Supplementary Table S1.The geometric parameters (r and  is in Åand , respectively) and the intramolecular hydrogen bond energies (kJmol-1)for APO and its derivatives in gas phase.

R / C=O / C-C / C=C / C-N / N-H11 / N-H12 / O…H / O…N / NHO / E*HB
H / 1.2417[1.2528] / 1.443[1.432] / 1.377[1.386] / 1.348[1.341] / 1.0188[1.0157] / 1.0055[1.0074] / 1.889[1.939] / 2.669[2.703] / 130.763[129.618] / -37.100[-32.179]
CF3 / 1.2394[1.2458] / 1.466[1.458] / 1.399[1.409] / 1.339[1.331] / 1.0231[1.0192] / 1.0060[1.0078] / 1.752 [1.789] / 2.561[2.583] / 133.015[131.85] / -57.495[-51.448]
CH3 / 1.2442[1.2557] / 1.453[1.442] / 1.386[1.394] / 1.350[1.346] / 1.0201[1.0169] / 1.0049[1.0066] / 1.803[1.839] / 2.598[2.621] / 131.867[131.008] / -48.873[-44.297]
COCH3 / 1.2418[1.2482] / 1.463[1.455] / 1.409[1.415] / 1.336[1.330] / 1.0231[1.0192] / 1.0065[1.0081] / 1.754[1.796] / 2.564[2.591] / 133.083[131.97] / -56.862[-50.142]
NH2 / 1.2440[1.2566] / 1.449[1.439] / 1.388[1.397] / 1.347[1.342] / 1.0194[1.0165] / 1.0052[1.0144] / 1.836[1.898] / 2.623[2.659] / 131.288[129.183] / -44.064[-37.015]
NHCH3 / 1.2426[1.2537] / 1.454[1.444] / 1.389[1.396] / 1.349[1.345] / 1.0186[1.0158] / 1.0055[1.0069] / 1.837[1.867] / 2.622[2.639] / 131.087[130.231] / -43.928[-40.595]
NO2 / 1.2379[1.2415] / 1.465[1.461] / 1.401[1.415] / 1.334[1.324] / 1.0229[1.0196] / 1.0066[1.0089] / 1.774[1.806] / 2.579[2.598] / 132.663[131.696] / -53.469[-48.539]
OCH3 / 1.2406[1.2511] / 1.451[1.440] / 1.380[1.388] / 1.354[1.346] / 1.0180[1.0149] / 1.0061[1.0071] / 1.875[1.912] / 2.655[2.674] / 130.794[129.473] / -38.929[-35.291]
OCHF2 / 1.2396[1.2481] / 1.447[1.438] / 1.382[1.389] / 1.346[1.339] / 1.0185[1.0157] / 1.0059[1.0075] / 1.873[1.911] / 2.652[2.675] / 130.609[129.512] / -39.123[-35.249]
OH / 1.2409[1.2525] / 1.449[1.435] / 1.379[1.387] / 1.353[1.344] / 1.0177[1.0152] / 1.0058[1.0068] / 1.879[1.919] / 2.656[2.680] / 130.541[129.323] / -38.419[-34.512]
SCH3 / 1.2421[1.2511] / 1.460[1.449] / 1.395[1.404] / 1.343[1.337] / 1.0213[1.0179] / 1.0058[1.0075] / 1.795[1.829] / 2.594[2.616] / 132.209[131.271] / -50.114[-45.348]
SCOCH3 / 1.2407[1.248] / 1.461[1.452] / 1.397[1.406] / 1.342[1.334] / 1.0214[1.018] / 1.0061[1.0078] / 1.799[1.837] / 2.596[2.619] / 132.052[131.025] / -49.45 [-44.313]
SH / 1.2419[1.2509] / 1.459[1.448] / 1.394[1.402] / 1.343[1.337] / 1.0212[1.0176] / 1.0057[1.0074] / 1.796[1.834] / 2.593[2.618] / 132.089[131.029] / -50.019[-44.736]
Br / 1.2412[1.2498] / 1.452[1.442] / 1.385[1.393] / 1.347[1.340] / 1.0189[1.0162] / 1.0053[1.0074] / 1.828[1.863] / 2.612[2.636] / 130.997[130.189] / -45.189[-40.897]
SCF3 / 1.2392[1.2462] / 1.464[1.454] / 1.400[1.409] / 1.338[1.331] / 1.0222[1.0182] / 1.0063[1.0081] / 1.789[1.834] / 2.591[2.618] / 132.349[131.097] / -50.864[-44.621]
