A dearomatization/aromatization strategy accesses the tetrahedral (crosslike) pentacene tetramer (tetrakis(4-((6,13-bis(TIPS-ethynyl)-pentacen-2-yl) ethynyl) phenyl) silane). This molecular caltrop and one of its derivatives form amorphous thin films, demonstrating the impact of the 3D-tetramerization on the bulk morphology of the otherwise crystalline TIPS-pentacene.