Table S1The geometrical parameters of aggregates of FHA and TFHA with MeNH2 at MP2/6-31+G* theoretical level.All the bond distances are in angstrom (Å), angles and dihedrals are in degrees ().
Parameters / 1Z MeNH2 I / Parameters / 1Z MeNH2 II / Parameters / 1Z MeNH2IIIFHA / TFHA / FHA / TFHA / FHA / TFHA
N2-C1 / 1.358 / 1.341 / N2-C1 / 1.359 / 1.342 / N2-C1 / 1.358 / 1.329
X3-C1 / 1.235 / 1.646 / X3-C1 / 1.234 / 1.646 / X3-C1 / 1.242 / 1.658
O4-N2 / 1.397 / 1.383 / O4-N2 / 1.398 / 1.384 / O4-N2 / 1.409 / 1.388
H5-O4 / 1.014 / 1.023 / H5-O4 / 1.014 / 1.021 / H5-O4 / 0.989 / 0.996
H6-C1 / 1.104 / 1.095 / H6-C1 / 1.104 / 1.095 / H6-C1 / 1.098 / 1.094
H7-N2 / 1.014 / 1.015 / H7-N2 / 1.015 / 1.015 / H7-N2 / 1.015 / 1.013
N8-H5 / 1.733 / 1.689 / N8-H5 / 1.739 / 1.698 / H8-X3 / 2.344 / 3.048
H9-N8 / 1.019 / 1.020 / H9-N8 / 1.020 / 1.020 / N9-H8 / 1.021 / 1.020
H10-N8 / 1.022 / 1.021 / H10-N8 / 1.023 / 1.022 / H10-N9 / 1.019 / 1.019
C11-N8 / 1.473 / 1.476 / C11-N8 / 1.472 / 1.474 / C11-N9 / 1.469 / 1.470
H12-C11 / 1.092 / 1.092 / H12-C11 / 1.097 / 1.096 / H12-C11 / 1.093 / 1.093
H13-C11 / 1.093 / 1.096 / H13-C11 / 1.092 / 1.092 / H13-C11 / 1.093 / 1.093
H14-C11 / 1.092 / 1.091 / H14-C11 / 1.092 / 1.092 / H14-C11 / 1.099 / 1.098
X3-C1-N2 / 125.6 / 128.0 / X3-C1-N2 / 125.7 / 128.2 / X3-C1-N2 / 121.3 / 123.4
O4-N2-C1 / 120.8 / 123.5 / O4-N2-C1 / 120.8 / 123.6 / O4-N2-C1 / 116.4 / 122.1
H5-O4-N2 / 104.1 / 104.8 / H5-O4-N2 / 103.9 / 105.2 / H5-O4-N2 / 101.5 / 101.5
H6-C1-N2 / 111.1 / 110.2 / H6-C1-N2 / 111.1 / 110.1 / H6-C1-N2 / 115.2 / 114.2
H7-N2-C1 / 120.0 / 121.6 / H7-N2-C1 / 119.7 / 121.3 / H7-N2-C1 / 121.2 / 126.0
N8-H5-O4 / 165.4 / 171.6 / N8-H5-O4 / 166.5 / 172.7 / H8-X3-C1 / 91.7 / 72.5
H9-N8-H5 / 121.7 / 119.7 / H9-N8-H5 / 115.5 / 115.3 / N9-H8-X3 / 131.7 / 117.9
H10-N8-H5 / 95.3 / 103.6 / H10-N8-H5 / 94.0 / 98.6 / H10-N9-H8 / 107.2 / 107.0
C11-N8-H5 / 110.1 / 105.8 / C11-N8-H5 / 117.3 / 114.2 / C11-N9-H8 / 109.9 / 110.0
H12-C11-N8 / 109.0 / 108.8 / H12-C11-N8 / 113.7 / 113.5 / H12-C11-N9 / 108.6 / 108.6
H13-C11-N8 / 113.6 / 113.4 / H13-C11-N8 / 108.5 / 108.5 / H13-C11-N9 / 109.0 / 108.9
H14-C11-N8 / 108.3 / 108.0 / H14-C11-H8 / 109.0 / 108.9 / H14-C11-N9 / 114.7 / 114.5
O4-N2-C1-X3 / 18.4 / 11.0 / O4-N2-C1-X3 / -18.8 / -12.2 / O4-N2-C1-X3 / -12.6 / 3.5
H5-O4-N2-C1 / -66.7 / -70.3 / H5-O4-N2-C1 / 67.0 / 69.7 / H5-O4-N2-C1 / 7.4 / -2.3
H6-C1-N2-O4 / 193.1 / 188.6 / H6-C1-N2-O4 / 166.6 / 170.5 / H6-C1-N2-O4 / 171.0 / 181.7
H7-N2-C1-X3 / -195.3 / -189.6 / H7-N2-C1-X3 / -164.2 / -170.1 / H7-N2-C1-X3 / -151.6 / -185.7
N8-H5-O4-N2 / 77.6 / 84.4 / N8-H5-O4-N2 / 307.3 / 302.9 / H8-O3-C1-N2 / 183.6 / 176.6
H9-N8-H5-X3 / -116.9 / -145.9 / H9-N8-H5-O4 / -122.5 / -138.4 / N9-H8-X3-C1 / -20.6 / -26.1
H10-N8-H5-X3 / -2.4 / -26.6 / H10-N8-H5-X3 / 11.1 / -29.8 / H10-N9-H8-X3 / 144.3 / 157.0
C11-N8-H5-O4 / 79.7 / 57.0 / C11-N8-H5-O4 / 104.5 / 92.2 / H11-N9-H8-X3 / 264.2 / 276.8
H12-C11-N8-O4 / 79.6 / 70.3 / H12-C11-N8-H10 / -60.8 / -61.7 / H12-C11-N9-H8 / 61.6 / 61.6
H13-C11-N8-O4 / 201.2 / 191.6 / H13-C11-N8-H10 / 60.1 / 59.1 / H13-C11-N9-H8 / 178.9 / 179.1
H14-C11-N8-O4 / 322.0 / 312.6 / H14-C11-N8-H10 / 177.7 / 177.0 / H14-C11-N9-H8 / 300.6 / 300.7
Table S2The geometrical parameters of aggregates of FHA and TFHA with MeNH2 at MP2/6-31+G* theoretical level.All the bond distances are in angstrom (Å), angles and dihedrals are in degrees ().
