Syntheses, crystal structures and magnetic properties of three new molecular solids based on bis(maleonitriledithiolate)copper(II) anion and ortho-position substituted benzyl isoquinolinium cations

• Published in: Synthetic metals Vol. 199; pp. 246 - 254
• Main Authors: Zhang, Zheng, Lin, Xue-Ni, Chen, Xiao-Min, Yao, Zi-Mei, Liao, Xuan, Zhang, Yao-Mou, Yang, Le-Min, Liu, Xiao-Ping, Ni, Chun-Lin
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 01.01.2015
• Subjects: Anions; Antiferromagnetism; Bis(maleonitriledithiolate)copper(II) anion; Cations; Columns (structural); Crystal structure; Magnetic permeability; Magnetic properties; Neural networks; Substituted benzyl isoquinolinium; Weak interactions; Substituted benzyl isoquinolinium; Bis(maleonitriledithiolate)copper(II) anion; Weak interactions; Magnetic properties
• ISSN: 0379-6779; 1879-3290
• DOI: 10.1016/j.synthmet.2014.11.027

[Display omitted] •Three molecular solids containing [Cu(mnt)2]2− dianion were prepared and characterized.•The [Cu(mnt)2]2− anions in 1 and 2 form a dimer by the side-to-side S⋯S, N⋯N and S⋯N interactions.•There are non-classical hydrogen bonds, X⋯N (X=F, Cl), Br⋯S, Cu⋯N and π⋯π interactions.•There exists an antiferromagnetic interaction in 1.•A change of magnetic exchange from weak ferromagnetic to antiferromagnetic exists in 2 and 3. Three molecular solids, [2RBzIQl]2[Cu(mnt)2] (mnt2−=maleonitriledithiolate; [2RBzIQl]+=1-(2′-R-benzyl) isoquinolinium, R=F(1), Cl(2) and Br(3)), have been prepared and systemically investigated. The crystal structural analysis reveals that three molecular metals crystallize in the monoclinic with space group P21/c, and the [2RBzIQl]+ cations stack into an one-dimensional column through CH⋯π, π⋯π and CH⋯X (X=F or Cl) interactions while the [Cu(mnt)2]2− anions in 1 and 2 form a dimer by the side-to-side S⋯S, N⋯N and S⋯N interactions. The anions (A) and cations (C) are arranged alternatively into one 1D column for 1 and 2 and two 1D columns for 3 with a ⋯ACCACCA⋯ sequence though CH⋯S, CH⋯π, CH⋯N or/and CH⋯Cu hydrogen bonds, and weak X⋯N (X=F, Cl), Br⋯S, Cu⋯N or/and π⋯π interactions. The magnetic susceptibilities measured in the temperature range 2.0–300K reveal that 1 shows an antiferromagnetic behavior, while 2 and 3 exhibit a change of magnetic exchange from weak ferromagnetic to antiferromagnetic around 48K upon the temperature is lowered.