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

研究成果査読

抄録

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.

本文言語English
ページ(範囲)1004-1014
ページ数11
ジャーナルCrystEngComm
26
7
DOI
出版ステータスPublished - 1月 10 2024

ASJC Scopus subject areas

  • 化学一般
  • 材料科学一般
  • 凝縮系物理学

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