A) Natural Electron Configuration of the Cu Ion in the Complexesof Hyperjovinol-Aand A

Table S 6

Natural electron configuration and natural atomic orbital occupancies of the Cu ion in the calculated complexes of hyperjovinol-A with a Cu2+ cation. Results in vacuo.

In the method columns, the psdp acronym refers to DFT/B3LYPcalculations with the 6- 31+G(d,p) basis set for the C, O and H atoms and the LANL2DZ pseudopotential for the Cu2+ ion; the non-psdpacronym refers to DFT/B3LYPcalculations utilizing the 6-31+G(d,p) basis set for all the atoms.

a) `Natural electron configuration of the Cu ion in the complexesof hyperjovinol-Aand a Cu2+ cation.

The natural electron configuration of the isolated Cu2+ion is [core]3d( 9.00).

complex / method / electron configuration of the copper ion
in the complex
d-w-v1-Cu(O19,pi) / psdp
no-psdp / [core] 4s(0.25) 3d(9.87) 4p(0.01)
[core] 4s(0.28) 3d(9.83) 4p(0.01)
d-w-f1-Cu(O8,O19) / psdp
no-psdp / [core] 4s(0.27) 3d(9.85) 4p(0.01)
[core] 4s(0.31) 3d(9.80) 4p(0.01)
d-w-f2-Cu(O19,pi) / psdp
no-psdp / [core] 4s(0.24) 3d(9.87) 4p(0.01)
[core] 4s(0.28) 3d(9.83) 4p(0.01)
d-r-v1-Cu(O19,pi) / psdp
no-psdp / [core] 4s(0.24) 3d(9.87) 4p(0.01)
[core] 4s(0.28) 3d(9.83) 4p(0.01)
d-r-f1-Cu(O8,O19) / psdp
no-psdp / [core] 4s(0.26) 3d(9.85) 4p(0.01)
[core] 4s(0.31) 3d(9.81) 4p(0.01)
s-w-f1-u-Cu(O19,pi) / psdp / [core] 4s(0.24) 3d(9.87) 4p(0.01)
s-w-f1-a-Cu(O19,pi) / psdp / [core] 4s(0.24) 3d(9.87) 4p(0.01)
d-r-f-1-Cu(O8,O19)- / psdp
no-psdp / [core] 4s(0.26) 3d(9.84) 4p(0.01)
[core] 4s(0.30) 3d(9.79) 4p(0.01)
d-r-q2-Cu(pi) / psdp
no-psdp / [core] 4s(0.26) 3d(9.91)
[core] 4s(0.29) 3d(9.88)
d-r-q2-Cu(O14) / psdp
no-psdp / [core] 4s(0.11) 3d(9.94) 4p(0.01)
[core] 4s(0.12) 3d(9.93) 4p(0.01)
s-w-q1-Cu(pi) / psdp
no-psdp / [core] 4s(0.24) 3d(9.91)
[core] 4s(0.26) 3d(9.88)
d-w-f1-a-Cu(pi) / psdp
no-psdp / [core] 4s(0.24) 3d( 9.91)
[core] 4s(0.27) 3d(9.88)
s-w-q1-Cu(O14) / psdp
no-psdp / [core] 4s(0.11) 3d(9.94) 4p(0.01)
[core] 4s(0.12) 3d(9.93) 4p(0.01)
d-w-Cu(O10,O19) / psdp
no-psdp / [core] 4s(0.23) 3d(9.88) 4p(0.01)
[core] 4s(0.28) 3d(9.85) 4p(0.01)
d-r-q2-Cu(O14)-b / psdp
no-psdp / [core] 4s(0.11) 3d(9.94) 4p(0.01)
[core] 4s(0.12) 3d(9.93) 4p(0.01)
d-w-f1-a-Cu(O14) / psdp
no-psdp / [core] 4s(0.11) 3d(9.94) 4p(0.01)
[core] 4s(0.13) 3d(9.93) 4p(0.01)
s-w-q1-Cu(O12) / psdp
no-psdp / [core] 4s(0.16) 3d(9.92) 4p(0.01)
[core] 4s(0.19) 3d(9.90) 4p(0.01)
d-w-Cu(O10,O19)-b / psdp
