31
[Ni(Phbpy)Br] geometry optimized at def2-TZVPP/B3LYP/COSMO-THF level prior to calculation of the absorption spectrum.
C -2.464505 -0.141986 0.395007
C -1.168687 -0.648492 0.284656
N -0.126021 0.204318 0.250927
C -0.283759 1.535609 0.318795
C -1.552877 2.090125 0.429254
C -2.647588 1.231059 0.467337
H -3.311105 -0.811945 0.424075
Ni 1.600442 -0.510215 0.113059
C 0.991808 2.267801 0.263160
C 1.102470 3.651672 0.309446
C 2.363147 4.230316 0.246825
C 3.475212 3.408199 0.139633
C 3.289870 2.032489 0.099231
N 2.081382 1.468565 0.159224
H 0.219920 4.268389 0.392574
H 2.471077 5.305937 0.281208
H 4.475025 3.814580 0.087533
H 4.123768 1.349948 0.016895
C -0.730386 -2.038129 0.194560
C 0.676293 -2.195199 0.097553
C 1.160665 -3.499990 0.005807
C 0.295767 -4.596650 0.009862
C -1.081813 -4.418235 0.106596
C -1.598227 -3.132482 0.199520
H 2.224657 -3.674878 -0.070147
H 0.703746 -5.597794 -0.063226
H -1.746089 -5.272605 0.109204
H -2.669000 -2.987755 0.274407
H -3.645955 1.638180 0.554238
Br 3.793905 -1.349922 -0.038883
H -1.690030 3.159361 0.484809

38
anionradical_[Ni((MeO)Ph(7-CF3)bpy)Br]_BP86d3_TZVP_COSMO_THF
  Ni     -0.999411      1.520676     -1.197368
  Br     -1.429465      0.377020     -3.265454
  C       0.164909      2.893867     -1.906767
  C       1.645095      4.713973     -1.142869
  N      -2.091496      0.317931      0.020351
  C      -2.439415     -0.249182      2.348388
  C       0.570778      3.189412     -3.206034
  H       0.173753      2.613375     -4.032310
  C       1.483569      4.212669     -3.492927
  H       1.763667      4.398003     -4.520384
  C       2.027512      4.972504     -2.457515
  O       2.934634      5.990216     -2.631595
  C       0.733725      3.695509     -0.881981
  C       0.254132      3.373882      0.462520
  C       0.572863      4.034621      1.641767
  H       1.276791      4.852736      1.655426
  C      -0.128594      3.673726      2.795598
  C      -1.043394      2.637508      2.791111
  C      -1.862417      2.462221      4.022776
  C      -1.219506      1.851914      1.599959
  N      -0.602408      2.336446      0.455837
  C      -1.939691      0.643532      1.367997
  C      -3.130874     -1.375734      1.975732
  H      -3.502558     -2.055678      2.732469
  C      -3.327885     -1.652615      0.607900
  H      -3.871386     -2.525410      0.273060
  C      -2.768364     -0.790369     -0.313435
  H      -2.842470     -0.981806     -1.376497
  H       0.012833      4.252301      3.697551
  H       2.068120      5.318486     -0.349237
  H      -2.247791     -0.067654      3.392593
  F      -3.166024      2.198337      3.763382
  F      -1.853864      3.572307      4.804588
  F      -1.427486      1.446263      4.834679
  C       3.306319      6.328321     -3.966148
  H       3.816350      5.495543     -4.458612
  H       3.988982      7.171215     -3.883593
  H       2.435417      6.623035     -4.557709

35
anionradical_[Ni((MeO)Phbpy)Br_BP86d3_TZVP_COSMO_THF
  Ni     -0.876426      1.547906     -1.243758
  Br     -1.267675      0.399757     -3.324791
  C       0.249170      2.966151     -1.913846
  C       1.594686      4.885453     -1.148559
  N      -1.963932      0.301548     -0.058127
  C      -2.603932     -0.074520      2.256225
  C       0.703548      3.236922     -3.202740
  H       0.379716      2.608936     -4.023300
  C       1.574594      4.295454     -3.486265
  H       1.896963      4.456830     -4.505516
  C       2.024890      5.118774     -2.454608
  O       2.891804      6.173635     -2.628148
  C       0.721720      3.832169     -0.887785
  C       0.207300      3.501850      0.446624
  C       0.426645      4.160553      1.640436
  H       1.046922      5.044857      1.676688
  C      -0.187909      3.655530      2.813632
  C      -0.981018      2.532145      2.758592
  C      -1.177606      1.872271      1.525621
  N      -0.575490      2.392373      0.398310
  C      -1.932575      0.694086      1.278683
  C      -3.293161     -1.205006      1.893748
  H      -3.804945     -1.796207      2.642912
  C      -3.316620     -1.592696      0.532004
  H      -3.838798     -2.480759      0.203333
  C      -2.637234     -0.814312     -0.382282
  H      -2.611018     -1.077586     -1.432485
  H      -0.032460      4.161870      3.758435
  H       1.956224      5.534037     -0.358684
  H      -2.563513      0.232757      3.293384
  H      -1.458641      2.153090      3.652330
  C       3.307942      6.478833     -3.957658
  H       3.878596      5.654349     -4.394879
  H       3.945797      7.356656     -3.879824
  H       2.452895      6.707467     -4.599444

