Ab Initio and DFT Computational Study …
229
corresponding conformers of c-DBPO and t-DBPO are somewhat different within
the HF results or the DFT results, whereas they are very close in the MP2 results.
The distance between the donor H atom and the closest C atom in the acceptor
aromatic B ring for the O–H···π interaction (Tables S94–S96; Figs. S87–S89) has
mostly very close values for corresponding conformers of the three molecules, with
the greatest discrepancy being ≈0.007 Å in the HF results. While the values for
corresponding conformers of c-DBPO and t-DBPOdiffer sufficiently in the HF and
DFT results to give clearly different curves in the diagrams, they are so close in the
MP2 results as to yield two mostly indistinguishable curves.
The values of the dipole moment (Tables S97–S99; Figs. S90–S92) are mostly
very close for corresponding conformers of the three molecules, in the results of each
method. Discrepancies involve differences smaller than 0.3 D in the HF and MP2
results, and smaller than 0.4 D in the DFT results.
The HOMO-LUMO energy gaps (Tables S100–S102; Figs. S93–S95) are also
mostly close for corresponding conformers of the three molecules. Some discrepancies appear for d-r-η-p-a-e-j-2y and d-r-η-p-a-e-j-2z, where the gap is smaller for
c-DBPO and t-DBPO than for MYRA. The curves for c-DBPO and t-DBPO are
much closer in the HF and MP2 results, and differ more in the DFT results.
Comparisons of the properties of corresponding conformers in the three solvents
considered may only concern MYRA, c-DBPO and t-DBPO, because calculations
in solution were not made for MODL, as they are more meaningful for actual
molecules. Comparison tables and figures consider individual properties for each
solvent, resulting in three tables for each property (in chloroform, in acetonitrile and
in water).
Tables S103–S121 and Figs. S96–S113 consider conformers with the same geometry of R and different geometries of ABDE. The relative energies (Tables S103–
S105; Figs. S96–S98) of corresponding conformers of the three molecules are very
close in the same solvent, and the corresponding curves overlap for most conformers,
or are close where they do not overlap. A discrepancy appears only for s-w-ε-q-b-f-k,
whose relative energy is higher for t-DBPO than for MYRA and c-DBPO.
Both the length of the first IHB (Tables S106–S108; Fig. S99–S101) and the
distance between the donor H atom and the closest C atom in the acceptor aromatic
B ring for the O–H···π interaction (Tables S109–S111; Figs. 102–S104) are very
close for corresponding conformers in each of the solvents. The curves highlighting
their trends largely overlap, and remain very close where they do not overlap. Similar
considerations hold for the values of the dipole moment of corresponding conformers
(Tables S112–S114; Figs. S105–S107) and for the values of their HOMO-LUMO
energy gaps (Tables S115–S117; Fig. S108–S110).
The free energy of solvation (Tables S118–S120, with synopsis in Table 121, and
Fig. S111–S113) is negative in chloroform, with greater magnitude for t-DBPO and
closer values for MYRA and c-DBPO. It is positive in acetonitrile, with the values for
c-DBPO being slightly higher than those of corresponding conformers of t-DBPO
and MYRA, and the values for t-DBPO and MYRA being closer to each other. The
values for water solution are considerably more negative than for chloroform, and
229
corresponding conformers of c-DBPO and t-DBPO are somewhat different within
the HF results or the DFT results, whereas they are very close in the MP2 results.
The distance between the donor H atom and the closest C atom in the acceptor
aromatic B ring for the O–H···π interaction (Tables S94–S96; Figs. S87–S89) has
mostly very close values for corresponding conformers of the three molecules, with
the greatest discrepancy being ≈0.007 Å in the HF results. While the values for
corresponding conformers of c-DBPO and t-DBPOdiffer sufficiently in the HF and
DFT results to give clearly different curves in the diagrams, they are so close in the
MP2 results as to yield two mostly indistinguishable curves.
The values of the dipole moment (Tables S97–S99; Figs. S90–S92) are mostly
very close for corresponding conformers of the three molecules, in the results of each
method. Discrepancies involve differences smaller than 0.3 D in the HF and MP2
results, and smaller than 0.4 D in the DFT results.
The HOMO-LUMO energy gaps (Tables S100–S102; Figs. S93–S95) are also
mostly close for corresponding conformers of the three molecules. Some discrepancies appear for d-r-η-p-a-e-j-2y and d-r-η-p-a-e-j-2z, where the gap is smaller for
c-DBPO and t-DBPO than for MYRA. The curves for c-DBPO and t-DBPO are
much closer in the HF and MP2 results, and differ more in the DFT results.
Comparisons of the properties of corresponding conformers in the three solvents
considered may only concern MYRA, c-DBPO and t-DBPO, because calculations
in solution were not made for MODL, as they are more meaningful for actual
molecules. Comparison tables and figures consider individual properties for each
solvent, resulting in three tables for each property (in chloroform, in acetonitrile and
in water).
Tables S103–S121 and Figs. S96–S113 consider conformers with the same geometry of R and different geometries of ABDE. The relative energies (Tables S103–
S105; Figs. S96–S98) of corresponding conformers of the three molecules are very
close in the same solvent, and the corresponding curves overlap for most conformers,
or are close where they do not overlap. A discrepancy appears only for s-w-ε-q-b-f-k,
whose relative energy is higher for t-DBPO than for MYRA and c-DBPO.
Both the length of the first IHB (Tables S106–S108; Fig. S99–S101) and the
distance between the donor H atom and the closest C atom in the acceptor aromatic
B ring for the O–H···π interaction (Tables S109–S111; Figs. 102–S104) are very
close for corresponding conformers in each of the solvents. The curves highlighting
their trends largely overlap, and remain very close where they do not overlap. Similar
considerations hold for the values of the dipole moment of corresponding conformers
(Tables S112–S114; Figs. S105–S107) and for the values of their HOMO-LUMO
energy gaps (Tables S115–S117; Fig. S108–S110).
The free energy of solvation (Tables S118–S120, with synopsis in Table 121, and
Fig. S111–S113) is negative in chloroform, with greater magnitude for t-DBPO and
closer values for MYRA and c-DBPO. It is positive in acetonitrile, with the values for
c-DBPO being slightly higher than those of corresponding conformers of t-DBPO
and MYRA, and the values for t-DBPO and MYRA being closer to each other. The
values for water solution are considerably more negative than for chloroform, and