Table S 16
Comparison across structures, for individual media, of relevant quantities of the calculated complexes of the structures utilized to investigate the influence of specific features on the formation of complexes with Cu2+.
DFT/B3LYPresults utilising the 6-31+G(d,p) basis set for all the atoms. The results in vacuo are from full-optimization calculations. The results in solution are from single point PCM calculations performed on the in-vacuo optimized geometry.
The comparisons concern hyperjovinol A (HPJ-A) andthe structures B, D, E, F, G, PHG1 and PHG, considering the conformers corresponding to those yielding the best complexes between hyperjovinol A and a Cu2+ ion.
The following comparisons are included:
a)Comparison of the complexes’ relative energies in vacuo
b)Comparison of the molecule-ion interaction energy in vacuo
c)Comparison of the natural charge on the Cu ion in the complex in vacuo
d)Comparison of the dipole moments of the complex in vacuo
e)Comparison of the complexes’ relative energies in chloroform
f)Comparison of the complexes’ relative total free energies in chloroform
g)Comparison of the molecule-ion interaction energy in chloroform
h)Comparison of the natural charge on the Cu atom in the complex in chloroform
i)Comparison of the dipole moments of the complex in chloroform
j)Comparison of the complexes’ relative energies in acetonitrile
k)Comparison of the complexes’ relative total free energies in acetonitrile
l)Comparison of the molecule-ion interaction energy in acetonitrile
m)Comparison of the natural charge on the Cu atom in the complex in acetonitrile
n)Comparison of the dipole moments of the complex in acetonitrile
o)Comparison of the complexes’ relative energies in water
p)Comparison of the complexes’ total relative free energies in water
q)Comparison of the molecule-ion interaction energy in water
r)Comparison of the natural charge on the Cu ion in the complex in water
s)Comparison of the dipole moments of the complex in water
The molecule-metal ion interaction energy is calculated as «energy of the complex minus energy of the closer conformer of the uncomplexed molecule minus energy of the Cu2+ ion», not corrected for ZPE or BSSE. The values in solution serve only as indication that the complexes still have considerable interaction energy in the given solvent, and for comparison purposes in terms of trends. They do not correspond to the actual values because of not taking into account the desolvation contributions (that is significant for the ligand and dominant for the cation, whose solvent-accessible surface is considerably decreased in the complex, as illustrated in figure S 6).
The nature of each structure is shown in figure 5.
Comparisons need to take into account that:
- for structures E and F, the d-w-v1-Cu(O19,pi) conformer is not possible because of the absence of the double bond in the geranyl chain