CH2Br / 1.2400[1.2463] / 1.460[1.455] / 1.398[1.411] / 1.339[1.329] / 1.0221[1.0188] / 1.0061[1.0082] / 1.798[1.837] / 2.597[2.622] / 132.169[131.178] / -49.515[-44.168]
CH2CL / 1.2406[1.2483] / 1.458[1.450] / 1.395[1.406] / 1.340[1.332] / 1.0219[1.0184] / 1.0059[1.0079] / 1.801[1.838] / 2.599[2.624] / 132.159[131.221] / -49.107[-44.063]
Cl / 1.2408[1.2494] / 1.449[1.439] / 1.383[1.391] / 1.347[1.340] / 1.0186[1.0159] / 1.0052[1.0071] / 1.847[1.883] / 2.626[2.650] / 130.646[129.762] / -42.642[-38.480]
CHO / 1.2401[1.2449] / 1.465[1.462] / 1.414[1.424] / 1.331[1.323] / 1.0246[1.0209] / 1.0073[1.0090] / 1.759[1.791] / 2.575[2.594] / 133.541[132.62] / -55.960[-50.853]
F / 1.2387[1.2496] / 1.442[1.427] / 1.369[1.378] / 1.355[1.343] / 1.0159[1.0142] / 1.0055[1.0068] / 1.934[1.981] / 2.694[2.726] / 129.233[128.079] / -32.509[-28.529]

values in brackets refer to calculation in water phase

Supplementary Table S2. The selected topological parameters of investigated molecules and the density of the total energy of electrons (H) and its two components, the kinetic (G) and potential (V) electron energy densities (in a.u.) in gas phase (values in brackets refer to calculation in water solution).

R / ρO…H / 2ρO…H / RCP / 2ρ RCP / G / V / H
H / 0.03214
[0.02901] / 0.11523
[0.10539] / 0.01534
[0.01469] / 0.09805
[0.09257] / 0.0285
[0.0254] / -0.0282
[-0.0245] / 0.0003
[0.0009]
CF3 / 0.04386
[0.04034] / 0.14963
[0.14328] / 0.01722
[0.01672] / 0.11393
[0.010985] / 0.0406
[0.0375] / -0.0437
[-0.0391] / -0.0031
[-0.0016]
CH3 / 0.03900
[0.03627] / 0.13765
[0.13104] / 0.01652
[0.01608] / 0.10773
[0.10382] / 0.0358
[0.0332] / -0.0372
[-0.0337] / -0.0014
[-0.0005]
COCH3 / 0.04351
[0.03963] / 0.14888
[0.14095] / 0.01721
[0.01661] / 0.11340
[0.10857] / 0.0403
[0.0367] / -0.0433
[-0.0381] / -0.0030
[-0.0014]
NH2 / 0.03624
[0.03193] / 0.12935
[0.11687] / 0.01597
[0.01519] / 0.10298
[0.09618] / 0.0329
[0.0287] / -0.0335
[-0.0281] / -0.0006
[0.0006]
NHCH3 / 0.03609
[0.03405] / 0.12987
[0.12457] / 0.01595
[0.01558] / 0.10277
[0.09967] / 0.0329
[0.0310] / -0.0334
[-0.0309] / -0.0005
[0.0001]
NO2 / 0.04167
[0.03871] / 0.14367
[0.13844] / 0.01683
[0.01636] / 0.10983
[0.10629] / 0.0383
[0.0358] / -0.0407
[-0.0369] / -0.0024
[-0.0011]
OCH3 / 0.03315
[0.03084] / 0.12005
[0.11355] / 0.01544
[0.01498] / 0.09789
[0.09436] / 0.0298
[0.0276] / -0.0296
[-0.0268] / 0.0002
[0.0008]
OCHF2 / 0.03328
[0.03083] / 0.12036
[0.11333] / 0.01553
[0.01506] / 0.09862
[0.09483] / 0.0299
[0.0276] / -0.0298
[-0.0268] / 0.0001
[0.0008]
OH / 0.03283
[0.03039] / 0.11923
[0.11157] / 0.01537
[0.01489] / 0.09754
[0.09357] / 0.0295
[0.0271] / -0.0292
[-0.0262] / 0.0003
[0.0009]
SCH3 / 0.03976
[0.03689] / 0.13896
[0.13276] / 0.01662
[0.01617] / 0.10763
[0.10387] / 0.0364
[0.0338] / -0.0381
