Table S1 The relative energies EMP2 (kJ/mol) of the 46 stable conformers of gaseous Hasp-at the level of MP2/aug-cc-pvdz//B3LYP/6-311++G**.

No. / EMP2a / No. / EMP2 / No. / EMP2 / No. / EMP2 / No. / EMP2
1 / 0.00 / 11 / 44.18 / 21 / 67.07 / 31 / 74.45 / 41 / 88.30
2 / 1.13 / 12 / 48.12 / 22 / 67.32 / 32 / 74.65 / 42 / 89.46
3 / 5.84 / 13 / 62.47 / 23 / 68.91 / 33 / 75.09 / 43 / 91.60
4 / 6.66 / 14 / 63.46 / 24 / 69.67 / 34 / 75.23 / 44 / 92.86
5 / 11.21 / 15 / 63.82 / 25 / 69.70 / 35 / 75.43 / 45 / 93.02
6 / 13.01 / 16 / 64.01 / 26 / 70.60 / 36 / 77.99 / 46 / 98.07
7 / 16.90 / 17 / 65.47 / 27 / 71.31 / 37 / 80.43
8 / 19.25 / 18 / 66.57 / 28 / 71.64 / 38 / 81.14
9 / 33.05 / 19 / 66.61 / 29 / 72.21 / 39 / 83.72
10 / 36.26 / 20 / 66.86 / 30 / 73.63 / 40 / 84.05

a EMP2stands for thesingle-point energy of each conformer relative to the most stable one Hasp-endo/D[a g] at the level of MP2/aug-cc-pvdz//B3LYP/6-311++G**.The single-point energy of the conformer Hasp-endo/D[a g]is computed to be -510.571506 Hartreeat this level.

Table S2 The relative energies EZPE (kJ/Mol) of the 28 stable conformers of gaseous[Hasp-Al(H2O)5]2+, obtained at the level of B3LYP/6-311++G**

No. / EZPE a / No. / EZPE / No. / EZPE / No. / EZPE / No. / EZPE
1 / 0.00 / 7 / 52.98 / 13 / 89.60 / 19 / 95.89 / 25 / 158.56
2 / 12.25 / 8 / 56.96 / 14 / 89.82 / 20 / 114.97 / 26 / 181.17
3 / 31.54 / 9 / 58.81 / 15 / 90.27 / 21 / 118.27 / 27 / 184.45
4 / 46.04 / 10 / 81.08 / 16 / 90.83 / 22 / 129.46 / 28 / 191.18
5 / 47.91 / 11 / 88.16 / 17 / 93.67 / 23 / 143.93
6 / 48.72 / 12 / 89.55 / 18 / 94.94 / 24 / 153.91

a EZPErepresents the zero-point corrected energy of each conformer relative to the most stable conformer 1at the level of B3LYP/6-311++G**. The total energy and zero-point energy of conformer 1are computed to be -1136.327069Hartree and 640.85kJ/mol at this level, respectively.

Table S3 The relative energies EZPE (kJ/mol) of the 38 stable conformers of gaseous [Asp-Al(H2O)5]+, obtained at the level of B3LYP/6-311++G**

No. / EZPEa / No. / EZPE / No. / EZPE / No. / EZPE / No. / EZPE
1 / 0.00 / 9 / 30.83 / 17 / 45.72 / 25 / 70.99 / 33 / 88.48
2 / 1.32 / 10 / 32.93 / 18 / 47.92 / 26 / 71.29 / 34 / 100.75
3 / 2.40 / 11 / 38.79 / 19 / 52.90 / 27 / 76.91 / 35 / 105.78
4 / 3.07 / 12 / 40.19 / 20 / 53.59 / 28 / 77.74 / 36 / 135.85
5 / 23.17 / 13 / 41.28 / 21 / 55.52 / 29 / 80.53 / 37 / 137.14
6 / 24.87 / 14 / 43.98 / 22 / 55.62 / 30 / 81.07 / 38 / 393.54
7 / 27.14 / 15 / 44.53 / 23 / 65.85 / 31 / 81.35
8 / 30.46 / 16 / 44.64 / 24 / 68.47 / 32 / 81.80

a EZPErepresents the zero-point corrected energy of each conformer relative to the most stable oneconformer 1at the level of B3LYP/6-311++G**. The total energy and zero-point energy of conformer 1are computed to be -1136.062960Hartree and 610.94kJ/mol at this level, respectively.