34
anionradical_[Ni(Ph(7-CF3)bpy)Br]_BP86d3_TZVP_COSMO_THF
  Ni     -0.979628      1.553229     -1.172314
  Br     -1.394022      0.436273     -3.257697
  C       0.187954      2.942832     -1.851629
  C       1.656920      4.754311     -1.047497
  N      -2.080158      0.329380      0.019339
  C      -2.446636     -0.272878      2.336315
  C       0.597005      3.259853     -3.150518
  H       0.202566      2.692702     -3.984370
  C       1.505510      4.292710     -3.400363
  H       1.803149      4.516225     -4.419390
  C       2.043465      5.038306     -2.351824
  H       2.750412      5.834936     -2.550187
  C       0.745636      3.725148     -0.806234
  C       0.256657      3.378803      0.526877
  C       0.567034      4.017841      1.720607
  H       1.273255      4.833303      1.754202
  C      -0.148634      3.643389      2.861098
  C      -1.068057      2.611289      2.830582
  C      -1.912409      2.427760      4.043787
  C      -1.228747      1.842129      1.627890
  N      -0.600526      2.342298      0.497152
  C      -1.942565      0.635220      1.372685
  C      -3.131825     -1.395830      1.942130
  H      -3.507535     -2.087841      2.685906
  C      -3.316740     -1.652721      0.568702
  H      -3.855497     -2.521883      0.217023
  C      -2.751420     -0.776311     -0.335612
  H      -2.815846     -0.953587     -1.401655
  H      -0.016867      4.209601      3.772390
  H       2.062866      5.333040     -0.226060
  H      -2.263121     -0.105755      3.384565
  F      -3.208803      2.157828      3.755684
  F      -1.926526      3.536463      4.827842
  F      -1.489239      1.412861      4.863131

31
anionradical_[Ni(Phbpy)Br]_BP86d3_TZVP_COSMO_THF
  Ni     -0.850867      1.497822     -1.192874
  Br     -1.231071      0.394109     -3.249792
  C       0.278085      2.898081     -1.860702
  C       1.545835      4.898591     -1.129246
  N      -1.951448      0.264411     -0.030263
  C      -2.674670     -0.090036      2.278076
  C       0.727926      3.153453     -3.169323
  H       0.424219      2.487800     -3.979323
  C       1.561701      4.244263     -3.456770
  H       1.893833      4.411972     -4.484737
  C       1.973134      5.120510     -2.440883
  H       2.621895      5.967959     -2.671753
  C       0.711680      3.807997     -0.839126
  C       0.205770      3.475809      0.489614
  C       0.423659      4.127661      1.696600
  H       1.044406      5.022724      1.729516
  C      -0.174862      3.612195      2.875975
  C      -0.965807      2.473254      2.812896
  H      -1.427479      2.070207      3.714882
  C      -1.177964      1.827445      1.575703
  N      -0.580113      2.350230      0.431517
  C      -1.952379      0.656373      1.318049
  C      -3.383050     -1.214983      1.897805
  H      -3.939395     -1.793277      2.636992
  C      -3.372642     -1.604515      0.530598
  H      -3.912194     -2.486170      0.185360
  C      -2.652663     -0.839953     -0.374346
  H      -2.612069     -1.095762     -1.435551
  H      -0.011907      4.111028      3.832229
  H       1.861024      5.575550     -0.330798
  H      -2.665162      0.232132      3.320679