- forstructure PHG1, there is no possibility of complexes with the Cu ion between two O, because of the lack of the additional OH. The values reported in the PHG1 column refer to the complex with the Cu ion attached to the O of the phloroglucinol moiety specified in the name of the complex in the first column.
a)Comparison of the complexes’ relative energies in vacuo
complex / relative energy of the complex (kcal/mol)HPJ-A / B / D / E / F / G / PHG1a
d-w-v1-Cu(O19,pi) / 0.000 / 0.0000 / 0.0000 / / / 0.0000 /
d-w-Cu(O8,O19) / 1.944 / 13.1680 / 3.2369 / 0.0000 / 0.0000 / 1.0515 / 7.8214
d-r-Cu(O8,O19) / 6.712 / 19.0600 / 7.1715 / 4.1375 / 4.2551 / 5.8602 / 11.7172
d-r-q2-Cu(O14) / 15.877 / 17.8152 / 19.0052 / 17.2220 / 16.7173 / 16.8444 / 1.8678
d-w-Cu(O10,O19) / 17.427 / 23.9902 / 16.4693 / 11.3434 / 11.1769 / 21.4175 / 20.0184
s-w-q1-Cu(O14) / 17.490 / 19.1935 / 21.2291 / * / 14.3471 / 17.8983 / 2.0588
b)Comparison of the molecule-ion interaction energy in vacuo
complex / molecule-ion interaction energy (kcal/mol)HPJ-A / B / D / E / F / G / PHG1a
d-w-v1-Cu(O19,pi) / -353.5633 / -357.5749 / -351.0741 / / / -350.9573 /
d-w-f1-Cu(O8,O19) / -351.6198 / -344.4069 / -347.8372 / -336.6746 / -335.9954 / -349.9059 / -289.4576
d-r-f1-Cu(O8,O19) / -345.7341 / -338.1784 / -342.7355 / -331.4801 / -330.6569 / -344.0164 / -284.4304
d-r-q2-Cu(O14) / -331.3163 / -329.3099 / -325.2224 / -314.4788 / -312.9682 / -327.7892 / -294.2798
d-w-Cu(O10,O19) / -335.4899 / -331.3506 / -334.2916 / -326.0887 / -324.2015 / -328.2966 / -277.2606
s-w-q1-Cu(O14) / -330.6648 / -330.8243 / -323.9602 / * / -316.3359 / -327.6120 / -294.7109
c)Comparison of the natural charge on the Cu ion in the complex in vacuo
complex / natural charge on the Cu ion (a.u.)HPJ-A / B / D / E / F / G / PHG1a
d-w-v1-Cu(O19,pi) / 0.88068 / 0.84352 / 0.89031 / / / 0.88048 /
d-w-Cu(O8,O19) / 0.86920 / 0.90096 / 0.85588 / 0.92916 / 0.92966 / 0.86864 / 0.96221
d-r-Cu(O8,O19) / 0.86986 / 0.90613 / 0.85618 / 0.92507 / 0.92497 / 0.86950 / 0.96362
d-r-q2-Cu(O14) / 0.93032 / 0.92964 / 0.93349 / 0.94339 / 0.94424 / 0.91316 / 0.94949
d-w-Cu(O10,O19) / 0.91954 / 0.89035 / 0.83678 / 0.87144 / 0.87262 / 0.83835 / 0.95694
s-w-q1-Cu(O14) / 0.93278 / 0.93230 / 0.93702 / 0.94376 / 0.91781 / 0.94959
d)Comparison of the dipole moments of the complex in vacuo
complex / dipole moment (debye)HPJ-A / B / D / E / F / G / PHG1a
d-w-v1-Cu(O19,pi) / 7.5691 / 7.9662 / 4.8324 / / / 9.8092 /
d-w-Cu(O8,O19) / 10.3559 / 12.2226 / 11.0060 / 12.6008 / 6.2845 / 7.7827 / 5.6744
d-r-Cu(O8,O19) / 10.9126 / 12.3452 / 7.4358 / 10.5237 / 3.9292 / 8.2398 / 5.6675
d-r-q2-Cu(O14) / 6.0763 / 8.3483 / 3.0766 / 17.5379 / 7.2621 / 5.5129 / 1.6246
d-w-Cu(O10,O19) / 8.7233 / 14.7711 / 12.1708 / 14.3069 / 7.2123 / 8.2184 / 10.5954
s-w-q1-Cu(O14) / 6.5024 / 7.4953 / 5.8331 / * / 4.4236 / 6.8426 / 2.0763
e)Comparison of the complexes’ relative energies in chloroform
complex / relative energy of the complex (kcal/mol)HPJ-A / B / D / E / F / G / PHG1a
d-w-v1-Cu(O19,pi) / 0.0000 / 0.0000 / 0.0000 / / / 0.0000 /
d-w-Cu(O8,O19) / 3.7912 / 16.2898 / 2.3344 / 0.0000 / 0.0000 / 3.1109 / 3.9788
d-r-Cu(O8,O19) / 7.6257 / 22.2906 / 7.1446 / 4.4472 / 4.3259 / 7.3177 / 8.1568