[-0.0345] / -0.0017
[-0.0007]
SCOCH3 / 0.03937
[0.03628] / 0.13806
[0.13108] / 0.01660
[0.01609] / 0.10725
[0.10321] / 0.0360
[0.0332] / -0.0376
[-0.0337] / -0.0016
[-0.0005]
SH / 0.03969
[0.03652] / 0.13899
[0.13187] / 0.01661
[0.01611] / 0.10761
[0.10344] / 0.0364
[0.0335] / -0.0381
[-0.0340] / -0.0017
[-0.0005]
Br / 0.03682
[0.03420] / 0.13233
[0.12551] / 0.01630
[0.01585] / 0.10375
[0.10007] / 0.0337
[0.0312] / -0.0344
[-0.0311] / -0.0007
[0.0001]
SCF3 / 0.04020
[0.03646] / 0.13982
[0.13156] / 0.01667
[0.01610] / 0.10808
[0.10333] / 0.0368
[0.0334] / -0.0387
[-0.0339] / -0.0019
[-0.0005]
CH2Br / 0.03946
[0.03624] / 0.13747
[0.13019] / 0.01655
[0.01600] / 0.10801
[0.10352] / 0.0360
[0.0331] / -0.0377
[-0.0336] / -0.0017
[-0.0005]
CH2Cl / 0.03922
[0.03618] / 0.13684
[0.13001] / 0.01654
[0.01601] / 0.10780
[0.10356] / 0.0358
[0.0330] / -0.0374
[-0.0335] / -0.0016
[-0.0005]
Cl / 0.03533
[0.03276] / 0.12762
[0.12057] / 0.01598
[0.01553] / 0.10163
[0.09789] / 0.0322
[0.0297] / -0.0324
[-0.0293] / -0.0002
[0.0004]
CHO / 0.04315
[0.04014] / 0.14569
[0.14063] / 0.01711
[0.01661] / 0.11214
[0.10837] / 0.0395
[0.0369] / -0.0426
[-0.0387] / -0.0031
[-0.0018]
F / 0.02913
[0.02658] / 0.10709
[0.09769] / 0.01470
[0.01417] / 0.09136
[0.08681] / 0.0258
[0.0231] / -0.0247
[-0.0217] / 0.0011
[0.0014]

Supplementary Table S3. Frequencies (in cm-1) of stretching (), and in-plane () and out-of-plane () bending, the occupation number labeled as O.N. with corresponding energies presented and some of the charge transfer energies in chelated rings of investigated molecules.

R / N-H / δ N-H / γ N-H / / E(2)LP*NH / O.N(LP) / O.N*NH / E(LP) / E*NH
H / 3429.03 / 1635.08 / 751.94 / 0 / 8.18 [6.71] / 1.8868 [1.8974] / 0.0325 [0.0284] / -0.2610 [-0.2728] / 0.4340 [0.4307]
CF3 / 3348.89 / 1626.33 / 827.87 / 80.14 / 13.26 [11.13] / 1.8819 [1.8908] / 0.0457 [0.0400] / -0.2929 [-0.2951] / 0.4133 [0.4208]
CH3 / 3396.81 / 1621.19 / 785.66 / 32.22 / 11.19 [9.77] / 1.8865 [1.8978] / 0.0388 [0.0350] / -0.2677 [-0.2806] / 0.4422 [0.4388]
COCH3 / 3348.5 / 1616.27 / 838.54 / 80.53 / 13.16 [10.92] / 1.8829 [1.8915] / 0.0454 [0.0395] / -0.2896 [-0.2922] / 0.4176 [0.4226]
NH2 / 3412.27 / 1621.74 / 784.05 / 16.76 / 9.9 [7.69] / 1.8863 [1.8996] / 0.0358 [0.0303] / -0.2666 [-0.2765] / 0.4384 [0.4346]
NHCH3 / 3424.51 / 1626.92 / 774.33 / 4.52 / 9.61 [8.27] / 1.8863 [1.8970] / 0.0352 [0.0322] / -0.2668 [-0.2791] / 0.4405 [0.4374]
NO2 / 3356.84 / 1626.97 / 827.35 / 72.19 / 12.17 [10.26] / 1.8820 [1.8896] / 0.043 [0.0380] / -0.3012 [-0.3015] / 0.3994 [0.4096]
OCH3 / 3438.96 / 1633.59 / 745.99 / -9.93 / 8.15 [7.08] / 1.8872 [1.8974] / 0.0321 [0.0287] / -0.2662 [-0.2780] / 0.4371 [0.4344]
OCHF2 / 3432.85 / 1633.64 / 758.45 / -3.82 / 8.17 [7.00] / 1.8849 [1.8943] / 0.0325 [0.0290] / -0.2788 [-0.2827] / 0.4204 [0.4255]