no-psdp / [core] 4s(0.23) 3d(9.88) 4p(0.01)
[core] 4s(0.28) 3d(9.85) 4p(0.01)
w-q1-Cu(O12,O14) / psdp
no-psdp / [core] 4s(0.11) 3d(9.94) 4p(0.01)
[core] 4s(0.12) 3d(9.93) 4p(0.01)
s-w-f2-Cu(O14) / psdp
no-psdp / [core] 4s(0.11) 3d(9.94) 4p(0.01)
[core] 4s(0.13) 3d(9.93) 4p(0.01)
s-r-q2-Cu(O14) / psdp
no-psdp / [core] 4s(0.10) 3d(9.94) 4p(0.01)
[core] 4s(0.12) 3d(9.93) 4p(0.01)
s-r-q1-Cu(O14) / psdp
no-psdp / [core] 4s(0.11) 3d(9.94) 4p(0.01)
[core] 4s(0.12) 3d(9.93) 4p(0.01)
d-r-f1-a-Cu(O14) / psdp
no-psdp / [core] 4s(0.11) 3d(9.94) 4p(0.01)
[core] 4s(0.13) 3d(9.93) 4p(0.01)
s-r-q1-Cu(O12) / psdp
no-psdp / [core] 4s(0.16) 3d(9.92) 4p(0.01)
[core] 4s(0.18) 3d(9.90) 4p(0.01)
s-r-q2-Cu(O12) / psdp
no-psdp / [core] 4s(0.16) 3d(9.92) 4p(0.01)
[core] 4s(0.18) 3d(9.90) 4p(0.01)
r-q2-Cu(O12,O14) / psdp
no-psdp / [core] 4s(0.11) 3d(9.94) 4p(0.01)
[core] 4s(0.12) 3d(9.93) 4p(0.01)
r-q1-Cu(O12,O14) / psdp
no-psdp / [core] 4s( 0.11)3d( 9.94)4p( 0.01)
[core] 4s(0.12) 3d(9.93) 4p(0.01)
d-w-v1-Cu(O19) / psdp
no-psdp / [core] 4s(0.13) 3d(9.94) 4p(0.01)
[core] 4s(0.16) 3d(9.93) 4p(0.01)
s-w-f2-Cu(O12) / psdp
no-psdp / [core] 4s(0.17 )3d(9.92) 4p(0.01)
[core] 4s(0.19) 3d(9.90) 4p(0.01)
r-q2-Cu(O8,O14) / psdp
no-psdp / [core] 4s(0.11) 3d(9.94) 4p(0.01)
[core] 4s(0.12) 3d(9.93) 4p(0.01)
r-q1-Cu(O8,O14) / psdp
no-psdp / [core] 4s(0.11) 3d(9.94) 4p(0.02)
[core] 4s(0.13) 3d(9.93) 4p(0.01)
s-w-Cu(O10,O19) / psdp
no-psdp / [core] 4s(0.23) 3d(9.88) 4p(0.01)
[core] 4s(0.28) 3d(9.85) 4p(0.01)
d-r-q2-Cu(O8) / psdp
no-psdp / [core] 4s(0.16) 3d(9.92) 4p(0.01)
[core] 4s(0.19) 3d(9.90) 4p(0.01)
d-r-v1-Cu(O19) / psdp
no-psdp / [core] 4s(0.13) 3d(9.94) 4p(0.01)
[core] 4s(0.16) 3d(9.93) 4p(0.01)
s-w-u-Cu(O8,O19) / psdp
no-psdp / [core] 4s(0.17) 3d(9.91) 4p(0.01)
[core] 4s(0.23) 3d(9.89) 4p(0.01)
d-r-q2-Cu(O12) / psdp
no-psdp / [core] 4s(0.13) 3d(9.94) 4p(0.01)
[core] 4s(0.17) 3d(9.92) 4p(0.01)
s-w-q1-Cu(O8,O19)- / psdp
no-psdp / [core] 4s(0.18) 3d(9.91) 4p(0.01)
[core] 4s(0.25) 3d(9.88) 4p(0.01)
s-r-Cu(O8,O19) / psdp
no-psdp / [core] 4s(0.19) 3d(9.91) 4p(0.01)
[core] 4s(0.25) 3d(9.88) 4p(0.01)
d-w-f1-a-Cu(O12) / psdp
no-psdp / [core] 4s(0.13) 3d(9.94) 4p(0.01)
[core] 4s(0.16) 3d(9.92) 4p(0.01)
d-r-f1-a-Cu(O12) / psdp
no-psdp / [core] 4s(0.13) 3d(9.94) 4p(0.01)
[core] 4s(0.16) 3d(9.92) 4p(0.01)
d-r-q2-Cu(O10) / psdp
no-psdp / [core] 4s(0.13) 3d(9.94) 4p(0.01)
[core] 4s(0.15) 3d(9.92) 4p(0.01)
d-r-q2-u-Cu(O12) / psdp
no-psdp / [core] 4s(0.10) 3d(9.95) 4p(0.01)
