Expanded Rosarin: A Versatile Fullerene (C60) Receptor.
An expanded rosarian (P3P6) with a bowl-like conformation has been prepared and characterized in a one-pot procedure that involves condensing a bispyrrole pyridine precursor (P1P2) with benzaldehyde, followed by oxidation. Single crystal X-ray diffraction analysis reveals a bowl-like conformation in the solid state with an upper rim diameter defined by the meso-phenyl substituents of ca. 13.5 Å and a depth of roughly 6.3 Å. P3P6forms both 1:1 and 2:1 complexes with C60in the solid state. DFT reveals similar energies for the two binding modes. A 1:1 binding stoichiometry dominates in 1,2-dichlorobenzene-d4at the millimolar concentrations dictated by solubility consideration. The solution phase interactions between rosarian and C60were studied using1H NMR, UV-vis, and femtosecond transient absorption spectroscopies in 1,2-dichlorobenzene-d4or toluene. To our knowledge, this is the first report of an unfunctionalized porphyrinoid that forms a well-defined complex with C60in solution as well as in solid state.
Department of Chemistry, The University of Texas at Austin , Austin, Texas 78712-1224, United States.
Xian-Sheng
0000-0002-0562-1039
XS
Ke
Department of Chemistry, Yonsei University , Seoul 120-749, Korea.
Taeyeon
T
Kim
Department of Chemistry, The University of Texas at Austin , Austin, Texas 78712-1224, United States.
James T
JT
Brewster
Department of Chemistry, The University of Texas at Austin , Austin, Texas 78712-1224, United States.
Vincent M
VM
Lynch
Department of Chemistry, Yonsei University , Seoul 120-749, Korea.
Dongho
0000-0001-8668-2644
D
Kim
Department of Chemistry, The University of Texas at Austin , Austin, Texas 78712-1224, United States.
Jonathan L
0000-0002-9576-1325
JL
Sessler