35
cationradical_[Ni((MeO)Phbpy)Br]_BP86d3_TZVP_COSMO_THF
  Ni     -0.800265      1.552717     -1.239057
  Br     -1.165963      0.481066     -3.236024
  C       0.305204      2.923052     -1.896997
  C       1.562151      4.909414     -1.139187
  N      -1.928411      0.292559     -0.044451
  C      -2.632022     -0.041959      2.235816
  C       0.749822      3.172994     -3.215629
  H       0.441924      2.509582     -4.022158
  C       1.574710      4.248483     -3.509663
  H       1.899147      4.412114     -4.535819
  C       1.986530      5.124929     -2.473689
  O       2.778814      6.188653     -2.656071
  C       0.740670      3.835446     -0.857722
  C       0.235479      3.504164      0.471739
  C       0.452164      4.156999      1.687409
  H       1.074522      5.049622      1.729808
  C      -0.143850      3.644569      2.842263
  C      -0.941485      2.500010      2.775759
  C      -1.131719      1.878886      1.536949
  N      -0.544330      2.391690      0.429358
  C      -1.927927      0.675764      1.269062
  C      -3.348175     -1.175573      1.848058
  H      -3.904402     -1.750833      2.588171
  C      -3.341456     -1.560227      0.506292
  H      -3.885914     -2.439336      0.164509
  C      -2.618936     -0.799130     -0.412245
  H      -2.578080     -1.051621     -1.472596
  H       0.013842      4.139028      3.800312
  H       1.897138      5.604349     -0.368474
  H      -2.622021      0.278592      3.276623
  C       3.259676      6.494082     -3.992113
  H       3.869375      5.664429     -4.374299
  H       3.871649      7.391718     -3.873417
  H       2.413632      6.696026     -4.662320
  H      -1.407427      2.096434      3.672792

34
cationradical_[Ni(Ph(7-CF3)bpy)Br]_BP86d3_TZVP_COSMO_THF
  Ni     -0.984280      1.597053     -1.167747
  Br     -2.088860      1.305154     -3.108435
  C       0.229443      2.929934     -1.856399
  C       1.616767      4.796980     -1.104491
  N      -2.046983      0.331654      0.041596
  C      -2.475242     -0.256833      2.320605
  C       0.735694      3.063738     -3.146360
  H       0.394194      2.421769     -3.956965
  C       1.692880      4.060994     -3.410911
  H       2.088140      4.160601     -4.422907
  C       2.120310      4.927751     -2.402745
  H       2.850912      5.706349     -2.624155
  C       0.671562      3.800053     -0.822807
  C       0.142137      3.518891      0.503100
  C       0.346431      4.228470      1.686113
  H       0.968242      5.121359      1.701497
  C      -0.287420      3.787708      2.838792
  C      -1.094845      2.639145      2.842739
  C      -1.788961      2.295155      4.146452
  C      -1.235693      1.903053      1.644873
  N      -0.633103      2.398076      0.529296
  C      -1.957476      0.630646      1.375641
  C      -3.120028     -1.421923      1.894565
  H      -3.524191     -2.113330      2.633599
  C      -3.230933     -1.688934      0.534024
  H      -3.728338     -2.583420      0.162230
  C      -2.667600     -0.784142     -0.366221
  H      -2.708917     -0.943393     -1.444078
  H      -0.166792      4.353878      3.760329
  H       1.973876      5.455989     -0.311319
  H      -2.372230     -0.077591      3.383436
  F      -3.122960      2.081705      3.970811
  F      -1.668273      3.291299      5.055407
  F      -1.266303      1.173129      4.729597

38
neutral_[Ni((MeO)Ph(7-CF3)bpy)Br]_BP86d3_TZVP_COSMO_THF
  Ni     -1.059208      1.617091     -1.134740
  Br     -1.797991      0.830204     -3.180172
  C       0.144560      2.897367     -1.862837
  C       1.562441      4.801641     -1.155151
  N      -2.073588      0.397489      0.019097
  C      -2.429441     -0.250280      2.309997
  C       0.618494      3.088486     -3.165455
  H       0.268724      2.444512     -3.972254
  C       1.536021      4.104530     -3.476878
  H       1.874676      4.212322     -4.506679
  C       2.006863      4.967966     -2.472934
  O       2.897630      5.990452     -2.681783
  C       0.654563      3.777544     -0.861880
  C       0.164377      3.496101      0.475116
  C       0.401432      4.197570      1.657968
  H       1.044183      5.076229      1.660503
  C      -0.230273      3.781424      2.822527
  C      -1.066485      2.654496      2.828504
  C      -1.778254      2.335078      4.119505
  C      -1.223988      1.918027      1.630020
  N      -0.633749      2.386961      0.495391
  C      -1.953051      0.661271      1.362919
  C      -3.078231     -1.411597      1.889535
  H      -3.448558     -2.123789      2.626866
  C      -3.230584     -1.647879      0.524140
  H      -3.732241     -2.539268      0.149076
  C      -2.703045     -0.726024     -0.375602
  H      -2.767455     -0.867661     -1.455261
  H      -0.092293      4.350045      3.739906
  H       1.941392      5.471957     -0.381588
  H      -2.283043     -0.083832      3.370639
  F      -3.110968      2.101450      3.935191
  F      -1.687254      3.353141      5.015482
  F      -1.262896      1.229498      4.752573
  C       3.367434      6.193048     -4.025538
  H       3.910159      5.308445     -4.394487
  H       4.050223      7.047495     -3.971864
  H       2.534376      6.427591     -4.706600