[core] 4s(0.12) 3d(9.93) 4p(0.01)
s-r-q2-Cu(O8) / psdp
no-psdp / [core] 4s(0.14) 3d(9.93) 4p(0.01)
[core] 4s(0.17) 3d(9.92) 4p(0.01)
d-w-v1-Cu(O10) / psdp
no-psdp / [core] 4s(0.09) 3d(9.95) 4p(0.01)
[core] 4s(0.11) 3d(9.94) 4p(0.01)
d-r-v1-Cu(O10) / psdp
no-psdp / [core] 4s(0.12) 3d(9.95) 4p(0.01)
[core] 4s(0.13) 3d(9.93) 4p(0.01)
s-r-q1-Cu(O10) / psdp
no-psdp / [core] 4s(0.10) 3d(9.95) 4p(0.01)
[core] 4s(0.11) 3d(9.94) 4p(0.01)
s-w-q1-Cu(O10) / psdp
no-psdp / [core] 4s(0.09) 3d(9.95) 4p(0.01)
[core] 4s(0.12) 3d(9.94) 4p(0.01)

b) Natural atomic orbital occupancies of valence orbitals in the isolated copperion and in the complexesof hyperjovinol-Aand a Cu2+ cation.

complex
and
method / valence orbital occupancy
4s / 3dxy / 3dxz / 3dyz / 3dx2y2 / 3dz2
isolated Cu ion
psdp
no-psdp / 0.00001
0.00000 / 1.99997
1.99994 / 1.99997
1.99994 / 1.99983
1.99993 / 1.24968
1.74979 / 1.74978
1.24968
d-w-v1-Cu(O19,pi)
psdp
no-psdp / 0.24570
0.27848 / 1.93142
1.90790 / 1.98590
1.98292 / 1.98858
1.98539 / 1.97936
1.97477 / 1.98064
1.97724
d-w-f1-Cu(O8,O19)
psdp
no-psdp / 0.26502
0.31413 / 1.99285
1.99049 / 1.97221
1.96110 / 1.99574
1.99680 / 1.92288
1.89690 / 1.96469
1.95962
d-w-f2-Cu(O19,pi)
psdp
no-psdp / 0.24494
0.27745 / 1.98611
1.98180 / 1.98140
1.97529 / 1.97969
1.98438 / 1.93703
1.91249 / 1.98693
1.98042
d-r-v1-Cu(O19,pi)
psdp
no-psdp / 0.24463
0.27748 / 1.93214
1.90873 / 1.98584
1.98285 / 1.98829
1.98501 / 1.97977
1.97533 / 1.98102
1.97767
d-r-f1-Cu(O8,O19)
psdp
no-psdp / 0.26095
0.31120 / 1.99296
1.99059 / 1.97320
1.96310 / 1.99552
1.99659 / 1.92339
1.89709 / 1.96523
1.95982
s-w-f1-u-Cu(O19,pi)
psdp / 0.23919 / 1.96422 / 1.97520 / 1.97721 / 1.96456 / 1.98884
s-w-f1-a-Cu(O19,pi)
psdp / 0.24040 / 1.96583 / 1.97438 / 1.97621 / 1.96581 / 1.98973
d-r-f-1-Cu(O8,O19)-
psdp
no-psdp / 0.25579
0.30322 / 1.98249
1.97609 / 1.97177
1.95687 / 1.99615
1.99701 / 1.92784
1.90297 / 1.96371
1.95806
d-r-q2-Cu(pi)
psdp
no-psdp / 0.26292
0.28659 / 1.94804
1.92891 / 1.99706
1.99727 / 1.99535
1.99402 / 1.97874
1.97655 / 1.98584
1.98381
d-r-q2-Cu(O14)
psdp
no-psdp / 0.10658
0.12390 / 1.98500
1.97957 / 1.99176
1.99079 / 1.99647
1.99659 / 1.99055
1.98872 / 1.98062
1.97862
s-w-q1-Cu(pi)
psdp
no-psdp / 0.23771
0.20392 / 1.97306
1.96633 / 1.98878
1.95548 / 1.98104
1.95075 / 1.97051
1.96917 / 1.99213
1.99201
s-w-q1-Cu(pi)
psdp
no-psdp / 0.23771
0.26560 / 1.97306
1.99500 / 1.98878
1.97526 / 1.98104
1.98465 / 1.97051
1.96615 / 1.99213
1.96034
d-w-f1-a-Cu(pi)
