A new class of C3‐symmetrical fullerene building blocks with a well‐defined spatial arrangement of addends has been developed. They comprise compounds with a e,e,e‐trisaddition pattern and a mixed octahedral hexakisaddition pattern. Fullerenophosphates with a e,e,e‐addition pattern were used for the spatial preorganization of the addends. After deprotection seven different trisbromides (12–16, 15a, 16a) with varying chain lengths and orientation of the functional groups were obtained. Acetylenes could be coupled to these compounds by click chemistry through an intermediate trisazide. For the synthesis of mixed hexakisadducts 19–21 a template system based on a central benzyl moiety was attached to the free hemisphere of the trisadduct fullerenophosphates. It was shown that the phosphate and the benzyl template can be removed independently. Fully deprotected building block 24 bearing both terminal bromide and hydroxy moieties was prepared. In addition, rather complex hybrid architecture 29 bearing three porphyrin units in the polar addend zone was successfully synthesized.

Scheme 1. Synthesis of phosphate trismalonates 8-12 with variable spacer length. a) pyridine or NEt 3 , 08C, THF; b) DHP, Dowex 50WX2,

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