OH / 3443.5 / 1632.09 / 741.43 / -14.5 / 8.06 [7.03] / 1.8867 [1.8976] / 0.0314 [0.0283] / -0.2668 [-0.2771] / 0.4371 [0.4338]
SCH3 / 3380.11 / 1615.34 / 806.87 / 48.92 / 11.38 [9.8] / 1.8838 [1.8941] / 0.0406 [0.0362] / -0.2750 [-0.2848] / 0.4276 [0.4284]
SCOCH3 / 3381.16 / 1617.44 / 811.1 / 47.87 / 11.06 [9.36] / 1.8834 [1.8925] / 0.0401 [0.0354] / -0.2865 [-0.2881] / 0.4151 [0.4231]
SH / 3382.44 / 1616.43 / 807 / 46.59 / 11.29 [9.56] / 1.8833 [1.8939] / 0.0402 [0.0354] / -0.2764 [-0.2847] / 0.4264 [0.4286]
Br / 3419.52 / 1618.23 / 776.63 / 9.51 / 9.25 [7.98] / 1.8796 [1.8892] / 0.0356 [0.0320] / -0.2741 [-0.2819] / 0.4257 [0.4274]
SCF3 / 3369.1 / 1619.75 / 825.89 / 59.93 / 11.56 [9.44] / 1.8818 [1.8919] / 0.0414 [0.0358] / -0.2877 [-0.2901] / 0.4118 [0.4201]
CH2Br / 3371.49 / 1626.42 / 819.49 / 57.54 / 11.51 [9.73] / 1.8851 [1.8950] / 0.0408 [0.0359] / -0.2858 [-0.2930] / 0.4166 [0.4189]
CH2Cl / 3375.37 / 1627.21 / 814.81 / 53.66 / 11.42 [9.74] / 1.8853 [1.8954] / 0.0404 [0.0358] / -0.2830 [-0.2901] / 0.4197 [0.4228]
Cl / 3428.13 / 1622.39 / 764.27 / 0.9 / 8.78 [7.53] / 1.8819 [1.8914] / 0.0339 [0.0304] / -0.2736 [-0.2817] / 0.4260 [0.4273]
CHO / 3329.4 / 1622.71 / 859.4 / 99.63 / 13.80 [11.82] / 1.8840 [1.8932] / 0.0462 [0.0410] / -0.2993 [-0.3016] / 0.4060 [0.4141]
F / 3474.84 / 1639.9 / 706.93 / -45.8 / 6.42 [5.41] / 1.8867 [1.8959] / 0.0267 [0.0241] / -0.2707 [-0.2780] / 0.4302 [0.4275]

Supplementary Table S4. The calculated dipole moments (°) (in Deby), the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies (in a.u.),the molecular orbital energy gap, ∆EH–L (in a.u.), chemical hardness (η), chemical potential (μ) in terms of a.u., the selected 1H chemical shifts and H (in ppm), spin-spin coupling constants for APO and its derivatives (values in brackets refer to calculation in water solution).

R / μ° / HOMO / LUMO / EH-L / μ / η / H / H / J(H11-O1) / J(H11-N9)
H / 3.599[5.135] / -0.2247[-0.2303] / -0.0399[-0.0475] / 0.1848 [0.1827] / -0.1323[-0.1389] / -0.0924[-0.0913] / 10.089 [9.532] / 0.0[0.0] / 5.949[5.317] / 72.129 [71.135]
CF3 / 3.656[5.101] / -0.2505[-0.2498] / -0.0563[-0.0553] / 0.1942 [0.1944] / -0.1534[-0.1526] / -0.0971[-0.0972] / 11.427 [10.857] / 1.337 [1.326] / 7.996[7.41] / 69.993 [69.646]
CH3 / 3.569[5.077] / -0.2107[-0.2152] / -0.0328[-0.0398] / 0.1779 [0.2550] / -0.1217[-0.0877] / -0.0889[-0.1275] / 10.622 [10.053] / 0.532 [0.521] / 7.354[6.856] / 70.954 [70.019]
COCH3 / 1.876[2.986] / -0.2366[-0.2391] / -0.0519[-0.0533] / 0.1847 [0.1857] / -0.1442[-0.1462] / -0.0923[-0.0928] / 11.399 [10.809] / 1.309 [1.278] / 7.857[7.242] / 70.017 [69.699]
NH2 / 2.601[3.838] / -0.2148[-0.2194] / -0.0339[-0.0405] / 0.1808 [0.1789] / -0.1243[-0.1299] / -0.0904[-0.0894] / 10.052 [10.052] / -0.038 [0.52] / 6.811[6.811] / 71.159 [71.159]
