, crystallisation from MeOH or CH2Cl2 resulted in the exclusive formation of the ?-conglomerates with the ?,?-enantiomers—a phenomenon we recently termed ‘absolute spontaneous resolution’. The analogous Mn-Tb-Mn complex crystallised from MeOH also resulted in the same phenomenon as that of Zn-Tb-Zn. In contrast, the meso-type (?,?) achiral isomer of the Mn-Tb-Mn complex was deposited for the first time in a series of MII-LnIII-MII trinuclear complexes from a CH2Cl2 or EtOH solution. Density functional theory calculations were performed to compare the thermodynamic stability of homochiral (?,?) and meso-type (?,?) complex cations of [(L)MnTbMn(L)]+ in MeOH and EtOH. Results were consistent with the molecular structures observed in the crystallographic analysis of the compounds deposited from these solvents.

Original languageEnglish
Pages (from-to)1004-1014
Number of pages11
JournalCrystEngComm
Volume26
Issue number7
DOIs
Publication statusPublished - Jan 10 2024

ASJC Scopus subject areas

  • General Chemistry
  • General Materials Science
  • Condensed Matter Physics

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