d-r-q2-Cu(O14) / 22.9981 / 25.6243 / 24.9282 / 20.6415 / 20.6189 / 23.4250 / 2.8473
d-w-Cu(O10,O19) / 15.2984 / 23.1044 / 11.2906 / 9.2919 / 9.1144 / 16.7438 / 14.0039
s-w-q1-Cu(O14) / 22.7778 / 26.4918 / 25.3096 / * / 18.2592 / * / 3.2456
f)Comparison of the complexes’ relative total free energies in chloroform
complex / relative free energy of the complex (kcal/mol)HPJ-A / B / D / E / F / G / PHG1a
d-w-v1-Cu(O19,pi) / 0.0000 / 0.0000 / 0.0000 / / / 0.0000
d-w-Cu(O8,O19) / 2.7560 / 16.4715 / 2.0350 / 0.0000 / 0.0000 / 2.7592 / 4.1485
d-r-Cu(O8,O19) / 6.6911 / 22.8238 / 6.9823 / 4.5852 / 4.4603 / 7.1480 / 8.5109
d-r-q2-Cu(O14) / 21.2700 / 26.5863 / 25.7009 / 21.5443 / 21.5236 / 24.5268 / 2.9280
d-w-Cu(O10,O19) / 13.6176 / 23.3527 / 11.0492 / 9.3260 / 9.1434 / 17.2690 / 13.8949
s-w-q1-Cu(O14) / 22.2138 / 27.8200 / 26.6647 / * / 19.7508 / * / 3.3333
g)Comparison of the molecule-ion interaction energy in chloroform
complex / molecule-ion interaction energy (kcal/mol)HPJ-A / B / D / E / F / G / PHG1a
d-w-v1-Cu(O19,pi) / -229.3707 / -234.2777 / -227.0904 / / / -228.6887 /
d-w-f1-Cu(O8,O19) / -225.5795 / -217.9878 / -224.7560 / -221.9034 / -221.7824 / -225.5778 / -188.6151
d-r-f1-Cu(O8,O19) / -222.1804 / -213.0586 / -220.3703 / -217.8573 / -217.9363 / -221.8598 / -184.5559
d-r-q2-Cu(O14) / -201.6503 / -200.1592 / -197.0585 / -196.5851 / -196.5436 / -200.5457 / -189.8654
d-w-Cu(O10,O19) / -213.6893 / -209.3602 / -215.6167 / -212.2921 / -212.3300 / -212.8752 / -178.5901
s-w-q1-Cu(O14) / -202.6816 / -201.4408 / -197.5580 / -199.6244 / * / -189.9239
h)Comparison of the natural charge on the Cu atom in the complex in chloroform
complex / natural charge on the Cu ion (a.u.)HPJ-A / B / D / E / F / G / PHG1a
d-w-v1-Cu(O19,pi) / 0.89534 / 0.85903 / 0.90737 / / / 0.89499 /
d-w-Cu(O8,O19) / 0.89116 / 0.92318 / 0.89006 / 0.93227 / 0.93209 / 0.88767 / 0.97189
d-r-Cu(O8,O19) / 0.89237 / 0.93071 / 0.89083 / 0.93405 / 0.93400 / 0.89072 / 0.97506
d-r-q2-Cu(O14) / 0.94086 / 0.94057 / 0.94513 / 0.95261 / 0.95270 / 0.92573 / 0.95545
d-w-Cu(O10,O19) / 0.86869 / 0.89667 / 0.84465 / 0.87875 / 0.87905 / 0.84578 / 0.96274
s-w-q1-Cu(O14) / 0.94291 / 0.94217 / 0.94813 / * / 0.95133 / * / 0.95578
i)Comparison of the dipole moments of the complex in chloroform
complex / dipole moment of the complexHPJ-A / B / D / E / F / G / PHG1a
d-w-v1-Cu(O19,pi) / 9.3024 / 9.5739 / 6.1674 / / / 11.4919 /
d-w-Cu(O8,O19) / 8.3590 / 11.1419 / 11.0060 / 14.6588 / 7.5298 / 5.9095 / 6.8813
d-r-Cu(O8,O19) / 9.3921 / 11.8700 / 7.4358 / 11.9765 / 4.6439 / 6.1436 / 7.0650
d-r-q2-Cu(O14) / 4.3464 / 7.4427 / 3.0766 / 21.1441 / 9.4238 / 4.6354 / 1.4243
d-w-Cu(O10,O19) / 9.8711 / 16.4104 / 12.1708 / 17.2033 / 9.7897 / 15.0281 / 13.5069
s-w-q1-Cu(O14) / 4.3580 / 5.1379 / 5.8331 / * / 5.9926 / * / 1.6521
j)Comparison of the complexes’ relative energies in acetonitrile
complex / relative energy of the complex (kcal/mol)HPJ-A / B / D / E / F / G / PHG1a
d-w-v1-Cu(O19,pi) / 0.0000 / 0.0000 / 0.0000 / / / 0.0000 /
d-w-Cu(O8,O19) / 3.9035 / 17.1353 / 0.9789 / 0.0000 / 0.0000 / 3.3296 / 2.8515
