Table 2.
Full geometry optimisation of G-0 dendrons 2a, 3 [51–54], solvation energies of G-0 and G-1 dendrons 2a, 3, D-Cl, D-N<P>NH [54] and lone pair (LP) electron occupation of piperazine Nsp3 nitrogens in dendrons 3 and D-N<P>NH [56–57].
| No. | Relative conformational total electronic Energy ΔE (kJ mol−1)a in the gas phase in DMSO |
ΔG of solvation (kJ mol−1) for the (a–a) major rotamera | LP electron occupation of piperazine Nsp3 nitrogens (e)b |
||||
| (s–s) | (a–s) | (a–a) | THFc | 1,4-dioxaned | THF | 1,4-dioxane | |
| 2a | 10.464 17.371 |
8.329 15.558 |
0.000 0.000 |
−146.37 | −104.39 | – | – |
| 3 | 4.395 5.923 |
4.730 4.504 |
0.000 0.000 |
−167.54 | −122.51 | 1.92 | 1.92 |
| D-Cl | – | – | – | −378.66 | −284.28 | – | – |
| D-N<P>NH | – | – | – | −401.81 | −301.36 | 1.93 | 1.92 |
aSee Experimental and Supporting Information File 1 (pp. S40 ff) for details of this DFT calculation. bElementary electric charge carried by a single electron. cDielectric constant, ε = 7.4257. dDielectric constant, ε = 2.2099.