Molecular tectonics: dimensionality and geometry control of silver coordination networks based on pyrazolyl appended thiacalixarenes

Combinations of six new coordinating tectons ( 3–8 ) tetrakis-pyrazolyl appended calix[4]arenes, blocked in 1,3-A conformation, based on 1 (tetrathiacalix[4]arene) and 2 (tetrathiatetramercaptocalix[4]arene) derivatives, with AgX salts (X = NO 3 − , BF 4 − , XF 6 − (X = P, As and Sb)) lead to nine new silver coordination networks. The flexible nature of tectons 3–8 (length of the spacer between the macrocycle and the pyrazolyl coordinating unit), their high number of potential coordinating sites and the loose coordination demand of Ag + cation lead to the formation of a large variety of networks with different dimensionality: from 1D ( 5 -AgSbF 6 , 5 -AgBF 4 , 7 -AgSbF 6 and 8 -AgNO 3 ) to extended 2D ( 6 -AgBF 4 and 8 -AgSbF 6 ) and to a series of three isostructural porous diamond-like 3D architectures ( 6 -AgXF 6 (X = P, As and Sb)).