Extremely Strong Halogen Bond. The Case of a Double-Charge-Assisted Halogen Bridge

Supporting Information Extremely Strong Halogen Bond. The Case of a Double-Charge-Assisted Halogen Bridge Małgorzata Domagała*, Aneta Lutyńska, Marcin Palusiak Theoretical and Structural Chemistry Group, Faculty of Chemistry, University of Lodz, Pomorska 163/165, 90-236 Lodz, Poland malgorzata.domagala@chemia.uni.lodz.pl Contents: page S2 page S6 page S6 page S7 page S7 page S8 page S8 page S12 page S15 page S20 page S24 Figure S1. Molecular graphs of studied (+/-)CAXB complexes. Figure S2. Molecular graphs of studied (+/-)CAXB complexes, view along halogen bond directions to quinuclidine cage (left) and its unsaturated derivative (right). Figure S3. Linear relation between CT in Quin_I and Quin_II (+/-)CAXB complexes. Figure S4. Linear relation between CT NBO vs CT AIM in Quin_I (full black circles) and Quin_II (empty black circles) (+/-)CAXB complexes. Figure S5. Molecular graphs of studied neutral complexes Quin_II-Br NCH and Quin_II-Cl NCH. Table S1. Bond length changes [Å] in cage of Quin_I and Quin_II (+/-)CAXB complexes. Table S2. Atom coordinates of (+/-)CAXB dimers with Quinu_I corresponding to optimized geometries with CP-correction at ωb97xd/aug-cc-pvtz level of theory. Table S3. Atom coordinates of (+/-)CAXB dimers with Quinu_II corresponding to optimized geometries with CP-correction at ωb97xd/aug-cc-pvtz level of theory. Table S4. Atom coordinates of partially charged dimers with Quinu_I corresponding to optimized geometries with CP-correction at ωb97xd/aug-cc-pvtz level of theory. Table S5. Atom coordinates of partially charged dimers with Quinu_II corresponding to optimized geometries with CP-correction at ωb97xd/aug-cc-pvtz level of theory. Table S6. Atom coordinates of neutral dimers with Quinu_II corresponding to optimized geometries with CP-correction at ωb97xd/aug-cc-pvtz level of theory. S1

H-Quin_I-Cl F CN-Quin_I-Cl F H-Quin_I-Cl Cl CN-Quin_I-Cl Cl H-Quin_I-Cl Br CN-Quin_I-Cl Br H-Quin_I-Cl CN CN-Quin_I-Cl CN S2

H-Quin_I-Br F CN-Quin_I-Br F H-Quin_I-Br Cl CN-Quin_I-Br Cl H-Quin_I-Br Br CN-Quin_I-Br Br H-Quin_I-Br CN CN-Quin_I-Br CN S3

H-Quin_II-Cl F CN-Quin_II-Cl F H-Quin_II-Cl Cl CN-Quin_II-Cl Cl H-Quin_II-Cl Br CN-Quin_II-Cl Br H-Quin_II-Cl CN CN-Quin_II-Cl CN S4

H-Quin_II-Br F CN-Quin_II-Br F H-Quin_II-Br Cl CN-Quin_II-Br Cl H-Quin_II-Br Br CN-Quin_II-Br Br H-Quin_II-Br CN CN-Quin_II-Br CN Figure S1. Molecular graphs of studied (+/-)CAXB complexes. S5

Figure S2. Molecular graphs of studied (+/-)CAXB complexes. View along halogen bond directions to quinuclidine cage (left) and its unsaturated derivative (right). 0.35 CT Quin_II 0.3 0.25 0.2 0.15 0.1 0.05 0 y = 1.1052x + 0.0361 R² = 0.9373 CT Quin_I 0 0.05 0.1 0.15 0.2 0.25 Figure S3. Linear relation between CT in Quin_I and Quin_II (+/-)CAXB complexes. S6

0.32 0.27 CT AIM y = 0.8242x + 0.0361 R² = 0.9783 0.22 0.17 0.12 0.07 y = 0.788x + 0.0327 R² = 0.984 CT NBO 0.02 0.02 0.12 0.22 0.32 0.42 Figure S4. Linear relation between CT NBO vs CT AIM in Quin_I (full black circles) and Quin_II (empty black circles) (+/-)CAXB complexes. Figure S5. Molecular graphs of studied neutral complexes Quin_II-Br NCH and Quin_II- Cl NCH. S7

