Theoretical and quantitative structural relationships of the electrochemical properties of Cis -unsaturated thiocrown ethers and n-type material bulk-heterojunction polymer solar cells as supramolecular complexes [X-UT-Y]@R (R=PCBM, p -EHO-PCBM, and p -EHO-PCBA)

AbstractSince the discovery of fullerenes as a class of nanostructure compounds, many potential applications have been suggested for their unusual structures and properties. The isolated pentagon rule (IPR) states that all pentagonal carbon rings are isolated in the most stable fullerene. Fullerenes Cn are a class of spherical carbon allotrope group with unique properties. Electron transfer between fullerenes and other molecules is thought to involve the transfer of electrons between the molecules surrounding the fullerene cage. One class of electron transfer molecules is the methanofullerene derivatives ([6,6]-phenyl C61-butyric acid methyl ester (PCBM), 4-(2-ethylhexyloxy)-[6,6]-phenyl C61-butyric acid methyl ester (p-EHO-PCBM), and 4-(2-ethylhexyloxy)-[6,6]-phenyl C61-butyric acid (p-EHO-PCBA), 10–12). It has been determined that C60 does not obey IPR. Supramolecular complexes 1–9 and 10–12 are shown to possess a previously unreported host–guest interaction for electron transfer processes. The unsaturated, cis-geometry, thiocrown ethers, (1–9) (described as [X-UT-Y], where X and Y indicate the numbers of carbon and sulfur atoms, respectively), are a group of crown ethers that display interesting physiochemical properties in the light of their conformational restriction compared with a corresponding saturated system, as well as the sizes of their cavities. Topological indices have been successfully used to construct mathematical methods that relate structural data to various chemical and physical properties. To establish a good relationship between the structures of 1–9with 10–12, a new index is introduced, μcs. This index is the ratio of the sum of the number of carbon atoms (nc) and the number of sulfur atoms (ns) to the product of these two numbers for 1–9. In this study, the relationships between this index and oxidation potential (oxE1) of 1–9, as well as the first to third free energies of electron transfer (Δ Get(n), for n=1−−3, which is given by the Rehm–Weller equation) between 1–9 and PCBM, p-EHO-PCBM, and p-EHO-PCBA (10–12) as [X-UT-Y]@R (where R is the adduct PCBM, p-EHO-PCBM, and p-EHO-PCBA group) (13–15) supramolecular complexes are presented and investigated.