d-r-Cu(O8,O19) / 7.4898 / 23.1816 / 6.0782 / 4.0981 / 4.2443 / 6.5642 / 7.1429
d-r-q2-Cu(O14) / 25.3395 / 28.2433 / 26.8960 / 22.2406 / 22.2732 / 25.3588 / 3.2091
d-w-Cu(O10,O19) / 13.5975 / 22.7832 / 9.0926 / 8.4389 / 8.4128 / 14.2037 / 12.0049
s-w-q1-Cu(O14) / 24.6624 / 28.7366 / 26.2862 / * / 19.9534 / 24.9582 / 3.6438
k)Comparison of the complexes’ relative totalfree energies in acetonitrile
complex / relative free energy of the complex (kcal/mol)HPJ-A / B / D / E / F / G / PHG1a
d-w-v1-Cu(O19,pi) / 0.0000 / 0.0000 / 0.0000 / / / 0.0000 /
d-w-Cu(O8,O19) / 3.0654 / 17.4416 / 0.5315 / 0.0000 / 0.0000 / 3.1551 / 3.0560
d-r-Cu(O8,O19) / 6.6955 / 23.8441 / 5.7354 / 4.2150 / 4.3631 / 6.5311 / 7.5307
d-r-q2-Cu(O14) / 23.7506 / 29.4270 / 27.6487 / 23.1739 / 23.2147 / 26.7827 / 3.2699
d-w-Cu(O10,O19) / 12.1084 / 23.1858 / 8.7192 / 8.4940 / 8.4676 / 14.7785 / 11.9133
s-w-q1-Cu(O14) / 23.9922 / 30.2579 / 27.4931 / * / 21.3730 / 26.6754 / 3.6960
l)Comparison of the molecule-ion interaction energy in acetonitrile
complex / molecule-ion interaction energy (kcal/mol)HPJ-A / B / D / E / F / G / PHG1a
d-w-v1-Cu(O19,pi) / -202.4621 / -207.6403 / -200.6159 / / / -201.8912 /
d-w-f1-Cu(O8,O19) / -198.5585 / -190.5051 / -199.6371 / -197.7226 / -197.6124 / -198.5617 / -167.1675
d-r-f1-Cu(O8,O19) / -196.1498 / -186.2601 / -195.6978 / -194.8670 / -194.6431 / -196.6028 / -163.5965
d-r-q2-Cu(O14) / -173.3752 / -172.1207 / -169.6124 / -171.9087 / -171.7271 / -172.8132 / -167.5303
d-w-Cu(O10,O19) / -188.7761 / -183.4521 / -191.3199 / -189.1492 / -189.0291 / -188.9787 / -158.0140
s-w-q1-Cu(O14) / -158.8781 / -173.4432 / -171.0696 / * / -174.7259 / -173.7572 / -167.4202
m)Comparison of the natural charge on the Cu atom in the complex in acetonitrile
complex / natural charge on the Cu ion (a.u.)HPJ-A / B / D / E / F / G / PHG1a
d-w-v1-Cu(O19,pi) / 0.90214 / 0.86632 / 0.91352 / / / 0.90171 /
d-w-Cu(O8,O19) / 0.90622 / 0.93930 / 0.90284 / 0.93215 / 0.93204 / 0.90076 / 0.97431
d-r-Cu(O8,O19) / 0.90788 / 0.89903 / 0.90694 / 0.93644 / 0.93618 / 0.90490 / 0.97838
d-r-q2-Cu(O14) / 0.94446 / 0.94412 / 0.94949 / 0.95493 / 0.95489 / 0.92935 / 0.95721
d-w-Cu(O10,O19) / 0.87211 / 0.94591 / 0.84817 / 0.88087 / 0.88123 / 0.84904 / 0.96441
s-w-q1-Cu(O14) / 0.95425 / 0.94569 / 0.95235 / * / 0.95314 / 0.93427 / 0.95756
n)Comparison of the dipole moments of the complex in acetonitrile
complex / dipole moment (debye)HPJ-A / B / D / E / F / G / PHG1a
d-w-v1-Cu(O19,pi) / 9.9049 / 10.1311 / 6.6887 / / / 12.0659 /
d-w-Cu(O8,O19) / 10.3559 / 9.2824 / 13.7621 / 15.1686 / 7.9310 / 5.1562 / 7.2527
d-r-Cu(O8,O19) / 7.1697 / 10.4024 / 10.0616 / 12.2584 / 4.9068 / 4.0207 / 7.5210
d-r-q2-Cu(O14) / 3.5502 / 7.0788 / 6.7880 / 21.9788 / 10.0427 / 4.5048 / 1.3950
d-w-Cu(O10,O19) / 13.3445 / 16.7649 / 13.1986 / 18.2509 / 10.8536 / 16.0237 / 14.5624
s-w-q1-Cu(O14) / 4.1515 / 3.6763 / 8.9009 / * / 6.4898 / 5.6431 / 1.5167
o)Comparison of the complexes’ relative energies in water
complex / relative energy of the complex (kcal/mol)HPJ-A / B / D / E / F / G / PHG1