Parameters / 2Z MeNH2 I / Parameters / 2Z MeNH2 IIFHA / TFHA / FHA / TFHA
N2-C1 / 1.292 / 1.293 / N2-C1 / 1.292 / 1.294
X3-C1 / 1.334 / 1.742 / X3-C1 / 1.348 / 1.746
O4-N2 / 1.443 / 1.428 / O4-N2 / 1.439 / 1.424
H5-X3 / 1.020 / 1.368 / H5-X3 / 0.982 / 1.341
H6-C1 / 1.086 / 1.087 / H6-C1 / 1.084 / 1.088
H7-O4 / 0.974 / 0.976 / H7-O4 / 0.974 / 0.975
N8-H5 / 1.716 / 1.963 / N8-H6 / 2.456 / 2.383
C9-N8 / 1.473 / 1.470 / C9-N8 / 1.469 / 1.469
H10-N8 / 1.020 / 1.019 / H10-N8 / 1.019 / 1.019
H11-N8 / 1.019 / 1.019 / H11-N8 / 1.020 / 1.020
H12-C9 / 1.092 / 1.093 / H12-C9 / 1.093 / 1.093
H13-C9 / 1.097 / 1.098 / H13-C9 / 1.093 / 1.093
H14-C9 / 1.091 / 1.092 / H14-C9 / 1.099 / 1.099
X3-C1-N2 / 130.6 / 131.8 / X3-C1-N2 / 126.1 / 129.0
O4-N2-C1 / 109.9 / 111.4 / O4-N2-C1 / 108.0 / 111.2
H5-X3-C1 / 115.0 / 100.1 / H5-X3-C1 / 107.3 / 96.0
H6-C1-N2 / 115.2 / 113.6 / H6-C1-N2 / 117.7 / 114.3
H7-O4-N2 / 100.5 / 100.8 / H7-O4-N2 / 102.3 / 102.1
N8-H5-X3 / 169.7 / 168.2 / N8-H6-C1 / 123.6 / 128.7
C9-N8-H5 / 110.3 / 105.9 / C9-N8-H6 / 110.2 / 106.9
H10-N8-H5 / 116.1 / 125.0 / H10-N8-H6 / 133.9 / 136.8
H11-N8-H5 / 101.3 / 96.0 / H11-N8-H6 / 78.0 / 78.9
H12-C9-N8 / 108.7 / 108.7 / H12-C9-N8 / 108.5 / 108.5
H13-C9-N8 / 113.7 / 114.3 / H13-C9-N8 / 108.9 / 108.9
H14-C9-N8 / 108.1 / 108.3 / H14-C9-N8 / 114.7 / 114.7
O4-N2-C1-X3 / -0.0 / -0.3 / O4-N2-C1-X3 / -0.0 / -0.1
H5-X3-C1-N2 / 0.9 / 3.2 / H5-X3-C1-N2 / 0.3 / 0.7
H6-C1-N2-O4 / 180.1 / 180.1 / H6-C1-N2-O4 / 180.0 / 180.3
H7-O4-N2-C1 / 179.9 / 178.3 / H7-O4-N2-C1 / 180.4 / 180.6
N8-H5-X3-C1 / 168.4 / 140.3 / N8-H6-C1-N2 / 7.3 / 12.9
C9-N8-H5-X3 / -86.4 / -62.9 / C9-N8-H6-C1 / 84.6 / 78.3
H10-N8-H5-X3 / 40.6 / 67.7 / H10-N8-H6-C1 / 235.2 / 227.3
H11-N8-H5-X3 / 156.6 / 183.7 / H11-N8-H6-C1 / 337.5 / 330.6
H12-C9-N8-H5 / 67.2 / 75.2 / H12-C9-N8-H6 / -22.5 / -22.2
H13-C9-N8-H5 / 188.5 / 196.7 / H13-C9-N8-H6 / 94.8 / 95.1
H14-C9-N8-H5 / 309.8 / 318.0 / H14-C9-N8-H6 / 216.4 / 216.7
Table S3The geometrical parameters of aggregates of FHA and TFHA with MeNH2 at MP2/6-31+G* theoretical level.All the bond distances are in angstrom (Å), angles and dihedrals are in degrees ().
Parameters / 2Z MeNH2 III / Parameters / 2Z MeNH2 IVFHA / TFHA / FHA / TFHA
N2-C1 / 1.289 / 1.292 / N2-C1 / 1.291 / 1.293
X3-C1 / 1.355 / 1.750 / X3-C1 / 1.351 / 1.749
O4-N2 / 1.439 / 1.425 / O4-N2 / 1.441 / 1.426
H5-X3 / 0.982 / 1.341 / H5-X3 / 0.981 / 1.341
H6-C1 / 1.084 / 1.085 / H6-C1 / 1.087 / 1.090
H7-O4 / 0.974 / 0.975 / H7-O4 / 0.973 / 0.975
H8-X3 / 2.513 / 3.232 / N8-H6 / 2.279 / 2.250
N9-H8 / 1.019 / 1.019 / H9-N8 / 1.019 / 1.019
H10-N9 / 1.019 / 1.019 / H10-N8 / 1.019 / 1.019
C11-N9 / 1.469 / 1.471 / C11-N8 / 1.472 / 1.472
H12-C11 / 1.099 / 1.098 / H12-C11 / 1.092 / 1.092
H13-C11 / 1.093 / 1.092 / H13-C11 / 1.098 / 1.098
H14-C11 / 1.093 / 1.093 / H14-C11 / 1.093 / 1.092
X3-C1-N2 / 125.9 / 129.2 / X3-C1-N2 / 125.9 / 128.7
O4-N2-C1 / 108.0 / 111.2 / O4-N2-C1 / 108.0 / 111.2
H5-X3-C1 / 107.1 / 95.9 / H5-X3-C1 / 107.2 / 96.1
H6-C1-N2 / 120.2 / 117.0 / H6-C1-N2 / 118.3 / 115.4
H7-O4-N2 / 102.1 / 101.9 / H7-O4-N2 / 102.1 / 101.9
H8-X3-C1 / 95.8 / 86.5 / H8-H6-C1 / 154.7 / 163.6
N9-H8-X3 / 115.2 / 90.9 / H9-N8-H6 / 127.9 / 123.3
H10-N9-H8 / 107.1 / 106.5 / H10-N8-H9 / 106.4 / 106.3
C11-N9-H8 / 110.0 / 110.2 / C11-N8-H6 / 97.9 / 94.4
H12-C11-N9 / 114.7 / 114.6 / H12-C11-N8 / 108.7 / 108.7
H13-C11-N9 / 108.6 / 108.6 / H13-C11-N8 / 114.5 / 114.4
H14-C11-N9 / 108.8 / 108.7 / H14-C11-N8 / 108.6 / 108.7
O4-N2-C1-X3 / -0.0 / -0.3 / O4-N2-C1-X3 / -0.1 / -0.3
H5-X3-C1-N2 / 0.4 / -2.7 / H5-X3-C1-N2 / -0.3 / -2.9
H6-C1-N2-O4 / 180.2 / 180.5 / H6-C1-N2-O4 / 179.7 / 179.2
H7-O4-N2-C1 / 180.3 / 179.6 / H7-O4-N2-C1 / -181.3 / 178.3
H8-X3-C1-N2 / 179.1 / 196.1 / N8-H6-C1-N2 / 3.5 / -1.6
N9-H8-X3-C1 / 29.6 / 8.6 / H9-N8-H6-C1 / 161.0 / 140.1
H10-N9-H8-X3 / -158.4 / -149.0 / H10-N8-H9-H6 / -122.0 / -130.3
C11-N9-H8-X3 / 81.6 / 91.4 / C11-N8-H6-C1 / 37.4 / 22.2
H12-C11-N9-H8 / 58.9 / 59.0 / H12-C11-N8-H10 / 64.7 / 64.9
H13-C11-N9-H8 / -62.2 / -62.4 / H13-C11-N8-H10 / -57.1 / -57.0
H14-C11-N9-H8 / 180.5 / 180.5 / H14-C11-N8-H10 / 181.6 / 181.6
Table S4 Atomic charges (NPA) on atoms of FHA (TFHA) in their aggregates withmethylamine at MP2/6-31+G* theoretical level.
