Crystal-to-crystal transformations of a microporous metal organic laminated framework triggered by guest exchange, dehydration and readsorption

被引:165
作者
Zeng, MH
Feng, XL
Chen, XM [1 ]
机构
[1] Sun Yat Sen Univ, Sch Chem & Chem Engn, Guangzhou 510275, Peoples R China
[2] GuangXi Normal Univ, Dept Chem & Chem Engn, Res Inst Bioinorgan Chem, Guilin 541004, Peoples R China
关键词
D O I
10.1039/b404483p
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Single crystals of a neutral, microporous, laminated metal-organic framework (MOF) [Fe(pydc)(4,4'-bipy)].H2O (1.H2O) (H(2)pydc = 2,5-dicarboxypyridine, 4,4'-bipy = 4,4'-bipyridine) were generated by hydrothermal synthesis, and its crystal structure was determined. 1.H2O retains the framework robustness to ca. 370 degreesC and is insoluble in common organic solvents. By soaking in MeOH and EtOH solutions, 1.H2O was transformed directly from the parent single crystals into single crystals of 1.MeOH or 1.EtOH, respectively. Meanwhile, 1.H2O shrank to the guest-free framework 1(h) or 1(v), respectively, under appropriate heating (up to 160 degreesC in N-2) or vacuum treatment (10 mmHg) at room temperature. Compared to that of 1.H2O, the unit-cell volume of 1.EtOH slightly increases by 2.9%, whereas those of 1(h) or 1(v) are reduced by 8.2 and 6.6%, respectively. The anhydrous 1(v) was found to be highly chemically reactive, taking up ethanol vapor to furnish the solvated crystal structure of an 'expanded' framework 1.EtOH. In a mixture of ethanol-DMF or ethanol-benzene, a selective exchange process was observed, with only ethanol molecules exchanged into the structure due to the limited free size of the channels in the framework of 1. All the transformed crystals have also been characterized by X-ray single-crystal diffraction to understand the crystal-to-crystal transformation, which have different free volumes (6.5-20.4%).
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页码:2217 / 2223
页数:7
相关论文
共 77 条
[1]   TOPOLOGICAL REARRANGEMENT WITHIN A SINGLE-CRYSTAL FROM A HONEYCOMB [CD(CN)2]N3D NET TO A DIAMOND NET [J].
ABRAHAMS, BF ;
HARDIE, MJ ;
HOSKINS, BF ;
ROBSON, R ;
WILLIAMS, GA .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (26) :10641-10643
[2]  
Abrahams BF, 1998, ANGEW CHEM INT EDIT, V37, P2656, DOI 10.1002/(SICI)1521-3773(19981016)37:19<2656::AID-ANIE2656>3.0.CO
[3]  
2-M
[4]   Pillared derivatives of γ-zirconium phosphate containing nonrigid alkyl chain pillars [J].
Alberti, G ;
Murcia-Mascarós, S ;
Vivani, R .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (36) :9291-9295
[5]  
Barrer RM., 1982, HYDROTHERMAL CHEM ZE
[6]  
Biradha K, 2002, ANGEW CHEM INT EDIT, V41, P3392, DOI 10.1002/1521-3773(20020916)41:18<3392::AID-ANIE3392>3.0.CO
[7]  
2-V
[8]  
Biradha K, 2002, ANGEW CHEM INT EDIT, V41, P3395, DOI 10.1002/1521-3773(20020916)41:18<3395::AID-ANIE3395>3.0.CO
[9]  
2-D
[10]   Inorganic crystal engineering using self-assembly of tailored building-blocks [J].
Blake, AJ ;
Champness, NR ;
Hubberstey, P ;
Li, WS ;
Withersby, MA ;
Schröder, M .
COORDINATION CHEMISTRY REVIEWS, 1999, 183 :117-138