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. P3P6 forms both 1:1 and 2:1 complexes with C60 in the solid state. DFT reveals similar energies for the two binding modes. A 1:1 binding stoichiometry dominates in 1,2-dichlorobenzene-d4 at the millimolar concentrations dictated by solubility consideration. The solution phase interactions between rosarian and C60 were studied using 1H NMR, UV-vis, and femtosecond transient absorption spectroscopies in 1,2-dichlorobenzene-d4 or toluene. To our knowledge, this is the first report of an unfunctionalized porphyrinoid that forms a well-defined complex with C60 in solution as well as in solid state.
Bibliographical noteFunding Information:
Work in Austin was supported by the National Science Foundation (CHE-1402004 to J.L.S.) and the Robert A. Welch Foundation. Research at Yonsei University was supported by the Global Research Laboratory Program (2013K1A1A2A02050183) funded by the Ministry of Science, ICT & Future, Korea (D.K.). Quantum mechanical calculations were supported by the National Institute of Supercomputing and Network (NISN)/Korea Institute of Science and Technology Information (KISTI) with supercomputing resources including technical support (KSC-2015-C3-024).
© 2017 American Chemical Society.
All Science Journal Classification (ASJC) codes
- Colloid and Surface Chemistry