Species / C1 / N2 / X3 / O4 / H5 / H6 / H71Z / 0.636
(-0.019) / -0.426
(-0.341) / -0.732
(-0.251) / -0.616
(-0.603) / 0.535
(0.531) / 0.173
(0.242) / 0.430
(0.447)
1Z MeNH2 I / 0.650
(-0.007) / -0.436
(-0.369) / -0.749
(-0.258) / -0.655
(-0.647) / 0.557
(0.558) / 0.152
(0.227) / 0.423
(0.429)
1Z MeNH2 II / 0.649
(-0.009) / -0.439
(-0.372) / -0.746
(-0.253) / -0.654
(-0.647) / 0.557
(0.559) / 0.152
(0.227) / 0.423
(0.429)
1Z MeNH2III / 0.628
(-0.011) / -0.421
(-0.344) / -0.762
(-0.297) / -0.617
(-0.606) / 0.536
(0.531) / 0.205
(0.274) / 0.431
(0.446)
2Z / 0.478
(-0.099) / -0.282
(-0.197) / -0.783
(0.025) / -0.703
(-0.677) / 0.547
(0.176) / 0.214
(0.248) / 0.528
(0.524)
2Z MeNH2 I / 0.497
(-0.089) / -0.313
(-0.217) / -0.829
(-0.016) / -0.704
(-0.683) / 0.570
(0.215) / 0.202
(0.244) / 0.516
(0.517)
2Z MeNH2 II / 0.482
(-0.094) / -0.310
(-0.226) / -0.781
(0.024) / -0.704
(-0.678) / 0.545
(0.173) / 0.242
(0.277) / 0.525
(0.521)
2Z MeNH2III / 0.469
(-0.090) / -0.285
(-0.209) / -0.797
(0.010) / -0.708
(-0.681) / 0.547
(0.171) / 0.242
(0.272) / 0.527
(0.521)
2Z MeNH2 IV / 0.471
(-0.098) / -0.303
(-0.218) / -0.785
(0.014) / -0.709
(-0.682) / 0.544
(0.172) / 0.248
(0.281) / 0.524
(0.520)
Table S5 Important orbital interactions and second order delocalization energies E(2) in kcal mol-1 inaggregates of FHA (TFHA) with methylamine at MP2/6-31+G* theoretical level.
Species / nN2C1-X3 / nN2 πC1-X3 / nX3 C1-N2 / nX3 πC1-N2 / nO4 C1-N2 / nO4 πC1-N2 / nX3 O4-H5 / nO4 X3-H51Z / 14.98
(-) / 32.68
(145.34) / 29.25
(15.92) / -
(-) / 4.36
(6.56) / -
(-) / 1.24+5.36
(13.71) / -
(-)
1Z MeNH2 I / 6.36
(-) / 64.78
(140.50) / 29.96
(19.38) / -
(-) / 6.57
(6.11) / -
(-) / -
(-) / -
(-)
1Z MeNH2 II / 10.23
(19.19) / 52.08
(138.3) / 30.05
(19.36) / -
(-) / 6.62
(6.28) / -
(-) / -
(-) / -
(-)
1Z MeNH2III / 12.00
(-) / 39.95
(147.62) / 28.19
(15.34) / -
(-) / 4.39
(6.46) / -
(-) / 1.44+5.50
(13.52) / -
(-)
2Z / 13.50
(14.57) / -
(-) / 8.63
(6.45) / 54.42
(39.47) / -
(-) / 13.22
(18.29) / -
(-) / 5.06
(2.61)
2Z MeNH2 I / 14.84
(14.49) / -
(-) / 12.27
(7.94) / 63.93
(41.11) / -
(-) / 12.33
(16.03) / -
(-) / 2.19
(1.28)
2Z MeNH2 II / 12.91
(14.25) / -
(-) / 8.59
(6.47) / 55.52
(39.78) / -
(-) / 12.44
(16.98) / -
(-) / 5.22
(2.57)
2Z MeNH2III / 13.60
(15.03) / -
(-) / 5.20+15.80
(6.27) / 4.85+18.11
(37.90) / 4.47
(-) / 4.91
(17.27) / -
(-) / 5.44
(2.44)
2Z MeNH2 IV / 13.05
(14.52) / -
(-) / 8.23
(6.24) / 51.66
(38.54) / -
(-) / 11.68
(16.67) / -
(-) / 5.35
(2.56)
Table S6The geometrical parameters of aggregates of 1Z of FHA and TFHA with MeOH at MP2/6-31+G* theoretical level.All the bond distances are in angstrom (Å), angles and dihedrals are in degrees ().
Parameters / 1Z MeOH I / Parameters / 1Z MeOH II / Parameters / 1Z MeOH IIIFHA / TFHA / FHA / TFHA / FHA / TFHA
N2-C1 / 1.356 / 1.336 / N2-C1 / 1.350 / 1.327 / N2-C1 / 1.358 / 1.327
X3-C1 / 1.237 / 1.650 / X3-C1 / 1.244 / 1.659 / X3-C1 / 1.239 / 1.659
O4-N2 / 1.398 / 1.383 / O4-N2 / 1.405 / 1.386 / O4-N2 / 1.416 / 1.388
H5-O4 / 0.998 / 1.005 / H5-O4 / 0.989 / 0.995 / H5-O4 / 0.990 / 0.998
H6-C1 / 1.103 / 1.094 / H6-C1 / 1.097 / 1.091 / H6-C1 / 1.099 / 1.091
H7-N2 / 1.014 / 1.015 / H7-N2 / 1.014 / 1.013 / H7-N2 / 1.024 / 1.028
O8-H5 / 1.746 / 1.695 / H8-X3 / 1.965 / 2.506 / O8-H7 / 1.962 / 1.810
H9-O8 / 0.983 / 0.983 / O9-H8 / 0.979 / 0.977 / H9-O8 / 0.976 / 0.973
C10-O8 / 1.434 / 1.438 / C10-O9 / 1.428 / 1.430 / C10-O8 / 1.435 / 1.442
H11-C10 / 1.090 / 1.089 / H11-C10 / 1.090 / 1.090 / H11-C10 / 1.089 / 1.089
H12-C10 / 1.094 / 1.095 / H12-C10 / 1.097 / 1.096 / H12-C10 / 1.094 / 1.093
H13-C10 / 1.096 / 1.093 / H13-C10 / 1.096 / 1.096 / H13-C10 / 1.095 / 1.093
X3-C1-N2 / 125.7 / 128.6 / X3-C1-N2 / 121.3 / 123.5 / X3-C1-N2 / 122.3 / 124.0
O4-N2-C1 / 121.2 / 124.5 / O4-N2-C1 / 117.1 / 122.3 / O4-N2-C1 / 114.8 / 120.7
H5-O4-N2 / 104.3 / 105.4 / H5-O4-N2 / 101.8 / 102.0 / H5-O4-N2 / 101.7 / 101.6
H6-C1-N2 / 111.4 / 110.2 / H6-C1-N2 / 114.8 / 113.7 / H6-C1-N2 / 113.4 / 112.3
H7-N2-C1 / 120.3 / 122.2 / H7-N2-C1 / 122.5 / 126.2 / H7-N2-C1 / 122.6 / 127.5
O8-H5-O4 / 158.3 / 166.5 / H8-X3-C1 / 98.3 / 77.5 / O8-H7-N2 / 135.7 / 177.2
H9-O8-H5 / 91.0 / 93.9 / O9-H8-X3 / 149.1 / 141.5 / H9-O8-H7 / 89.2 / 116.7
C10-O8-H9 / 109.2 / 109.1 / C10-O9-H8 / 109.0 / 108.6 / C10-O8-H9 / 109.4 / 109.2
H11-C10-O8 / 106.5 / 106.4 / H11-C10-O9 / 106.6 / 106.4 / H11-C10-O8 / 106.2 / 105.9
H12-C10-O8 / 110.7 / 111.0 / H12-C10-O9 / 111.6 / 111.5 / H12-C10-O8 / 111.0 / 110.6
H13-C10-O8 / 111.3 / 110.5 / H13-C10-O9 / 111.6 / 111.5 / H13-C10-O8 / 111.3 / 111.1
O4-N2-C1-X3 / -18.8 / -9.5 / O4-N2-C1-X3 / -11.3 / -0.7 / O4-N2-C1-X3 / -12.3 / -0.2
H5-O4-N2-C1 / 66.4 / 65.4 / H5-O4-N2-C1 / 6.0 / -0.7 / H5-O4-N2-C1 / 6.5 / 0.3
H6-C1-N2-O4 / 166.4 / 172.2 / H6-C1-N2-O4 / 172.0 / 178.8 / H6-C1-N2-O4 / 171.4 / -180.1
H7-N2-C1-X3 / -165.0 / -175.7 / H7-N2-C1-X3 / -154.8 / -177.7 / H7-N2-C1-X3 / -147.1 / 180.0
O8-H5-O4-N2 / -59.4 / -56.7 / H8-X3-C1-N2 / 178.4 / 169.0 / O8-H7-N2-C1 / 132.5 / 145.6
H9-H5-O4-N2 / -12.1 / -5.8 / O9-H8-X3-C1 / 0.1 / 8.2 / H9-O8-H7-O4 / -1.5 / -72.6
C10-O8-H9-X3 / 260.3 / 133.7 / C10-O9-H8-H6 / 143.3 / 139.9 / C10-O8-H9-H7 / 219.6 / -137.1
H11-C10-O8-H9 / 176.5 / 183.2 / H11-C10-O9-H8 / 181.4 / 181.0 / H11-C10-O8-H9 / 180.0 / 179.3
H12-C10-O8-H9 / 295.2 / 302.4 / H12-C10-O9-H8 / 300.2 / 299.8 / H12-C10-O8-H9 / 298.5 / 297.7
H13-C10-O8-H9 / 57.3 / 64.6 / H13-C10-O9-H8 / 62.7 / 62.3 / H13-C10-O8-H9 / 61.0 / 60.6
Table S7The geometrical parameters of aggregates of 2Z of FHA and TFHA with MeOH at MP2/6-31+G* theoretical level.All the bond distances are in angstrom (Å), angles and dihedrals are in degrees ().
