3.2 Characteristics of Superalkali salts of Graphynes
The atomic charges on the OM3 subunits of
OM3@GYs (M = Li, Na, and K) were explored to analyze the
electron transfer. Charge calculations were performed by using five
methods including Merz-Kollman (MK), natural population analysis (NPA),
atoms in molecules
(AIM),54 atomic dipole
moment corrected Hirshfeld (ADCH)
population,55 and Becke
population52 (see Table
S1 in the ESI). Here, the MK charges are selected to show the electron
transfer, which are listed in Table 1. As shown in Table 1, the
superalkali subunits exhibit positive MK charges in the range of
0.473–1.011 |e |, indicating that the doping
superalkali donates electron to the GYs moiety. Molecular orbital (MO)
analysis shows that the frontier MOs are the contributions of GYs
(without OM3 contribution), also exhibiting the electron
transfer. Since these superalkali-doped systems have similar MO
character, the highest occupied molecular orbitals (HOMOs) of three
OLi3-doped model systems are taken as examples and
depicted in Figure 4. Therefore, the OM3@GYs complexes
are, in fact, superalkali salts of graphynes, and can be written as
OM3+@GYs–.