Metal-organic frameworks (MOFs), a hybrid class of materials comprising inorganic nodes and organic struts, have potential application in many areas due to their high surface areas and uniform pores and channels. One of the key challenges to be overcome in MOF synthesis is the strong propensity for catenation (growth of multiple independent networks within a given crystal), as catenation reduces cavity sizes and diminishes porosity. Here we demonstrate that rational design of organic building blocks, which act as strut-impervious scaffolds, can be exploited to generate highly desired noncatenated materials in a controlled fashion.