Parameters / 2Z MeOH I / Parameters / 2Z MeOH II / Parameters / 2Z MeOH IIIFHA / TFHA / FHA / TFHA / FHA / TFHA
N2-C1 / 1.291 / 1.293 / N2-C1 / 1.290 / 1.294 / N2-C1 / 1.288 / 1.292
X3-C1 / 1.337 / 1.745 / X3-C1 / 1.347 / 1.747 / X3-C1 / 1.357 / 1.750
O4-N2 / 1.442 / 1.430 / O4-N2 / 1.427 / 1.409 / O4-N2 / 1.436 / 1.424
H5-X3 / 0.999 / 1.349 / H5-X3 / 0.983 / 1.342 / H5-X3 / 0.982 / 1.342
H6-C1 / 1.085 / 1.087 / H6-C1 / 1.083 / 1.085 / H6-C1 / 1.083 / 1.085
H7-O4 / 0.974 / 0.976 / H7-O4 / 0.990 / 0.990 / H7-O4 / 0.974 / 0.975
O8-H5 / 1.737 / 2.094 / O8-H7 / 1.825 / 1.826 / O8-H6 / 2.590 / 2.320
H9-O8 / 0.976 / 0.976 / H9-O8 / 0.977 / 0.977 / H9-O8 / 0.974 / 0.973
C10-O8 / 1.437 / 1.432 / C10-O8 / 1.437 / 1.437 / C10-O8 / 1.430 / 1.436
H11-C10 / 1.089 / 1.090 / H11-C10 / 1.095 / 1.095 / H11-C10 / 1.096 / 1.095
H12-C10 / 1.094 / 1.095 / H12-C10 / 1.094 / 1.094 / H12-C10 / 1.096 / 1.095
H13-C10 / 1.095 / 1.097 / H13-C10 / 1.089 / 1.089 / H13-C10 / 1.090 / 1.090
X3-C1-N2 / 131.1 / 132.2 / X3-C1-N2 / 125.9 / 128.6 / X3-C1-N2 / 125.8 / 129.3
O4-N2-C1 / 110.7 / 111.7 / O4-N2-C1 / 108.5 / 111.9 / O4-N2-C1 / 107.9 / 111.2
H5-X3-C1 / 114.0 / 98.5 / H5-X3-C1 / 106.4 / 95.1 / H5-X3-C1 / 107.3 / 95.7
H6-C1-N2 / 115.2 / 113.4 / H6-C1-N2 / 119.1 / 115.5 / H6-C1-N2 / 119.8 / 116.3
H7-O4-N2 / 100.8 / 101.3 / H7-O4-N2 / 100.9 / 100.9 / H7-O4-N2 / 102.3 / 101.9
O8-H5-X3 / 172.4 / 152.5 / O8-H7-O4 / 149.7 / 150.3 / O8-H6-C1 / 112.2 / 126.2
H9-O8-H5 / 91.2 / 78.1 / H9-O8-H7 / 87.1 / 87.3 / H9-O8-H6 / 72.0 / 132.4
C10-O8-H9 / 109.4 / 108.6 / C10-O8-H9 / 108.7 / 108.7 / C10-O8-H9 / 108.9 / 108.8
H11-C10-O8 / 106.2 / 106.4 / H11-C10-O8 / 111.1 / 111.2 / H11-C10-O8 / 111.6 / 111.3
H12-C10-O8 / 110.7 / 111.4 / H12-C10-O8 / 110.9 / 110.9 / H12-C10-O8 / 111.6 / 111.5
H13-C10-O8 / 111.2 / 111.4 / H13-C10-O8 / 106.2 / 106.2 / H13-C10-O8 / 106.3 / 105.9
O4-N2-C1-X3 / -0.1 / -0.5 / O4-N2-C1-O3 / 0.1 / 0.1 / O4-N2-C1-X3 / -0.0 / 0.1
H5-X3-C1-N2 / 0.7 / 10.6 / H5-X3-C1-N2 / 0.7 / 1.0 / H5-X3-C1-N2 / -1.1 / -0.4
H6-C1-N2-O4 / 179.9 / 180.6 / H6-C1-N2-O4 / 180.2 / 180.1 / H6-C1-N2-O4 / 180.2 / 179.8
H7-O4-N2-C1 / 174.9 / 169.5 / H7-O4-N2-C1 / 182.2 / 181.0 / H7-O4-N2-C1 / 178.8 / 179.6
O8-H5-X3-C1 / 144.2 / 81.3 / O8-H7-O4-N2 / -2.8 / -3.5 / O8-H6-C1-N2 / 171.8 / 200.0
H9-O8-H5-O4 / 0.6 / 4.5 / H9-O8-H7-N2 / 6.1 / 6.2 / H9-O8-H6-X3 / -1.3 / -76.6
C10-O8-H9-O4 / 240.9 / 240.6 / C10-O8-H9-N2 / 114.3 / 114.8 / C10-O8-H9-X3 / 225.4 / 257.2
H11-C10-O8-H5 / 74.9 / 94.3 / H11-C10-O8-H7 / 38.0 / 38.1 / H11-C10-O8-H9 / -62.2 / -62.7
H12-C10-O8-H5 / 193.6 / 213.0 / H12-C10-O8-H7 / 160.4 / 160.5 / H12-C10-O8-H9 / 60.4 / 60.4
H13-C10-O8-H5 / 316.0 / 335.6 / H13-C10-O8-H7 / 279.0 / 279.1 / H13-C10-O8-H9 / 179.1 / 178.8
Table S8Atomic charges (NPA) in aggregates of 1Z and 2Z conformers of FHA (TFHA) withMeOH at MP2/6-31+G* theoretical level.
