Interactions between two aromatic rings with various substituents in a near-sandwich configuration havebeen quantitatively studied by using the triptycene derived molecular models. This model system allowsa stacking arrangement of two arenes to assume a near-perfect face-to-face configuration in its groundstate conformation. Comparing to our previous study of the parallel displaced configuration, repulsiveinteractions are predominant for most arenes currently studied. However, if one arene is strongly electrondeficient (Ar
2 = pentafluorobenzoate), attractive interactions were observed regardless of the characterof the other arene (Ar
1). For stacking interactions between Me
2NC
6H
4 and C
6F
5CO groups, a
H of-1.84 ± 0.2 kcal/mol and a
S of -2.9 ± 0.8 cal/(mol·K) were determined. The general trend in theattractive stacking interaction toward a pentafluorobenzoate is Me
2NC
6H
4 > Me
3C
6H
2 > Me
2C
6H
3 >MeC
6H
4 > MeOC
6H
4 > C
6H
5 > O
2NC
6H
4. The observed trend is consistent with a donor-acceptorrelationship and the acceptor is a C
6F
5CO group.