d-w-v1-Cu(O19,pi) / 0.0000 / 0.0000 / 0.0000 / / / 0.0000 /
d-w-Cu(O8,O19) / 2.5800 / 15.9625 / 0.8977 / 0.0000 / 0.0000 / 2.0570 / 1.7628
d-r-Cu(O8,O19) / 5.8152 / 22.7784 / 6.2517 / 3.2202 / 3.2797 / 5.6963 / 6.0956
d-r-q2-Cu(O14) / 25.8262 / 28.1540 / 29.6000 / 24.5328 / 24.4763 / 25.0807 / 3.5696
d-w-Cu(O10,O19) / 9.4578 / 20.2287 / 8.0624 / 7.6087 / 7.3598 / 11.5428 / 10.2537
s-w-q1-Cu(O14) / 25.3057 / 28.9080 / 28.6315 / * / 22.4563 / 25.2881 / 4.5299
p)Comparison of the complexes’ relative total free energies in water
complex / relative free energy of the complex (kcal/mol)HPJ-A / B / D / E / F / G / PHG1
d-w-v1-Cu(O19,pi) / 0.3922 / 0.0000 / 0.0000 / / / 0.0000 /
d-w-Cu(O8,O19) / 1.9767 / 16.2481 / 0.3909 / 0.0000 / 0.0000 / 1.8775 / 1.9810
d-r-Cu(O8,O19) / 5.2334 / 23.4280 / 5.8227 / 3.3252 / 3.3917 / 5.6407 / 6.5029
d-r-q2-Cu(O14) / 24.5469 / 29.4879 / 30.5289 / 25.6657 / 25.6187 / 26.7620 / 3.6019
d-w-Cu(O10,O19) / 8.2335 / 20.6676 / 7.6487 / 7.6575 / 7.4109 / 12.2471 / 10.1362
s-w-q1-Cu(O14) / 25.5271 / 30.6808 / 30.1142 / * / 24.2087 / 27.3424 / 4.5469
q)Comparison of the molecule-ion interaction energy in water
complex / molecule-ion interaction energy (kcal/mol)HPJ-A / B / D / E / F / G / PHG1
d-w-v1-Cu(O19,pi) / -164.4778 / -169.2352 / -165.0745 / / / -163.8574 /
d-w-f1-Cu(O8,O19) / -161.8978 / -153.2727 / -164.1768 / -162.8108 / -162.5802 / -161.8004 / -135.8561
d-r-f1-Cu(O8,O19) / -161.3153 / -149.6802 / -161.7239 / -162.1964 / -162.0057 / -160.8412 / -133.3947
d-r-q2-Cu(O14) / -137.6027 / -136.4648 / -134.3718 / -137.2815 / -137.1700 / -137.7680 / -135.9207
d-w-Cu(O10,O19) / -154.9307 / -147.5965 / -157.1034 / -155.0416 / -155.1038 / -154.9075 / -127.3653
s-w-q1-Cu(O14) / -138.7298 / -137.0466 / -135.9375 / * / -139.7793 / -138.0313 / -135.5577
r)Comparison of the natural charge on the Cu ion in the complex in water
complex / natural charge on the Cu ion (a.u.)HPJ-A / B / D / E / F / G / PHG1a
d-w-v1-Cu(O19,pi) / 0.91285 / 0.87415 / 0.92231 / / / 0.91245 /
d-w-Cu(O8,O19) / 0.93557 / 0.97084 / 0.90705 / 0.93277 / 0.93249 / 0.92651 / 0.98101
d-r-Cu(O8,O19) / 0.93818 / 0.97643 / 0.91321 / 0.93872 / 0.93833 / 0.93335 / 0.98547
d-r-q2-Cu(O14) / 0.94994 / 0.94910 / 0.95690 / 0.95971 / 0.95984 / 0.93493 / 0.96128
d-w-Cu(O10,O19) / 0.87203 / 0.89770 / 0.84946 / 0.88082 / 0.88078 / 0.85025 / 0.96764
s-w-q1-Cu(O14) / 0.95295 / 0.95182 / 0.96057 / * / 0.95800 / 0.94069 / 0.96169
s)Comparison of the dipole moments of the complex in water
complex / dipole moment (debye)HPJ-A / B / D / E / F / G / PHG1a
d-w-v1-Cu(O19,pi) / 10.7599 / 10.8989 / 7.4815 / / / 12.8716 /
d-w-Cu(O8,O19) / 8.9400 / 6.8514 / 14.4165 / 15.6845 / 8.5031 / 8.2302 / 7.6859
d-r-Cu(O8,O19) / 5.1795 / 6.7139 / 10.4489 / 12.4333 / 5.2967 / 4.6986 / 8.0775
d-r-q2-Cu(O14) / 6.1955 / 11.8613 / 11.7934 / 22.7683 / 10.7106 / 7.7075 / 1.4883
d-w-Cu(O10,O19) / 18.5456 / 20.1097 / 14.3842 / 19.4515 / 12.1751 / 17.0458 / 15.8538
s-w-q1-Cu(O14) / 3.7198 / 4.5314 / 15.4234 / * / 6.8947 / 6.8690 / 1.5003