State Key Laboratory of Materials-Oriented Chemical Engineering and College of Science, Nanjing University of Technology, Nanjing 210009, PR China.
Inorg Chem. 2011 May 2;50(9):3970-80. doi: 10.1021/ic102406u. Epub 2011 Apr 4.
Three [1-N-(4'-R-benzyl)-4-aminopyridinium][Pt(mnt)(2)] compounds were structurally and magnetically characterized, where the substituent was attached to the para-position of the phenyl ring (R = CN (1), Cl (2), and H (3); mnt(2-) = maleonitriledithiolate). 1 and 2 crystallized in the monoclinic space group P2(1)/c, with the cations and anions forming segregated columnar stacks. Their structural differences involved two aspects: (1) both anion and cation stacks were regular in 1 and irregular in 2; (2) the neighboring cations were arranged in the boat-type pattern in 1, whereas these cations were in the chair-type pattern in 2 within the cation stack. 3 belonged to the triclinic space group P ̅1, where the anions were assembled into the stack with a tetrameric Pt(mnt)(2) subunit, but the cations did not form the columnar stack. Magnetic measurements disclosed that a spin-Peierls-type transition occurred around 240 K for 1, whereas a long-range, antiferromagnetic ordering took place at about 5.8 K, and a metamagnetic phenomenon was observed with H(C) ≈ 1000 Oe for 2; 3 showed very strong antiferromagnetic interactions with diamagnetism in the temperature range 5-300 K. Combined with our previous studies, the correlation between the stacking pattern of benzylpyridinium derivatives in a cation stack and the spin-Peierls-type transition is discussed for the series of quasi-1-D M(mnt)(2) (M = Ni, Pd and Pt) compounds.
三种[1-N-(4'-R-苄基)-4-氨基吡啶鎓][Pt(mnt)(2)]化合物进行了结构和磁性表征，其中取代基连接在苯基环的对位（R = CN（1）、Cl（2）和 H（3）；mnt(2-) = 丙二腈二硫代）。1 和 2 结晶于单斜空间群 P2(1)/c，阳离子和阴离子形成分离的柱状堆积。它们的结构差异涉及两个方面：（1）在 1 中，阴离子和阳离子堆积都是规则的，而在 2 中则是不规则的；（2）在 1 中，相邻的阳离子排列成船型模式，而在 2 中，这些阳离子在阳离子堆积中排列成椅型模式。3 属于三斜空间群 P ̅1，其中阴离子组装成具有四聚体Pt(mnt)(2)亚基的堆积体，但阳离子未形成柱状堆积。磁性测量表明，1 中发生了自旋-佩尔斯型转变，大约在 240 K 左右，2 中发生了长程反铁磁有序，在 5.8 K 左右，并且观察到了一个具有 H(C)≈1000 Oe 的顺磁现象；3 在 5-300 K 的温度范围内表现出非常强的反铁磁相互作用和抗磁性。结合我们之前的研究，讨论了在一系列准一维M(mnt)(2)（M = Ni、Pd 和 Pt）化合物中，阳离子堆积中苄基吡啶鎓衍生物的堆积模式与自旋-佩尔斯型转变之间的相关性。