35
neutral_[Ni((MeO)Phbpy)Br]_BP86d3_TZVP_COSMO_THF
  Ni     -0.818672      1.527692     -1.235929
  Br     -1.190252      0.440333     -3.250075
  C       0.308725      2.925064     -1.905663
  C       1.568464      4.916613     -1.149565
  N      -1.938243      0.282638     -0.041890
  C      -2.635309     -0.045057      2.245319
  C       0.758952      3.187045     -3.203249
  H       0.462028      2.532878     -4.023497
  C       1.594427      4.280068     -3.489652
  H       1.919244      4.441517     -4.516943
  C       2.000766      5.147174     -2.463069
  O       2.814403      6.239609     -2.643483
  C       0.737615      3.825126     -0.879625
  C       0.231794      3.492069      0.446875
  C       0.447390      4.144613      1.664959
  H       1.070082      5.037766      1.700027
  C      -0.143407      3.640051      2.825804
  C      -0.941935      2.494820      2.764725
  C      -1.134315      1.872402      1.528105
  N      -0.552041      2.372745      0.404208
  C      -1.933265      0.669238      1.271015
  C      -3.354630     -1.179348      1.869378
  H      -3.907726     -1.750566      2.615286
  C      -3.353710     -1.569717      0.527450
  H      -3.900393     -2.450351      0.191981
  C      -2.634569     -0.812630     -0.395846
  H      -2.597157     -1.067963     -1.456307
  H       0.018052      4.139187      3.781321
  H       1.889514      5.599387     -0.360552
  H      -2.618749      0.282261      3.284244
  C       3.266994      6.508825     -3.980497
  H       3.869753      5.674065     -4.372287
  H       3.888125      7.407633     -3.905968
  H       2.419072      6.701001     -4.656640
  H      -1.406959      2.092503      3.663028

34
neutral_[Ni(Ph(7-CF3)bpy)Br]_BP86d3_TZVP_COSMO_THF
  Ni     -1.031894      1.625688     -1.113385
  Br     -1.758762      0.858895     -3.169869
  C       0.192056      2.900130     -1.821964
  C       1.607596      4.796701     -1.097125
  N      -2.069423      0.404980      0.024330
  C      -2.464762     -0.248410      2.306178
  C       0.690702      3.073251     -3.120715
  H       0.348416      2.424146     -3.926384
  C       1.620228      4.084659     -3.405175
  H       1.992566      4.197074     -4.425853
  C       2.076732      4.950050     -2.400978
  H       2.797147      5.735143     -2.636094
  C       0.684189      3.776995     -0.809909
  C       0.171524      3.495206      0.517179
  C       0.393495      4.194166      1.705042
  H       1.034628      5.073865      1.718001
  C      -0.248317      3.772325      2.861471
  C      -1.082052      2.643019      2.855944
  C      -1.795720      2.311970      4.143271
  C      -1.231273      1.913969      1.652497
  N      -0.627066      2.385851      0.526478
  C      -1.965638      0.662445      1.370413
  C      -3.116424     -1.402864      1.870735
  H      -3.504153     -2.114454      2.599697
  C      -3.248784     -1.633459      0.502797
  H      -3.751799     -2.519375      0.116768
  C      -2.700420     -0.711780     -0.385016
  H      -2.749336     -0.848630     -1.466109
  H      -0.118945      4.336542      3.782757
  H       1.965901      5.458704     -0.305880
  H      -2.334763     -0.087568      3.369580
  F      -3.131264      2.095681      3.958084
  F      -1.692366      3.314667      5.054749
  F      -1.290859      1.191387      4.757650

