在单晶X射线衍射实验的基础上,对孔道结构化合物V9P8-en的类质同象物V9(P,B)8-en的晶体结构和晶体化学进行了深入研究.结果表明,该化合物的晶体学数据为:P2(1)/n,a=1.43134(9)nm,b=1.01256(6)nm,c=1.83156(12)nm,β=90.280(2)°,V=2.6545(3)nm3,Z=2,R=0.0540,wR2=0.1551.结构中,沿着三个结晶轴方向发育复杂而规整的三维孔道,最大孔径达1.83nm(∥b轴),质子化乙二胺和水分子居于孔道中.硼部分替代四面体配位的磷,替代率为B8:P8=0.1838:7.8162;其中B与{P-OH}位P的替代量大于与[P-O]位P的替代量.相对于V9P8-en来说,V9(P,B)8-en的晶胞参数发生了变化,导致b轴增长(1.0150→1.0256nm)和c轴缩短(1.8374→1.8316nm),同时β角变小(90.39→90.278(2)°).二者的化学计量比也不同,体现在结构与孔容的关系、电荷平衡、满足亲水-疏水作用的结晶水的数量及有机模板分子的赋存状态等方面都有差异.
参考文献
[1] | Sch(u)th F;Schmidt W .Advanced Materials Progress Report on Microporous and Mesoporous Materials[J].Advanced Materials,2002,14(09):629-639. |
[2] | Myriam Riou-Cavellec;Didier Riou;Gerard Ferey .Magnetic iron phosphates with an open framework[J].Inorganica Chimica Acta,1999(1/2):317-325. |
[3] | Finn R C;Zubieta J;Haushalter R C .Crystal Chemistry of Organically Templated Vanadium Phosphates and Organophosphonates[J].Progress in Inorganic Chemistry,2003,51:421-601. |
[4] | SOGHOMONIAN V;Chen Q;Haushalter R C .Vanadium Phosphate Framework Solid Constructed of Octahedra, Square Pyramids, and Tetrahedra with a Cavity Diameter of 18.4A[J].Angewandte Chemie International Edition,1993,32:610-611. |
[5] | Roca M.;Amoros P.;Beltranporter A.;Edwards AJ. Beltranporter D.;Marcos MD. .SYNTHETIC STRATEGIES TO OBTAIN V-P-O OPEN FRAMEWORKS CONTAINING ORGANIC SPECIES AS STRUCTURAL DIRECTING AGENTS - CRYSTAL STRUCTURE OF THE V(IV)-FE(III) BIMETALLIC PHOSPHATE [H3N(CH2)(2)NH3](2)[H3N(CH2)(2)NH2][FE-III(H2O)(2)((VO)-O-IV)(8)(OH)(4)(HP O4[J].Inorganic Chemistry: A Research Journal that Includes Bioinorganic, Catalytic, Organometallic, Solid-State, and Synthetic Chemistry and Reaction Dynamics,1996(19):5613-5621. |
[6] | 杜洪兵,廖立兵,杨赞中,马哲生,熊明.新型磷酸钒孔道结构化合物(H3NCH2CH2NH3)3-[(VO)4(PO4)2(HPO4)4]的水热合成及结构表征[J].化学学报,2001(02):274-278. |
[7] | Zanzhong Yang,Libing Liao,Hongbing Du,Ming Xiong,Zhesheng Ma.Preparation and Composition-Structure-Thermal Stability Relation of a Novel Open-framework Vanadium Phosphate (H3NCH2CH2NH3)3[(VO)4(PO4)2(HPO4)4][J].北京科技大学学报(英文版),2002(01):36-39. |
[8] | 杨赞中,廖立兵,杜洪兵,熊明.三维孔道结构化合物V9P8-4en合成及热稳定性[J].材料科学与工艺,2003(02):123-127. |
[9] | Brown I D;Altermatt D .Bond-valence Parameters Obtained from a Systematic Analysis of the Inorganic Crystal Structure Database[J].Acta Crystallographica,1985,B41:244-247. |
[10] | Brown I D .The Bond-valence Method: An Empirical Approach to Chemical Structure and Bonding[J].Structure and Bonding,1981,11:1-30. |
[11] | Zavalij P Y;Whittingham M S .Lead Article: Structural Chemistry of Vanadium Oxides with Open Frameworks[J].Acta Crystallographica,1999,B55:627-663. |
[12] | S. Boudin;A. Guesdon;A. Leclaire;M.-M. Borel .Review on vanadium phosphates with mono and divalent metallic cations: syntheses, structural relationships and classification, properties[J].International journal of inorganic materials,2000(6):561-579. |
上一张
下一张
上一张
下一张
计量
- 下载量()
- 访问量()
文章评分
- 您的评分:
-
10%
-
20%
-
30%
-
40%
-
50%