Solid-state 13C NMR investigations of 4,7-dihydro-1H-tricyclopenta[def,jkl,pqr]triphenylene (sumanene) and indeno[1,2,3-cd]fluoranthene: Buckminsterfullerene moieties.
4,7-Dihydro-1H-tricyclopenta[def,jkl,pqr]triphenylene (sumanene) and indeno[1,2,3-cd]fluoranthene (indenofluoranthene) are structural moieties related to Buckminsterfullerene (C(60)). As such, understanding their structural characteristics is of great interest because of the insight they shed upon C(60). Hence, solid-state NMR (ssNMR) and ab initio quantum mechanical calculations with Gaussian03 are used in order to understand and to better characterize the molecular conformation and properties of sumanene and indenofluoranthene. Sumanene has bowl shaped curvature in its natural conformation and indenofluoranthene is planar in its natural conformation, which led us to examine how altering the curvature affects the chemical shifts in relation to those of C(60). Using X-ray structures of both sumanene and indenofluoranthene as our starting model, we calculate the energy and chemical shielding tensors and compare these data with those collected utilizing the (13)C ssNMR FIREMAT experiment. We define curvature of sumanene and indenofluoranthene using the pi-orbital axis vector (POAV) pyramidalization angle (theta(p)). We calculate the energy of varying conformations of indenofluoranthene versus their theta(p) associated with each deformed conformation.
Department of Chemistry, University of Utah, Salt Lake City, Utah 84112, USA.
Merrill D
MD
Halling
Anita M
AM
Orendt
Mark
M
Strohmeier
Mark S
MS
Solum
Vikki M
VM
Tsefrikas
Toshikazu
T
Hirao
Lawrence T
LT
Scott
Ronald J
RJ
Pugmire
David M
DM
Grant
D002247:Carbon Isotopes / Q000737:chemistry; D018360:Crystallography, X-Ray; D005449:Fluorenes / Q000737:chemistry*; D037741:Fullerenes / Q000737:chemistry*; D007192:Indenes / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008968:Molecular Conformation; D011084:Polycyclic Aromatic Hydrocarbons / Q000138:chemical synthesis / Q000737:chemistry*; D011789:Quantum Theory; D013816:Thermodynamics
D002247:Carbon Isotopes; D005449:Fluorenes; D037741:Fullerenes; D007192:Indenes; D011084:Polycyclic Aromatic Hydrocarbons; C505028:sumanene; C007738:fluoranthene