psdp
no-psdp / 0.24054
0.26560 / 1.99586
1.99500 / 1.97743
1.97526 / 1.98902
1.98465 / 1.97288
1.96615 / 1.97051
1.96034
s-w-q1-Cu(O14)
psdp
no-psdp / 0.10598
0.08526 / 1.97656
1.98786 / 1.99405
1.99277 / 1.99306
1.99840 / 1.99168
1.97480 / 1.98845
1.99056
d-w-Cu(O10,O19)
psdp
no-psdp / 0.23033
0.28023 / 1.97111
1.96149 / 1.99049
1.98760 / 1.99515
1.99616 / 1.95292
1.93706 / 1.97136
1.96621
d-r-q2-Cu(O14)-b
psdp
no-psdp / 0.10644
0.12469 / 1.98882
1.98447 / 1.99229
1.99072 / 1.99579
1.99533 / 1.98651
1.98283 / 1.98099
1.98017
d-w-f1-a-Cu(O14)
psdp
no-psdp / 0.10851
0.12535 / 1.97924
1.97169 / 1.99393
1.99410 / 1.99234
1.99130 / 1.99230
1.99122 / 1.98594
1.98555
s-w-q1-Cu(O12)
psdp
no-psdp / 0.15989
0.11937 / 1.96131
1.98128 / 1.98666
1.99300 / 1.99260
1.99850 / 1.98885
1.97376 / 1.98849
1.98905
d-w-Cu(O10,O19)-b
psdp
no-psdp / 0.22830
0.27758 / 1.95918
1.94724 / 1.99601
1.99293 / 1.99678
1.99719 / 1.96360
1.95049 / 1.96641
1.96198
w-q1-Cu(O12,O14)
psdp
no-psdp / 0.10632
0.12043 / 1.98102
1.97442 / 1.99147
1.98972 / 1.98754
1.98508 / 1.99397
1.99409 / 1.98965
1.98909
s-w-f2-Cu(O14)
psdp
no-psdp / 0.10920
0.12543 / 1.98978
1.98029 / 1.99305
1.99275 / 1.99460
1.99489 / 1.98219
1.98189 / 1.98331
1.98196
s-r-q2-Cu(O14)
psdp
no-psdp / 0.10451
0.12203 / 1.99087
1.98990 / 1.98406
1.98184 / 1.99508
1.99593 / 1.98712
1.98026 / 1.98706
1.98518
s-r-q1-Cu(O14)
psdp
no-psdp / 0.10522
0.06759 / 1.97636
1.99515 / 1.99408
1.99738 / 1.99312
1.99955 / 1.99167
1.98048 / 1.98865
1.99301
d-r-f1-a-Cu(O14)
psdp
no-psdp / 0.10895
0.12526 / 1.97951
1.97268 / 1.99434
1.99436 / 1.99167
1.99061 / 1.99155
1.99069 / 1.98678
1.98588
s-r-q1-Cu(O12)
psdp
no-psdp / 0.15646
0.12493 / 1.96008
1.96453 / 1.98726
1.99311 / 1.99137
1.99599 / 1.99212
1.99070 / 1.98865
1.98953
s-r-q2-Cu(O12)
psdp
no-psdp / 0.15898
0.18388 / 1.98051
1.97451 / 1.99867
1.99897 / 1.99264
1.99040 / 1.96380
1.95549 / 1.98301
1.97989
r-q2-Cu(O12,O14)
psdp
no-psdp / 0.10669
0.11849 / 1.99374
1.99291 / 1.98746
1.98657 / 1.99168
1.98968 / 1.97731
1.97088 / 1.99247
1.99094
r-q1-Cu(O12,O14)
psdp
no-psdp / 0.10590
0.12009 / 1.98116
1.97375 / 1.99152
1.98968 / 1.98714
1.98480 / 1.99354
1.99372 / 1.98972
1.98913
d-w-v1-Cu(O19)
psdp
no-psdp / 0.13463
0.15666 / 1.97575
1.96930 / 1.99020
1.98771 / 1.98774
1.98753 / 1.99441
1.99387 / 1.99388
1.99325
s-w-f2-Cu(O12)
psdp
no-psdp / 0.16585
0.19107 / 1.95466
1.94701 / 1.99754
1.99780 / 1.99383
1.99100 / 1.98787
1.98142 / 1.98337
1.98076
