摘要:

IntroductionThe development of coordination polymer chemistry over recent years has led to the discovery of many unusual frameworks1and topological phenomena, such as interpenetration2and polyknotting,3using both d-4and more recently f-block metals.5It is clear that one of the key features of this chemistry is the development of the “building-block” methodology which will ultimately allow the rational construction of desired frameworks. Although significant advances have been made, the evolution of new building-blocks which increase predictability in a given system is still highly desirable. To this end we6as well as others7,8have used diketonate anions, which act as chelating ligands to many transition metals, not only to construct neutrally-charged coordinationpolymers but also to control the degree of polymeric propagation. As the diketonate anion blocks two coordination sites per metal positive charge, diketonate complexes are often one-dimensional. A recent study7reports an example of a one-dimensional helical polymer constructed using Mn(hfpd)2(hfpd = 1,1,1,5,5,5,-hexafluoro-2,4-pentanedionate) and 1,3-bis(4-pyridyl)propane in which the helical moieties interact to afford homochiral single crystals. The unusual homochiral arrangement is attributed to the intermeshing of the hfpd units on adjacent helical strands.We have previously studied the construction of one-dimensional coordination polymers using Ag(hfpd) and the thioether macrocycles 1,4,7-trithiacyclononane ([9]aneS3) and 1,4,8,11-tetrathiacyclotetradecane ([14]aneS4).6In these compounds the diketonate anions coordinate to the metal centre in a chelating fashion inhibiting polymeric propagation in all three dimensions and affording one-dimensional polymers in which the thioether macrocycles bridge Ag(i) centres. In this study we extend our investigations into the employment of asymmetric diketonate anions as coordination polymer building-blocks by using the Fod (2,2-dimethyl-6,6,7,7,8,8,8-heptafluoro-3,5-octanedionate) anion (Scheme 1).The diketonate anion used in this study, Fod, and hfpd used in previous studies.6

ISSN:1466-8033    

DOI:10.1039/b200491g

出版商:RSC    

年代:2002

数据来源: RSC