Role of Pyrazine-N,N鈥?dioxide in [W(CN)8]n鈭?/sup>-Based Hybrid Networks: Anion鈭捪€ Interactions

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• 作者：Robert Podgajny ; Dawid Pinkowicz ; Bernard Czarnecki ; Marcin Kozie艂 ; Szymon Chor膮偶y ; Magdalena Wis ; Wojciech Nitek ; Micha艂 Rams ; Barbara Sieklucka
• 刊名：Crystal Growth & Design
• 出版年：2014
• 出版时间：August 6, 2014
• 年：2014
• 卷：14
• 期：8
• 页码：4030-4040
• 全文大小：668K
• ISSN：1528-7505

文摘

Pyrazine-N,N鈥?dioxide (pzdo) was used as a linker in the design and synthesis of hybrid octacyanometalate-based networks. Four new compounds Na₆[W^V(CN)₈]₂(pzdo)₇路5H₂O (1), K₃[W^V(CN)₈](pzdo)₂路4H₂O (2), {Mn^II₆(pzdo)₄(MeOH)₁₀[W^V(CN)₈]₄}路4MeOH (3), and {Mn^II₂(pzdo)(H₂O)₄[W^IV(CN)₈]}路4H₂O (4) reveal specific M-pzdo-[W(CN)₈]^{3鈥?4鈥?/sup> (M = NaI, KI, MnII) structural arrangements where pzdo plays a significant role. Apart from typical supramolecular interactions including hydrogen bonding and van der Waals interactions, the {[M(渭-pzdo)M][W(CN)₈]_x} (x = 1 or 2) structural motifs in 1鈥?b>4 are organized by specific supramolecular interactions of the pzdo molecule and the octacyanotungstate anions: face-to-face sandwich type interactions between the plane of the pzdo aromatic ring and N₄ square face of [W(CN)₈]n鈭?/sup> anions, edge-to-face interactions between the plane of the pyrazine ring and a pair of neighboring N_CN atoms of the [W(CN)₈]-moiety, and end-to-face interactions between the plane of the pyrazine ring and a single N_CN atoms of the [W(CN)₈]-moiety. The related intermolecular arrangements show features typical for anion鈭捪€ interactions, unprecedented in the octacyanometalate chemistry. The specific interactions of the octacyanotungstate and the pzdo molecule in 1 and 2 lead to significant modification of their electronic spectra. Magnetic studies revealed that 1, 2, and 4 are paramagnetic, although 3 orders antiferromagnetically at T_c = 17.5 K.}