Species / C1 / N2 / X3 / O4 / H5 / H6 / H71Z / 0.636
(-0.019) / -0.426
(-0.347) / -0.732
(-0.251) / -0.616
(-0.603) / 0.535
(0.531) / 0.173
(0.242) / 0.430
(0.447)
1Z MeOH I / 0.656
(0.008) / -0.433
(-0.357) / -0.758
(-0.266) / -0.632
(-0.628) / 0.559
(0.560) / 0.161
(0.233) / 0.428
(0.435)
1Z MeOH II / 0.637
(-0.003) / -0.414
(-0.339) / -0.775
(-0.296) / -0.610
(-0.600) / 0.537
(0.532) / 0.199
(0.268) / 0.437
(0.449)
1Z MeOH III / 0.638
(-0.013) / -0.438
(-0.358) / -0.746
(-0.293) / -0.645
(-0.617) / 0.539
(0.528) / 0.173
(0.239) / 0.465
(0.485)
2Z / 0.478
(-0.099) / -0.282
(-0.197) / -0.783
(0.025) / -0.703
(-0.677) / 0.547
(0.176) / 0.214
(0.248) / 0.528
(0.524)
2Z MeOH I / 0.497
(-0.089) / -0.301
(-0.208) / -0.808
(0.018) / -0.716
(-0.695) / 0.568
(0.197) / 0.208
(0.249) / 0.524
(0.527)
2Z MeOH II / 0.483
(-0.096) / -0.315
(-0.225) / -0.786
(0.017) / -0.722
(-0.697) / 0.549
(0.181) / 0.210
(0.243) / 0.559
(0.557)
2Z MeOH III / 0.470
(-0.092) / -0.273
(-0.208) / -0.808
(0.016) / -0.705
(-0.681) / 0.554
(0.168) / 0.236
(0.271) / 0.529
(0.521)
Table S9 Important orbital interactions and second order electron delocalization energies E(2) in kcal mol-1for orbital interactions in aggregates of FHA (TFHA) with MeOH at MP2/6-31+G* theoretical level.
Species / nN2C1-X3 / nN2 πC1-X3 / nX3 C1-N2 / nX3 πC1-N2 / nO4 C1-N2 / nO4 πC1-N2 / nX3 O4-H5 / nO4 X3-H51Z / 14.98
(-) / 32.68
(145.34) / 29.25
(15.92) / -
(-) / 4.36
(6.56) / -
(-) / 1.24+5.36
(13.71) / -
(-)
1Z MeOH I / -
(-) / 91.13
(-) / 28.35
(16.25) / -
(-) / 6.31
(6.73) / -
(2.23) / -
(-) / -
(-)
1Z MeOH II / 9.47
(-) / 51.67
(152.51) / 27.53
(15.41) / -.
(-) / 4.65
(6.58) / -
(-) / 1.56+4.73
(2.13+12.08) / -
(-)
1Z MeOH III / 12.77
(-) / 37.70
(164.00) / 28.29
(14.89) / -
(-) / 3.89
(6.20) / -
(-) / 6.17
(1.85+15.43) / -
(-)
2Z / 13.50
(14.57) / -
(-) / 8.63
(6.45) / 54.42
(39.47) / -
(-) / 13.22
(18.29) / -
(-) / 5.06
(2.61)
2Z MeOH I / 15.24
(14.60) / -
(-) / 7.63+18.61
(6.79+4.03) / 7.12+20.80
(28.55) / -
(-) / 5.26
(10.31) / -
(-) / 1.67
(0.99)
2Z MeOH II / 13.35
(14.58) / -
(-) / 8.53
(6.36) / 54.81
(39.04) / -
(-) / 14.88
(21.06) / -
(-) / 5.98
(3.03)
2Z MeOH III / 13.73
(14.91) / -
(-) / 7.35
(6.16) / 42.75
(38.00) / -
(-) / 11.70
(17.17) / -
(-) / 5.51
(2.52)
Table S10The geometrical parameters of the aggregates of 1Z of FHA and TFHA with AcOH at MP2/6-31+G* theoretical level. All the bond distances are in angstrom (Å), angles and dihedrals are in degrees ().
Parameters / 1Z AcOH I / Parameters / 1Z AcOH II / Parameters / 1Z AcOH IIIFHA / TFHA / FHA / TFHA / FHA / TFHA
N2-C1 / 1.350 / 1.339 / N2-C1 / 1.361 / 1.343 / N2-C1 / 1.353 / 1.328
X3-C1 / 1.238 / 1.645 / X3-C1 / 1.234 / 1.644 / X3-C1 / 1.241 / 1.658
O4-N2 / 1.393 / 1.385 / O4-N2 / 1.401 / 1.390 / O4-N2 / 1.413 / 1.390
H5-O4 / 0.994 / 0.997 / H5-O4 / 0.985 / 0.988 / H5-O4 / 0.990 / 0.999
H6-C1 / 1.101 / 1.093 / H6-C1 / 1.102 / 1.094 / H6-C1 / 1.099 / 1.091
H7-N2 / 1.015 / 1.016 / H7-N2 / 1.015 / 1.015 / H7-N2 / 1.024 / 1.026
O8-H5 / 1.755 / 1.734 / O8-H5 / 1.908 / 1.828 / O8-H7 / 1.916 / 1.864
C9-O8 / 1.237 / 1.236 / H9-O8 / 0.994 / 0.991 / C9-O8 / 1.229 / 1.230
O10-C9 / 1.334 / 1.337 / C10-O8 / 1.367 / 1.372 / O10-C9 / 1.354 / 1.352
H11-O10 / 1.000 / 0.999 / O11-C10 / 1.219 / 1.218 / H11-O10 / 0.982 / 0.982
C12-C9 / 1.500 / 1.499 / C12-C10 / 1.502 / 1.501 / C12-C9 / 1.497 / 1.497
H13-C12 / 1.089 / 1.089 / H13-C12 / 1.089 / 1.089 / H13-C12 / 1.093 / 1.094
H14-C12 / 1.093 / 1.093 / H14-C12 / 1.094 / 1.094 / H14-C12 / 1.089 / 1.090
H15-C12 / 1.094 / 1.094 / H15-C12 / 1.093 / 1.093 / H15-C12 / 1.093 / 1.092
X3-C1-N2 / 125.6 / 128.1 / X3-C1-N2 / 125.4 / 128.3 / X3-C1-N2 / 122.3 / 123.8
O4-N2-C1 / 120.2 / 122.1 / O4-N2-C1 / 119.9 / 122.9 / O4-N2-C1 / 115.3 / 120.4
H5-O4-N2 / 104.8 / 105.7 / H5-O4-N2 / 104.7 / 105.3 / H5-O4-N2 / 101.4 / 101.4
H6-C1-N2 / 112.0 / 110.8 / H6-C1-N2 / 111.6 / 110.2 / H6-C1-N2 / 113.5 / 112.4
H7-N2-C1 / 120.9 / 121.6 / H7-N2-C1 / 120.0 / 121.6 / H7-N2-C1 / 123.3 / 128.0
O8-H5-O4 / 168.3 / 169.2 / O8-H5-O4 / 147.3 / 158.8 / O8-H7-N2 / 169.0 / 168.6
C9-O8-H5 / 123.2 / 119.6 / H9-O8-H5 / 93.7 / 98.1 / C9-O8-H7 / 124.4 / 124.1
O10-C9-O8 / 124.1 / 123.9 / C10-O8-H9 / 110.3 / 110.1 / O10-C9-O8 / 121.5 / 121.4
H11-O10-C9 / 110.8 / 110.7 / O11-C10-O8 / 122.6 / 122.2 / H11-O10-C9 / 106.9 / 107.0
C12-C9-O10 / 112.3 / 112.3 / C12-C10-O11 / 126.3 / 126.7 / C12-C9-O10 / 112.2 / 112.3
H13-C12-C9 / 109.6 / 109.6 / H13-C12-C10 / 109.3 / 109.3 / H13-C12-C9 / 109.5 / 108.8
H14-C12-C9 / 109.8 / 109.8 / H14-C12-C10 / 109.7 / 109.6 / H14-C12-C9 / 110.0 / 110.0
H15-C12-C9 / 109.2 / 109.2 / H15-C12-C10 / 109.8 / 109.9 / H15-C12-C9 / 109.0 / 109.7
