Theoretical Basis.

To investigate the geometric and electronic properties of all of the compounds,

quantum calculations using the Gaussian 03 program have been performed.29 The calculations were
optimized using the restricted B3LYP/6-31 G (d) functions at the DFT level. The calculated typical
torsion angles of compounds 1a, 1b, 2b, and 4a−4d are listed in Table 2. As expected, the result of
geometry optimizations is consistent with the experimental data obtained from single-crystal structures.
For 1b, the calculated angle (2.49°) well agrees with the experimental data (2.83°). Conversely, the
calculated angle for 4c (26.33°) slightly deviates from the corresponding experimental data (16.78°).
The discrepancy between the calculation results and experimental data may have been caused by
intermolecular interactions in the latter. The calculated HOMOs and LUMOs of all of the compounds
are shown in Figures 4, S12, and S13. The density of all of the compounds in terms of HOMOs and
LUMOs was predominantly localized on the tetracyclic structure. The C−C condensation products
1a−1d exhibited stronger ICT character and effective electronic communication between the
diethylamino group and pyrazolopyridine core. This result was previously confirmed by the
photophysical properties.