We have studied the supramolecular structures and photoelectronic properties of inclusion complexes of cyclic porphyrin dimers (M
2-CPD
Py, M=Ni, 2H) and fullerenes (C
60, C
70, PCBM ([6,6]-phenyl-C
61-butyric acid methyl ester) and Li
+@C
60). The porphyrin dimers have self-assembling 4-pyridyl groups at the meso positions and include fullerenes in their cavities with high affinities (
Kassoc≈10
5 M
-1). In crystals, C
60⊂Ni
2-CPD
Py and PCBM⊂Ni
2-CPD
Py give self-assembled porphyrin nanotubes containing the linear arrays of fullerene molecules. These self-assemblies are induced mainly by the non-classical hydrogen bonds between pyridyl nitrogens and porphyin β C-H groups. On the other hand, in the crystals of C
60⊂H
4-CPD
Py and C
70⊂H
4-CPD
Py, the included fullerene molecules show zigzag chains through van der Waals contacts with each other. Due to these well-ordered arrays of C
60, both crystals of C
60⊂Ni
2-CPD
Py and C
60⊂H
4-CPD
Py have high charge mobilities (Σμ>0.1 cm
2 V
-1 s
-1). C
60⊂H
4-CPD
Py shows photoinduced electron transfer from the porphyrin moieties to C
60 and photovoltaic activity with
IPCEmax=17% in photoelectrochemical cells. Moreover, the inclusion complexes of lithium-ion-encapsulated C
60(Li
+@C
60) and M
2-CPD
Py exhibit photoinduced charge separation with very long lifetimes reaching submillisecond order.
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