NHCH3 / 2.704[3.884] / -0.2057[-0.2082] / -0.0371[-0.0434] / 0.1685 [0.1648] / -0.1214[-0.1258] / -0.0843[-0.0824] / 10.039 [9.572] / -0.051 [0.041] / 6.778[6.405] / 71.313 [70.602]
NO2 / 4.649[6.632] / -0.2576[-0.2575] / -0.0852[-0.0918] / 0.1723 [0.3494] / -0.1714[-0.0828] / -0.0862[-0.1747] / 11.014 [10.638] / 0.924 [1.107] / 7.523[6.929] / 70.576 [70.091]
OCH3 / 3.308[4.948] / -0.2151[-0.2189] / -0.0413[-0.0468] / 0.1737 [0.1720] / -0.1282[-0.1328] / -0.0869[-0.0860] / 9.349[8.905] / -0.741[-0.626] / 6.158[5.706] / 70.542 [70.894]
OCHF2 / 2.605[3.746] / -0.2359[-0.2343] / -0.0546[-0.0535] / 0.1812 [0.1807] / -0.1452[-0.1439] / -0.0906[-0.0903] / 9.578[9.116] / -0.512[-0.416] / 6.182[5.672] / 71.395 [70.944]
OH / 3.077[5.021] / -0.2155[-0.2183] / -0.0415[-0.0445] / 0.1739 [0.1738] / -0.1285[-0.1314] / -0.0869[-0.0869] / 9.256[8.801] / -0.833[-0.731] / 6.117[5.659] / 70.936 [70.877]
SCH3 / 3.298[4.769] / -0.2242[-0.2292] / -0.0418[-0.0462] / 0.1823 [0.1830] / -0.1330[-0.1377] / -0.0912[-0.0915] / 10.901 [10.351] / 0.811[0.819] / 7.336[6.832] / 70.723 [70.007]
SCOCH3 / 4.388[6.205] / -0.2335[-0.2335] / -0.0550[-0.0519] / 0.1784 [0.1815] / -0.1442[-0.1427] / -0.0892[-0.0907] / 10.986 [10.461] / 0.896[0.929] / 7.247[6.669] / 70.689 [70.173]
SH / 3.235[4.629] / -0.2296[-0.2319] / -0.0434[-0.0467] / 0.1861 [0.1852] / -0.1365[-0.1393] / -0.0931[-0.0926] / 10.909 [10.305] / 0.819[0.773] / 7.341 [6.771] / 70.849 [70.129]
Br / 3.103[4.428] / -0.2228[-0.2258] / -0.0485[-0.0518] / 0.1742 [0.1739] / -0.1356[-0.1388] / -0.0871[-0.0869] / 10.210 [9.760] / 0.121 [0.229] / 6.897[6.379] / 71.615 [70.767]
SCF3 / 3.750[5.203] / -0.2468[-0.2448] / -0.0553[-0.0532] / 0.1914 [0.1916] / -0.1510[-0.1490] / -0.0957[-0.0958] / 11.176 [10.519] / 1.086[0.988] / 7.324[6.639] / 70.697 [70.14]
CH2Br / 3.903[6.190] / -0.2316[-0.2341] / -0.0547[-0.0593] / 0.1768 [0.1747] / -0.1431[-0.1467] / -0.0884[-0.0873] / 11.004 [10.521] / 0.915[0.989] / 7.187[6.507] / 70.685 [70.063]
CH2CL / 3.748[5.612] / -0.2323[-0.2342] / -0.0495[-0.0506] / 0.1828 [0.1836] / -0.1409[-0.1424] / -0.0914[-0.0918] / 10.956 [10.428] / 0.866 [0.896] / 7.201[6.607] / 70.724 [70.037]
CL / 3.146[4.478] / -0.2228[-0.2261] / -0.048 0[-0.0516] / 0.1748 [0.1744] / -0.1354[-0.1389] / -0.0874[-0.0872] / 9.890 [9.45] / -0.199[-0.081] / 6.634[6.104] / 71.783 [70.939]
CHO / 2.579[3.680] / -0.2471[-0.248] / -0.0598[-0.0579] / 0.1872 [0.1900] / -0.1534[-0.1529] / -0.0936[-0.0950] / 11.653 [11.149] / 1.563[1.617] / 7.614[7.094] / 69.863 [69.398]
F / 3.073[4.611] / -0.2228[-0.2244] / -0.0501[-0.0515] / 0.1726 [0.1728] / -0.1364[-0.1379] / -0.0863[-0.0864] / 8.463[8.067] / -1.626[-1.465] / 5.357[4.859] / 71.947 [71.476]