O4-N2-C1-X3 / -17.0 / -13.4 / O4-N2-C1-X3 / 20.4 / 14.3 / O4-N2-C1-X3 / -11.3 / -2.1
H5-O4-N2-C1 / 77.7 / 443.6 / H5-O4-N2-C1 / -74.6 / -74.3 / H5-O4-N2-C1 / 7.3 / 1.1
H6-C1-N2-O4 / 167.2 / 168.9 / H6-C1-N2-O4 / -164.7 / -168.2 / H6-C1-N2-O4 / 172.2 / 178.4
H7-N2-C1-X3 / -166.4 / -169.3 / H7-N2-C1-X3 / 163.8 / 169.6 / H7-N2-C1-X3 / -151.5 / -174.4
O8-H5-O4-N2 / 258.9 / -131.1 / O8-H5-O4-N2 / 66.6 / 58.5 / O8-H7-N2-C1 / 146.1 / 157.2
C9-O8-H5-O4 / 4.3 / 19.1 / H9-O8-H5-X3 / 9.5 / 10.0 / C9-O8-H7-N2 / 361.8 / 355.8
O10-C9-O8-H5 / 26.1 / 26.1 / C10-O8-H9-X3 / 159.8 / 169.2 / O10-C9-O8-H7 / 178.8 / 178.6
H11-O10-C9-X3 / -7.8 / -11.6 / O11-C10-O8-H9 / -0.0 / -0.8 / H11-O10-C9-O8 / -0.3 / 0.2
C12-C9-O10-H11 / 185.5 / -173.3 / C12-C10-O11-O8 / -179.9 / -179.8 / C12-C9-O10-H11 / 179.2 / 181.1
H13-C12-C9-O8 / 8.6 / 8.5 / H13-C12-C10-O11 / -0.9 / -2.5 / H13-C12-C9-O10 / 52.9 / 69.3
H14-C12-C9-O8 / 130.3 / 130.3 / H14-C12-C10-O11 / 119.8 / 118.1 / H14-C12-C9-O10 / 174.7 / 189.7
H15-C12-C9-O8 / -111.8 / -111.9 / H15-C12-C10-O11 / -121.7 / -123.5 / H15-C12-C9-O10 / 295.5 / 311.7
Table S11The geometrical parameters of the aggregates of 1Z of FHA and TFHA with AcOH at MP2/6-31+G* theoretical level.All the bond distances are in angstrom (Å), angles and dihedrals are in degrees ().
Parameters / 1Z AcOH IV / Parameters / 1Z AcOH V / Parameters / 2Z AcOH IFHA / TFHA / FHA / TFHA / FHA / TFHA
N2-C1 / 1.362 / 1.335 / N2-C1 / 1.342 / 1.324 / N2-C1 / 1.290 / 1.294
X3-C1 / 1.238 / 1.652 / X3-C1 / 1.250 / 1.662 / X3-C1 / 1.343 / 1.742
O4-N2 / 1.421 / 1.399 / O4-N2 / 1.401 / 1.386 / O4-N2 / 1.417 / 1.399
H5-O4 / 0.993 / 1.003 / H5-O4 / 0.988 / 0.994 / H5-X3 / 0.984 / 1.342
H6-C1 / 1.098 / 1.091 / H6-C1 / 1.095 / 1.091 / H6-C1 / 1.082 / 1.085
H7-N2 / 1.028 / 1.028 / H7-N2 / 1.013 / 1.013 / H7-O4 / 0.992 / 0.993
O8-H7 / 1.919 / 1.885 / H8-X3 / 1.775 / 2.297 / O8-H7 / 1.794 / 1.798
C9-O8 / 1.233 / 1.234 / O9-H8 / 0.999 / 0.995 / C9-O8 / 1.236 / 1.235
O10-C9 / 1.344 / 1.344 / C10-O9 / 1.345 / 1.347 / O10-C9 / 1.339 / 1.340
H11-O10 / 0.994 / 0.992 / O11-C10 / 1.231 / 1.229 / H11-O10 / 1.002 / 1.003
C12-C9 / 1.499 / 1.499 / C12-C10 / 1.503 / 1.502 / C12-C9 / 1.500 / 1.500
H13-C12 / 1.093 / 1.093 / H13-C12 / 1.093 / 1.093 / H13-C12 / 1.093 / 1.093
H14-C12 / 1.089 / 1.089 / H14-C12 / 1.089 / 1.089 / H14-C12 / 1.093 / 1.093
H15-C12 / 1.093 / 1.094 / H15-C12 / 1.093 / 1.093 / H15-C12 / 1.089 / 1.089
X3-C1-N2 / 122.1 / 123.8 / X3-C1-N2 / 120.6 / 123.4 / X3-C1-N2 / 125.4 / 128.1
O4-N2-C1 / 113.4 / 118.6 / O4-N2-C1 / 118.2 / 122.8 / O4-N2-C1 / 109.4 / 112.8
H5-O4-N2 / 101.9 / 101.8 / H5-O4-N2 / 101.7 / 102.3 / H5-X3-C1 / 106.7 / 95.1
H6-C1-N2 / 113.5 / 112.3 / H6-C1-N2 / 115.9 / 114.1 / H6-C1-N2 / 119.3 / 115.7
H7-N2-C1 / 121.5 / 126.9 / H7-N2-C1 / 124.1 / 125.9 / H7-O4-N2 / 102.0 / 102.0
O8-H7-N2 / 152.3 / 150.5 / H8-O3-C1 / 114.5 / 91.8 / O8-H7-O4 / 163.5 / 163.8
C9-O8-H7 / 123.9 / 124.6 / O9-H8-X3 / 177.9 / 177.2 / C9-O8-H7 / 123.1 / 122.5
O10-C9-O8 / 123.4 / 123.4 / C10-O9-H8 / 108.6 / 109.1 / O10-C9-O8 / 123.6 / 123.5
H11-O10-C9 / 108.9 / 109.1 / O11-C10-C9 / 123.4 / 123.6 / H11-O10-C9 / 108.9 / 108.8
C12-C9-O10 / 112.2 / 112.2 / C12-C10-O9 / 111.9 / 111.6 / C12-C9-O8 / 123.9 / 124.0
H13-C12-C9 / 109.4 / 109.7 / H13-C12-C10 / 109.7 / 109.7 / H13-C12-C9 / 109.5 / 109.5
H14-C12-C9 / 109.6 / 109.6 / H14-C12-C10 / 109.6 / 109.6 / H14-C12-C9 / 109.5 / 109.5
H15-C12-C9 / 109.7 / 109.2 / H15-C12-C10 / 109.6 / 109.6 / H15-C12-C9 / 109.6 / 109.6
O4-N2-C1-X3 / -11.6 / 6.7 / O4-N2-C1-X3 / -9.7 / -0.9 / O4-N2-C1-X3 / -0.0 / -0.0
H5-O4-N2-C1 / 4.9 / -0.6 / H5-O4-N2-C1 / 6.2 / 2.0 / H5-X3-C1-N2 / -0.0 / 0.1
H6-C1-N2-O4 / 171.9 / 185.3 / H6-C1-N2-O4 / 173.2 / 179.9 / H6-C1-N2-O4 / 180.0 / 180.0
H7-N2-C1-X3 / -143.3 / -202.0 / H7-N2-C1-X3 / -159.7 / -179.1 / H7-O4-N2-C1 / 179.9 / 180.0
O8-H7-N2-C1 / 122.1 / 225.5 / H8-O3-C1-N2 / 182.9 / 186.6 / O8-H7-O4-N2 / -0.1 / 0.4
C9-O8-H7-N2 / 0.4 / 2.3 / O9-H8-X3-C1 / 8.8 / 109.5 / C9-O8-H7-O4 / 0.2 / -0.5
O10-C9-O8-H7 / 3.1 / -6.4 / C10-O9-H8-X3 / -10.8 / -113.3 / O10-C9-O8-H7 / -0.1 / 0.0
H11-O10-C9-O4 / -0.9 / 1.5 / O11-C10-O9-H8 / -0.0 / 0.1 / H11-O10-C9-N2 / -0.0 / -0.0
C12-C9-O10-H11 / 181.2 / 178.0 / C12-C10-O9-H8 / 179.9 / 180.0 / C12-C9-O8-H7 / 179.9 / 180.0
H13-C12-C9-O10 / 62.0 / 54.2 / H13-C12-C10-O9 / 58.2 / 58.2 / H13-C12-C9-O8 / 121.2 / 121.1
H14-C12-C9-O10 / 182.8 / 175.7 / H14-C12-C10-O9 / 179.3 / 179.3 / H14-C12-C9-O8 / 239.0 / 239.0
H15-C12-C9-O10 / 304.2 / 296.4 / H15-C12-C10-O9 / 300.3 / -59.7 / H15-C12-C9-O8 / 360.1 / 360.1
Table S12The geometrical parameters of the aggregates of 1Z and 2Z of FHA and TFHA with AcOH at MP2/6-31+G* theoretical level.All the bond distances are in angstrom (Å), angles and dihedrals are in degrees ().