31
neutral_[Ni(Phbpy)Br]_BP86d3_TZVP_COSMO_THF
  Ni     -0.843561      1.501677     -1.205324
  Br     -1.213915      0.414921     -3.218328
  C       0.283672      2.902055     -1.873567
  C       1.542798      4.893533     -1.123021
  N      -1.963213      0.252954     -0.012561
  C      -2.662214     -0.077731      2.273027
  C       0.729855      3.156139     -3.177317
  H       0.429586      2.496827     -3.992013
  C       1.563585      4.251494     -3.452350
  H       1.897272      4.425362     -4.477844
  C       1.970913      5.120499     -2.432124
  H       2.618633      5.969221     -2.657461
  C       0.709387      3.799442     -0.844399
  C       0.202611      3.464464      0.479859
  C       0.416012      4.115974      1.699631
  H       1.037710      5.009733      1.736337
  C      -0.175281      3.609953      2.859045
  C      -0.972802      2.463531      2.796676
  H      -1.438295      2.060067      3.694194
  C      -1.162911      1.842470      1.559547
  N      -0.580151      2.344502      0.436899
  C      -1.960137      0.638329      1.300339
  C      -3.379417     -1.212747      1.895195
  H      -3.932450     -1.785402      2.640017
  C      -3.376429     -1.601818      0.553130
  H      -3.921369     -2.482919      0.216113
  C      -2.657268     -0.842703     -0.368724
  H      -2.618422     -1.096944     -1.429362
  H      -0.015320      4.108541      3.815100
  H       1.855951      5.566802     -0.321921
  H      -2.647410      0.248655      3.312209

62
triplet_cation_[Ni(hapto2-(MeO)Phbpy)Br]_BP86d3-TZVP_COSMO_THF
  Ni     -0.774531      1.097051     -0.633344
  C       2.677495      3.882118      0.227868
  C       1.023720      3.211476     -1.393250
  N      -2.033017      0.237851      0.712214
  C      -3.215432      0.608811      2.743105
  C       3.632188      3.902853     -0.778749
  H       4.651436      4.180818     -0.542001
  C       3.308700      3.561119     -2.089268
  H       4.075469      3.572435     -2.850059
  C       1.994780      3.206797     -2.397403
  O       1.563164      2.834664     -3.625337
  C       1.360432      3.517978     -0.077264
  C       0.361982      3.411217      1.006398
  C       0.322397      4.326051      2.062208
  H       1.005143      5.163270      2.076237
  C      -0.617835      4.159205      3.064418
  C      -1.489854      3.077700      3.016078
  C      -1.403787      2.195420      1.946351
  N      -0.499548      2.383387      0.962299
  C      -2.253532      0.988517      1.811206
  C      -3.945870     -0.554350      2.528048
  H      -4.697189     -0.861093      3.243933
  C      -3.702145     -1.315307      1.392198
  H      -4.250879     -2.223831      1.188740
  C      -2.733249     -0.878772      0.500947
  H      -2.509561     -1.413496     -0.412358
  H      -0.675789      4.865038      3.882677
  H       0.003752      3.010970     -1.695521
  H      -3.401135      1.205688      3.623362
  C      -3.861474      4.317734     -1.347979
  C      -2.400007      3.906955     -1.242024
  C      -3.746220      1.939355     -1.430732
  C      -4.496153      3.108839     -2.045783
  O      -2.413668      2.454981     -1.136429
  H      -1.838581      4.182033     -2.137393
  H      -1.897527      4.310180     -0.364694
  H      -3.980397      5.243241     -1.909815
  H      -4.294417      4.458824     -0.355639
  H      -5.569258      3.037249     -1.868800
  H      -4.317147      3.148469     -3.122478
  H      -3.627088      1.084466     -2.091627
  H      -4.199781      1.617111     -0.491016
  C       2.531000      2.661106     -4.665416
  H       3.014133      3.608113     -4.918600
  H       1.975166      2.289991     -5.521979
  H       3.287570      1.929460     -4.373647
  H      -2.218611      2.933975      3.799488
  O       0.979118      0.014341     -0.171196
  H       0.508223     -1.290166      1.359688
  H       0.107226     -1.873706     -0.278348
  C       0.848762     -1.350301      0.328423
  C       2.232844     -1.948721      0.149213
  H       2.209187     -3.038005      0.130637
  C       2.665088     -1.329719     -1.185776
  H       2.893955     -1.624550      0.955720
  H       3.743322     -1.348861     -1.342554
  C       2.130457      0.091734     -1.078874
  H       2.842673      0.780984     -0.624889
  H       2.183992     -1.850088     -2.015420
  H       1.782696      0.485195     -2.030429
  Br     -1.057629     -0.146731     -2.716645
  H       2.959129      4.118167      1.244931
