1,2,4-Triazole functionalized adamantanes: A new library of polydentate tectons for designing structures of coordination polymers

摘要

A series of functionalized adamantanes: 1,3-bis(1,2,4-triazol-4-yl)(tr _2ad); 1,3,5-tris(1,2,4-triazol-4-yl)-(tr 3ad); 1,3,5,7-tetrakis(1,2,4-triazol-4-yl)adamantanes (tr _4ad) and 3,5,7-tris(1,2,4-triazol-4-yl)-1-azaadamantane (tr _3ada) were developed as a new family of geometrically rigid polydentate tectons for supramolecular synthesis of framework solids. The coordination compounds were prepared under hydrothermal conditions; their structures reveal a special potential of the triazolyl adamantanes for the generation of highly-connected and open frameworks as well as structures based upon polynuclear metal clusters assembled with short-distance N _1,N _2-triazole bridges. Complexes [Cd{L} _2]A·nH _2O [L = tr 3ad, A = 2NO _3 - (4), CdCl _4 ~(2-) (5); L = tr 3ada, A = CdI _4 ~(2-) (7)] are isomorphous and adopt a layered 3,6-connected structure of CdI _2 type. [{Cu _3(OH)} _2(SO _4) _5(H _2O) _2{tr _3ad} _3]·26H _2O (6) is a layered polymer based upon Cu _3(μ _3-OH) nodes and trigonal tr _3ad links. In [Cu _3(OH) _2{tr _3ada} _2(H _2O) _4](ClO _4) _4 (8), [Cu _2{tr _3ada} _2(H _2O) _3](SO _4) _2·7H _2O (9) and [Cd _2{tr 3ada} _3]Cl _4· 28H _2O (10) (UCl _3-type net) the organic tripodal ligands bridge polynuclear metal clusters. Complexes [Ag{tr _4ad}]NO _3·3.5H _2O (11) and [Cu{tr _4ad}(H _2O)](ClO _4) _2·3H _2O (12) have _3D SrAl _2-type frameworks with the metal ions and adamantane tectons as topologically equivalent tetrahedral nodes, while in [Cd _3Cl _6{tr _4ad} -2]·9H _2O (13) the ligands bridge trinuclear six-connected Cd _3Cl _6(μ-tr) _4(tr) _2 clusters. In the compounds [Cd _2{tr _2ad} _4(H _2O) -4](CdBr -4) -2·2H -2O (2) and [Cd{tr _2ad} _4{CdI _3} _2]·4H _2O (3) the bitopic ligands provide simple links between the metal ions, while in [Ag _2{tr -2ad} _2](NO _3) _2· 2H _2O (1) the ligand is tetradentate and generates a 3D framework.