r-q2-Cu(O8,O14)
psdp
no-psdp / 0.10985
0.06156 / 1.98002
1.99878 / 1.98818
1.99718 / 1.99054
1.99780 / 1.99596
1.99743 / 1.98867
1.99864
r-q1-Cu(O8,O14)
psdp
no-psdp / 0.11417
0.12588 / 1.99574
1.99468 / 1.98891
1.98610 / 1.99163
1.99172 / 1.98406
1.97995 / 1.98138
1.97650
s-w-Cu(O10,O19)
psdp
no-psdp / 0.22750
0.27667 / 1.96665
1.95614 / 1.99185
1.98835 / 1.99523
1.99582 / 1.95721
1.94258 / 1.97046
1.96562
d-r-q2-Cu(O8)
psdp
no-psdp / 0.15566
0.18879 / 1.98610
1.99190 / 1.99719
1.99871 / 1.98791
1.97921 / 1.96367
1.94479 / 1.98537
1.98402
d-r-v1-Cu(O19)
psdp
no-psdp / 0.13450
0.15636 / 1.97586
1.96966 / 1.99079
1.98816 / 1.98843
1.98788 / 1.99435
1.99394 / 1.99352
1.99320
s-w-u-Cu(O8,O19)
psdp
no-psdp / 0.17078
0.06034 / 1.98646
1.99731 / 1.98672
1.99886 / 1.98641
1.99916 / 1.96764
1.99792 / 1.98496
1.99635
d-r-q2-Cu(O12)
psdp
no-psdp / 0.13254
0.17095 / 1.99082
1.98651 / 1.96671
1.95808 / 1.99416
1.99179 / 1.99570
1.99482 / 1.98911
1.98651
s-w-q1-Cu(O8,O19)-
psdp
no-psdp / 0.18214
0.24694 / 1.96337
1.94374 / 1.99126
1.98650 / 1.98951
1.98524 / 1.98395
1.98636 / 1.98072
1.98043
s-r-Cu(O8,O19)
psdp
no-psdp / 0.18572
0.24678 / 1.97844
1.96760 / 1.98124
1.97314 / 1.98317
1.98039 / 1.97860
1.97722 / 1.98415
1.98412
d-w-f1-a-Cu(O12)
psdp
no-psdp / 0.12752
0.16242 / 1.99107
1.98818 / 1.98463
1.98281 / 1.98031
1.97396 / 1.99104
1.98758 / 1.99181
1.98983
d-r-f1-a-Cu(O12)
psdp
no-psdp / 0.12732
0.16131 / 1.99209
1.99011 / 1.98498
1.98425 / 1.97915
1.97177 / 1.99106
1.98678 / 1.99195
1.98983
d-r-q2-Cu(O10)
psdp
no-psdp / 0.13037
0.15359 / 1.99311
1.99154 / 1.99860
1.99935 / 1.99669
1.99491 / 1.96035
1.94865 / 1.98668
1.98399
d-r-q2-u-Cu(O12)
psdp
no-psdp / 0.10335
0.12424 / 1.98960
1.98163 / 1.99769
1.99535 / 1.98737
1.97904 / 1.97985
1.98255 / 1.99323
1.99438
s-r-q2-Cu(O8)
psdp
no-psdp / 0.13666
0.23002 / 1.99071
1.99581 / 1.99210
1.99965 / 1.99505
1.99895 / 1.96816
1.99637 / 1.98869
1.99873
d-w-v1-Cu(O10)
psdp
no-psdp / 0.08958
0.08163 / 1.99060
1.97233 / 1.98805
1.99785 / 1.98348
1.99597 / 1.99553
1.99812 / 1.99699
1.99219
d-r-v1-Cu(O10)
psdp
no-psdp / 0.11655
0.13459 / 1.97780
1.96883 / 1.99063
1.99429 / 1.99586
1.99810 / 1.99079
1.98505 / 1.99293
1.98802
s-r-q1-Cu(O10)
psdp
no-psdp / 0.09685
0.09589 / 1.98277
1.97077 / 1.99859
1.99757 / 1.99812
1.99308 / 1.98569
1.99196 / 1.98866
1.99188
s-w-q1-Cu(O10)
psdp
no-psdp / 0.09299
0.11545 / 1.99286
1.99041 / 1.99484
1.99434 / 1.99266
1.99456 / 1.98228
1.97624 / 1.98915
1.98700