Parameters / 2Z AcOH II / Parameters / 2Z AcOH III / Parameters / 2Z AcOH IVFHA / TFHA / FHA / TFHA / FHA / TFHA
N2-C1 / 1.291 / 1.294 / N2-C1 / 1.292 / 1.293 / N2-C1 / 1.291 / 1.293
X3-C1 / 1.347 / 1.748 / X3-C1 / 1.335 / 1.741 / X3-C1 / 1.343 / 1.740
O4-N2 / 1.441 / 1.422 / O4-N2 / 1.449 / 1.437 / O4-N2 / 1.431 / 1.417
H5-X3 / 0.983 / 1.342 / H5-X3 / 0.993 / 1.347 / H5-X3 / 0.982 / 1.341
H6-C1 / 1.083 / 1.086 / H6-C1 / 1.085 / 1.087 / H6-C1 / 1.083 / 1.087
H7-O4 / 0.990 / 0.990 / H7-O4 / 0.976 / 0.977 / H7-O4 / 0.974 / 0.976
O8-H7 / 1.876 / 1.904 / O8-H5 / 1.833 / 2.160 / O8-H6 / 2.423 / 2.361
C9-O8 / 1.232 / 1.232 / C9-O8 / 1.232 / 1.228 / C9-O8 / 1.228 / 1.228
O10-C9 / 1.349 / 1.350 / O10-C9 / 1.346 / 1.352 / O10-C9 / 1.351 / 1.351
H11-O10 / 0.991 / 0.991 / H11-O10 / 0.994 / 0.991 / H11-O10 / 0.996 / 0.997
C12-C9 / 1.499 / 1.499 / C12-C9 / 1.499 / 1.501 / C12-C9 / 1.502 / 1.502
H13-C12 / 1.089 / 1.089 / H13-C12 / 1.089 / 1.089 / H13-C12 / 1.089 / 1.089
H14-C12 / 1.093 / 1.093 / H14-C12 / 1.093 / 1.093 / H14-C12 / 1.093 / 1.093
H15-C12 / 1.094 / 1.093 / H15-C12 / 1.094 / 1.093 / H15-C12 / 1.093 / 1.093
X3-C1-N2 / 126.7 / 129.2 / X3-C1-N2 / 130.3 / 131.4 / X3-C1-N2 / 125.8 / 128.8
O4-N2-C1 / 107.6 / 110.8 / O4-N2-C1 / 109.0 / 110.6 / O4-N2-C1 / 108.9 / 112.1
H5-X3-C1 / 106.6 / 95.3 / H5-X3-C1 / 113.6 / 98.2 / H5-X3-C1 / 107.8 / 96.0
H6-C1-N2 / 118.4 / 115.0 / H6-C1-N2 / 115.7 / 113.7 / H6-C1-N2 / 117.9 / 114.3
H7-O4-N2 / 103.2 / 103.2 / H7-O4-N2 / 101.3 / 101.5 / H7-O4-N2 / 103.1 / 102.9
O8-H7-O4 / 144.8 / 141.9 / O8-H5-X3 / 155.8 / 147.9 / O8-H6-C1 / 129.0 / 134.8
C9-O8-H7 / 110.1 / 110.3 / C9-O8-H5 / 124.9 / 119.1 / C9-O8-H6 / 127.0 / 125.2
O10-C9-O8 / 123.2 / 123.2 / O10-C9-O8 / 123.1 / 122.9 / O10-C9-O8 / 123.2 / 123.2
H11-O10-C9 / 107.9 / 107.9 / H11-O10-C9 / 107.8 / 107.8 / H11-O10-C9 / 107.8 / 108.0
C12-C9-O8 / 124.7 / 124.7 / C12-C9-O8 / 124.5 / 125.2 / C12-C9-O8 / 125.0 / 125.0
H13-C12-C9 / 109.5 / 109.5 / H13-C12-C9 / 109.5 / 109.5 / H13-C12-C9 / 109.5 / 109.5
H14-C12-C9 / 109.8 / 109.7 / H14-C12-C9 / 109.7 / 109.7 / H14-C12-C9 / 109.7 / 109.6
H15-C12-C9 / 109.3 / 109.4 / H15-C12-C9 / 109.4 / 109.5 / H15-C12-C9 / 109.6 / 109.7
O4-N2-C1-X3 / 1.5 / 1.0 / O4-N2-C1-X3 / -0.4 / 0.8 / O4-N2-C1-X3 / -0.0 / -0.0
H5-X3-C1-N2 / 3.9 / 9.2 / H5-X3-C1-N2 / -2.9 / 0.2 / H5-X3-C1-N2 / -0.0 / 0.0
H6-C1-N2-O4 / 181.6 / 181.2 / H6-C1-N2-O4 / 179.9 / 180.9 / H6-C1-N2-O4 / 180.0 / 180.0
H7-O4-N2-C1 / 195.4 / 183.4 / H7-O4-N2-C1 / 195.9 / 194.0 / H7-O4-N2-C1 / 179.9 / 180.0
O8-H7-O4-N2 / 248.0 / 242.4 / O8-H5-X3-C1 / 214.8 / 234.8 / O8-H6-C1-N2 / -0.0 / -0.2
C9-O8-H7-O4 / 9.8 / 9.9 / C9-O8-H5-X3 / 103.6 / 75.2 / C9-O8-H6-C1 / -0.1 / 0.4
O10-C9-O8-H7 / -3.9 / -3.2 / O10-C9-O8-H5 / 20.6 / 27.8 / O10-C9-O8-H6 / 0.1 / -0.2
H11-O10-C9-O4 / -0.5 / -0.2 / H11-O10-C9-O4 / -7.8 / -5.7 / H11-O10-C9-N2 / 0.0 / -0.0
C12-C9-O8-H7 / 175.8 / 176.6 / C12-C9-O8-H5 / 200.1 / 207.4 / C12-C9-O8-H6 / 180.0 / 179.9
H13-C12-C9-O8 / 4.4 / 2.1 / H13-C12-C9-O8 / 5.0 / 2.3 / H13-C12-C9-O8 / 0.5 / -0.6
H14-C12-C9-O8 / 125.9 / 123.4 / H14-C12-C9-O8 / 126.4 / 123.4 / H14-C12-C9-O8 / 121.6 / 120.3
H15-C12-C9-O8 / 243.8 / 241.2 / H15-C12-C9-O8 / 244.3 / 241.4 / H15-C12-C9-O8 / 239.6 / 238.3
1
Table S13The geometrical parameters of the aggregates of 2Z of FHA and TFHA with AcOH at MP2/6-31+G* theoretical level.All the bond distances are in angstrom (Å), angles and dihedrals are in degrees ().
