POMs无机—有机杂化材料的水热合成

【作者】 鹿颖；

【导师】 王恩波；

【作者基本信息】 东北师范大学 ， 无机化学， 2002， 硕士

【摘要】 本文利用水热技术，通过调节反应条件和反应原料合成了五种未见文献报道的钒氧及钒磷氧无机一有机杂化材料：[{Mn（phen）₂}₂V₄O₁2]·1/2H₂O 1，[{Co（phen）₂}₂V₄O₁2]·H₂O 2，[Zn（2,2’-bipy）₃]₃[V₁5O₃6Cl)·3H₂O 3，[Co（2,2’-bipy）₃]₃[V₁5O₃6Cl]·3H₂O 4，(V₄O₇（HPO₄）₂（2,2’-bipy）₂]5。利用单晶X-ray衍射测定了这五种化合物的结构，并对影响钒氧、钒磷氧骨架结构的因素进行了探讨。化合物1和2是由共价键连着两个[M（phen）₂]²+碎片（M=Mn，Co）的V₄O₁2⁴-簇组成的双金属簇化合物。这两个化合物的V₄O₁2⁴-簇具有不同的结构，化合物1中的V₄O₁2⁴-簇为椅式构型，而化合物2中的V₄O₁2⁴-簇为船式构型。在这两个化合物中，孤立的双金属簇之间通过phen基团间的π-π相互作用进一步延展成有趣的三维超分子结构。化合物3和4是两个笼形混价多氧钒酸盐。它们具有相同的包裹着Cl-离子的笼形[VIV8Vv7O36Cl]6-钒氧簇。化合物5是一层状钒磷酸盐化合物。该化合物具有独特的4，6，8-网层状结构，有机配体2，2’-bipy直接配位于层上并伸向层间区域。相邻的层通过其间的2，2’-bipy基团的π-π堆积作用而稳定的堆积在一起，显示了一个有趣的三维超分子结构。同时，在本文中还通过元素分析、红外光谱、电子自旋共振波谱和热重分析等手段对上述五种化合物进行了表征。更多还原

【Abstract】 In this paper, five novel V-O and V-P-O inorganic-organic hybrid materials [{Mn（phen）₂}₂V₄O₁2]·1/2H₂O 1，[{Co（phen）₂}₂V₄O₁2]·H₂O 2，[Zn（2,2’-bipy）₃]₃[V₁5O₃6Cl)·3H₂O 3，[Co（2,2’-bipy）₃]₃[V₁5O₃6Cl]·3H₂O 4，(V₄O₇（HPO₄）₂（2,2’-bipy）₂] 5 have been hydrothermally synthesized through moditying synthetic conditions and starting materials. Structures of the five complexes have been determined by single crystal X-ray diffraction, and the influencing factors on V-O and V-P-O framework have been discussed. Both complexes 1 and 2 are bimetallic cluster complexes which are composed of discrete V40i24" clusters covalently attached to two [M（phen）2]2+ （ M = Mn, Co ） fragments. The V4Oi24" clusters in the two complexes possess different structures, which exhibit chair-like configuration in complex 1 while boat-like configuration in complex 2. In these two complexes, the discrete bimetallic clusters are further extended into interesting three-dimensional supermolecular arrays via n-n stacking interactions of phen groups. Complexes 3 and 4 are two cage-like mixed-valent polyoxovanadates, which possess the same oxo vanadium clusters composed of spherical [VIV8VV7036C1]6" cage with a Cl" ion encapsulated. Complexe 5 is a layered vanadium phosphate, which exhibits an unique 4,6,8-net structure with organonitrogen donors of 2,2’-bipy ligand directly coordinated to the vanadium phosphate framework. The adjacent layers of this complexes are stably packed together to form an interesting 3D supramolecular array through TT-TC stacking interactions between 2,2’-dipy groups. Other characterizations for these five complexes by elemental analysis, IR, ESR and thermal analysis have also been described.更多还原