Design of Layered Crystalline Materials Using Coordination Chemistry and Hydrogen Bonds
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- 作者：John C. MacDonald ; Pieter C. Dorrestein ; Malissa M. Pilley ; Mary M. Foote ; Jaina L. Lundburg ; Robert W. Henning ; Arthur J. Schultz ; and Jamie L. Manson
- 刊名：Journal of the American Chemical Society
- 出版年：2000
- 出版时间：November 29, 2000
- 年：2000
- 卷：122
- 期：47
- 页码：11692 - 11702
- 全文大小：595K
- 年卷期：v.122,no.47(November 29, 2000)
- ISSN：1520-5126
文摘
The supramolecular chemistry and crystal structures of five bis(imidazolium 2,6-pyridinedicarboxylate)M(II) trihydrate complexes, where M = Mn2+, Co2+, Ni2+, Cu2+, or Zn2+ (1-5, respectively), are reported.These complexes serve as supramolecular building blocks that self-assemble when crystallized to generate asingle, well-defined, predictable structure in the solid state. 2,6-Pyridinedicarboxylate anions and imidazoliumcations form strong ionic hydrogen bonds that dominate crystal packing in compounds 1-5 by forming two-dimensional networks, or layers of molecules. This layer motif serves as a platform with which to control andpredict molecular packing by design for engineering the structures of crystals. Moreover, compounds 1-5create a robust organic host lattice that accommodates five different transition metals without significantlyaltering molecular packing. Growth of crystals from solutions that contain two or more different metal complexesproduces mixed crystals in which mixtures of the different metal complexes are incorporated in the samerelative molar ratio present in solution. Epitaxial growth of crystals from one metal complex on the surface ofa seed crystal that contains a second metal complex generates composite crystals in which the different metalcomplexes are segregated into different regions of the crystals. Compounds 1-5 form crystalline solids thatrepresent a new class of modular materials in which the organic ligands serve as a structural component thatdefines a single packing arrangement that persists over a range of structures, and in which the metal serves asan interchangeable component with which to vary the physical properties of the material.