Parameters / 2Z AcOH VFHA / TFHA
N2-C1 / 1.287 / 1.291
X3-C1 / 1.361 / 1.756
O4-N2 / 1.435 / 1.420
H5-X3 / 0.983 / 1.342
H6-C1 / 1.082 / 1.085
H7-O4 / 0.974 / 0.976
O8-H6 / 2.416 / 2.467
C9-O8 / 1.227 / 1.226
O10-C9 / 1.353 / 1.357
H11-O10 / 0.988 / 0.987
C12-C9 / 1.501 / 1.501
H13-C12 / 1.089 / 1.089
H14-C12 / 1.093 / 1.093
H15-C12 / 1.093 / 1.093
X3-C1-N2 / 125.1 / 128.6
O4-N2-C1 / 108.0 / 111.3
H5-X3-C1 / 107.5 / 95.9
H6-C1-N2 / 120.4 / 116.5
H7-O4-N2 / 102.4 / 102.1
O8-H6-C1 / 129.9 / 123.7
C9-O8-H6 / 128.2 / 130.5
O10-C9-O8 / 123.0 / 122.8
H11-O10-C9 / 107.6 / 107.2
C12-C9-O8 / 125.3 / 125.6
H13-C12-C9 / 109.5 / 109.4
H14-C12-C9 / 109.7 / 109.6
H15-C12-C9 / 109.6 / 109.7
O4-N2-C1-X3 / 0.2 / -0.1
H5-X3-C1-N2 / -0.9 / 5.4
H6-C1-N2-O4 / 180.3 / 179.6
H7-O4-N2-C1 / 179.7 / 180.8
O8-H6-C1-X3 / -10.4 / 36.9
C9-O8-H6-C1 / 1.1 / 35.6
O10-C9-O8-H6 / 2.8 / -36.2
H11-O10-C9-X3 / -0.2 / 1.2
C12-C9-O8-H6 / 182.6 / 143.9
H13-C12-C9-O8 / 1.7 / -1.1
H14-C12-C9-O8 / 122.8 / 119.8
H15-C12-C9-O8 / 240.8 / 237.8
1
Table S14Atomic charges (NPA) on atoms of FHA (TFHA) in their aggregates with acetic acid at MP2/6-31+G* theoretical level.
Species / C1 / N2 / X3 / O4 / H5 / H6 / H71Z / 0.636
(-0.019) / -0.426
(-0.347) / -0.732
(-0.251) / -0.616
(-0.603) / 0.535
(0.531) / 0.173
(0.242) / 0.430
(0.447)
1Z AcOH I / 0.672
(0.012) / -0.423
(-0.365) / -0.772
(-0.230) / -0.632
(-0.628) / 0.560
(0.559) / 0.166
(0.235) / 0.430
(0.434)
1Z AcOH II / 0.664
(0.002) / -0.435
(-0.373) / -0.746
(-0.227) / -0.618
(-0.612) / 0.548
(0.552) / 0.165
(0.234) / 0.429
(0.435)
1Z AcOH III / 0.635
(-0.010) / -0.439
(-0.358) / -0.756
(-0.285) / -0.637
(-0.626) / 0.539
(0.530) / 0.173
(0.242) / 0.469
(0.485)
1Z AcOH IV / 0.640
(-0.010) / -0.436
(-0.367) / -0.739
(-0.243) / -0.662
(-0.652) / 0.550
(0.536) / 0.180
(0.247) / 0.471
(0.487)
1Z AcOH V / 0.641
(0.004) / -0.405
(-0.334) / -0.802
(-0.304) / -0.607
(-0.598) / 0.539
(0.533) / 0.221
(0.282) / 0.442
(0.451)
2Z / 0.478
(-0.099) / -0.282
(-0.197) / -0.783
(0.025) / -0.703
(-0.677) / 0.547
(0.176) / 0.214
(0.248) / 0.528
(0.524)
2Z AcOH I / 0.510
(-0.071) / -0.345
(-0.258) / -0.780
(0.031) / -0.708
(-0.683) / 0.552
(0.184) / 0.214
(0.246) / 0.567
(0.563)
2Z AcOH II / 0.483
(-0.098) / -0.280
(-0.188) / -0.783
(0.024) / -0.753
(-0.726) / 0.547
(0.175) / 0.215
(0.249) / 0.568
(0.566)
2Z AcOH III / 0.507
(-0.082) / -0.301
(-0.212) / -0.796
(0.028) / -0.723
(-0.701) / 0.571
(0.203) / 0.212
(0.250) / 0.532
(0.531)
2Z AcOH IV / 0.517
(-0.060) / -0.349
(-0.269) / -0.773
(0.044) / -0.686
(-0.662) / 0.547
(0.174) / 0.248
(0.283) / 0.528
(0.523)
2Z AcOH V / 0.468
(-0.093) / -0.268
(-0.190) / -0.820
(0.002) / -0.705
(-0.678) / 0.559
(0.180) / 0.248
(0.274) / 0.530
(0.524)
Table S15Important orbital interactions and second order delocalization energiesE(2) in kcal mol-1in the aggregates of FHA (TFHA)with acetic acid at MP2/6-31+G* theoretical level.
Species / nN2→ π*C1-X3 / nN2→ σ*C1-X3 / nX3→ σ*C1-N2 / nX3→ π*C1-N2 / nO4→ π*C1-N2 / nX3→ σ*O4-H5 / nO4→ σ*X3-H51Z / 32.68
(145.34) / 14.98
(-) / 29.25
(15.92) / -
(-) / -
(-) / 1.24+5.36
(13.71) / -
(-)
1Z AcOH I / 83.07
(119.21) / 3.18
(-) / 24.31
(5.65+13.74) / -
(-) / -
(-) / -
(-) / -
(-)
1Z AcOH II / 84.12
(60.30) / -
(15.45) / 28.36
(3.85+17.12) / -
(-) / -
(-) / -
(-) / -
(-)
1Z AcOH III / 50.50
(160.63) / 8.82
(-) / 28.02
(14.86) / -
(-) / -
(-) / 1.37+6.28
(1.94+16.50) / -
(-)
1Z AcOH IV / 31.57
(124.80) / 14.47
(-) / 28.24
(14.85) / -
(-) / -
(-) / 1.74+7.50
(2.22+19.02) / -
(-)
1Z AcOH V / 75.91
(156.96) / 4.76
(-) / 26.60
(16.54) / -
(-) / -
(-) / 2.14+3.80
(2.88+9.62) / -
(-)
2Z / -
(-) / 13.50
(14.57) / 8.63
(6.45) / 54.42
(39.47) / 13.22
(18.29) / -
(-) / 5.06
(2.61)
2Z AcOH I / -
(-) / 12.80
(13.80) / 8.45
(-) / 57.51
(41.60) / 15.66
(21.89) / -
(-) / 5.92
(3.06)
2Z AcOH II / -
(-) / 13.51
(14.55) / 6.48+10.72
(6.13) / 4.05+26.60
(34.10) / 4.27
(13.73) / -
(-) / 5.84
(2.71)
2Z AcOH III / -
(-) / 14.24
(13.94) / 7.71+17.39
(6.42) / 6.67+23.20
(26.83) / 2.13
(6.03) / -
(-) / 2.18
(1.71)
2Z AcOH IV / -
(-) / 12.42
(13.52) / 8.55
(6.40) / 59.06
(43.53) / 12.51
(17.01) / -
(-) / 4.86
(2.48)
2Z AcOH V / -
(-) / 13.70
(14.96) / 7.18
(5.75) / 46.86
(34.74) / 13.50
(18.35) / -
(-) / 5.86
(2.58)
1