Three Polymorphic Forms of a Monomeric Mo(VI) Complex: Building Blocks for Two Metal鈥揙rganic Supramolecular Isomers. Intermolecular Interactions and Ligand Substituent Effects

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• 作者：Vi拧nja Vrdoljak ; Biserka Prugove膷ki ; Dubravka Matkovi膰-膶alogovi膰 ; Tomica Hrenar ; Renata Dreos ; Patrizia Siega
• 刊名：Crystal Growth & Design
• 出版年：2013
• 出版时间：August 7, 2013
• 年：2013
• 卷：13
• 期：8
• 页码：3773-3784
• 全文大小：544K
• 年卷期：v.13,no.8(August 7, 2013)
• ISSN：1528-7505

文摘

Three polymorphic forms of the molybdenum(VI) complex [MoO₂(L)(EtOH)] (1伪, 1尾, and 1纬) (L^{2鈥?/sup> = 4-methoxy-2-oxybenzaldehyde isonicotinylhydrazonate) were synthesized by the reaction of H₂L with the dioxobis(acetylacetonato)molybdenum(VI) complex, [MoO₂(acac)₂], in ethanol. Removal of the coordinated ethanol molecule upon grinding or heating led to the solid-state transformation of the polymorphs 1伪, 1尾, or 1纬 into the coordination polymer [MoO₂(L)]_n (2a). The square inclusion complex [MoO₂(L)]₄CH₂Cl₂路4CH₂Cl₂ (2bCH₂Cl₂路4CH₂Cl₂) was obtained by a self-assembly reaction in dichloromethane. Standard Gibbs energies of binding for molybdenum(VI) compounds [MoO₂(L)(D)] with the sixth coordination site occupied by a nitrogen or an oxygen donor D were estimated using quantum chemical calculations. Crystal and molecular structures of the molybdenum(VI) compounds [MoO₂(L)(EtOH)] (1伪, 1尾, and 1纬), [MoO₂(L)]₄CH₂Cl₂路4CH₂Cl₂ (2bCH₂Cl₂路4CH₂Cl₂), [MoO₂(L)(纬-pic)]路纬-pic (3路纬-pic), [MoO₂(L)(py)] (4), and [MoO₂(L)(DMSO)] (5) were determined by the single crystal X-ray diffraction method. The compounds were further characterized by chemical analysis, thermogravimetric, and differential scanning calorimetry measurements, IR, UV鈥搗is, one- and two-dimensional NMR spectroscopies, and the powder X-ray diffraction method.}