Table S1. Bond length changes [Å] in cage Quin_I and Quin_II (+/-)CAXB complexes. Quin_I Quin_II N-C C-C C-C N-C C=C C-C H/Cl F 0.002 0.000-0.002 0.001 0.002-0.004 H/Cl Cl 0.001-0.001-0.001 0.001 0.001-0.002 H/Cl Br 0.001-0.001-0.001 0.001 0.001-0.002 H/Cl NC 0.001-0.002 0.001 0.001 0.001-0.001 H/Br F 0.002 0.001-0.004 0.002 0.001-0.004 H/Br Cl 0.002 0.000-0.003 0.002 0.000-0.003 H/Br Br 0.002 0.000-0.003 0.002 0.000-0.003 H/Br NC 0.002-0.002 0.000 0.002-0.002 0.000 CN/Cl F 0.004-0.001-0.003 0.004 0.001-0.005 CN/Cl Cl 0.003-0.002-0.001 0.003 0.001-0.003 CN/Cl Br 0.003-0.002-0.001 0.003 0.001-0.004 CN/Cl NC 0.003-0.002 0.000 0.003 0.000-0.001 CN/Br F 0.005 0.000-0.005 0.004 0.002-0.005 CN/Br Cl 0.004-0.001-0.004 0.004 0.001-0.005 CN/Br Br 0.004-0.001-0.004 0.004 0.001-0.006 CN/Br NC 0.004-0.001-0.002 0.003 0.001-0.003 Table S2. Atom coordinates of (+/-)CAXB dimers with Quinu_I corresponding to optimized geometries with CP-correction at ωb97xd/aug-cc-pvtz level of theory. H-Quin_I-Cl F C 0.651099-0.504717-0.082579 C 1.287243 1.915608-0.001865 C 0.124063 0.929045 0.091672 H 0.409320-0.928035-1.055794 H 0.304960-1.188810 0.689872 H -0.607665 1.154497-0.681137 H -0.373441 1.045093 1.053237 C 2.727272 0.246018-1.188657 H 3.801668 0.301906-1.023298 H 2.541338-0.382819-2.057252 C 2.065901 1.630624-1.285419 H 2.823971 2.397512-1.429219 H 1.390096 1.678649-2.137804 C 2.214923 1.689276 1.191248 H 3.104994 2.306677 1.080853 H 1.715014 2.001812 2.105509 C 2.588690 0.200258 1.276360 H 3.658885 0.028739 1.375008 CN-Quin_I-Cl F C 0.620213-0.481859-0.104303 C 1.279972 1.932941-0.000545 C 0.117532 0.949463 0.111310 H 0.406516-0.874543-1.096040 H 0.272810-1.193758 0.640807 H -0.632922 1.187050-0.639935 H -0.353612 1.050219 1.087672 C 2.739928 0.285839-1.197176 H 3.805635 0.360494-0.992101 H 2.589115-0.355970-2.062112 C 2.039123 1.644660-1.293728 H 2.780724 2.422887-1.462271 H 1.347164 1.662895-2.134095 C 2.223830 1.711465 1.179088 H 3.125948 2.305222 1.041338 H 1.746158 2.050291 2.096119 C 2.569526 0.224089 1.302422 H 3.631228 0.022617 1.424581 S8

H 2.077372-0.317761 2.085687 N 2.153082-0.471918 0.002552 H 2.498851-1.425535 0.004290 Cl 0.665631 3.629620-0.005074 F -0.065970 5.646019-0.008865 HF= -889.300967781659 H-Quin_I-Cl Cl C 0.656734-0.526364-0.074671 C 1.299544 1.887663-0.001787 C 0.132007 0.906095 0.110971 H 0.407087-0.942404-1.048700 H 0.310418-1.211878 0.695796 H -0.611459 1.133268-0.649389 H -0.348277 1.022963 1.080793 C 2.727922 0.217729-1.192415 H 3.802132 0.280600-1.030371 H 2.542948-0.412505-2.059632 C 2.061481 1.598641-1.296104 H 2.814920 2.366272-1.455968 H 1.373619 1.637386-2.138853 C 2.241959 1.668295 1.182837 H 3.134576 2.277937 1.054502 H 1.756768 1.991543 2.100758 C 2.602042 0.176859 1.272424 H 3.670882 0.000205 1.371680 H 2.088077-0.331413 2.085841 N 2.158898-0.497235 0.002615 H 2.502804-1.451864 0.004354 Cl -0.259083 6.214094-0.010365 Cl 0.691296 3.575868-0.004991 HF= -1249.707614895927 H-Quin_I-Cl Br C 0.661765-0.534390-0.091678 C 1.301678 1.878491-0.000452 C 0.133325 0.896338 0.096817 H 0.421827-0.945094-1.070340 H 0.308215-1.224129 0.671595 H -0.603418 1.126513-0.669095 H -0.355644 1.007720 1.062889 C 2.742972 0.217417-1.185298 H 3.815367 0.281398-1.012386 H 2.567600-0.408397-2.057606 C 2.075582 1.597851-1.289430 H 2.829425 2.367122-1.438816 H 1.395369 1.639365-2.138177 C 2.233102 1.655802 1.192139 H 3.126392 2.266569 1.074677 H 1.739233 1.974358 2.107007 C 2.592965 0.164100 1.277912 H 3.660861-0.011837 1.387288 H 2.071246-0.348055 2.083851 N 2.163043-0.504091 0.000511 H 2.507977-1.458434 0.000856 H 2.019190-0.287266 2.089349 N 2.152043-0.474265 0.000678 C 2.623254-1.776954-0.000143 N 3.012144-2.853148-0.001652 Cl 0.661712 3.656657 0.001837 F -0.041508 5.644220 0.008383 HF= -981.489056795566 CN-Quin_I-Cl Cl C 0.629984-0.504538-0.109483 C 1.288016 1.906611-0.001489 C 0.123126 0.923769 0.113588 H 0.417793-0.890440-1.103991 H 0.277115-1.218652 0.630428 H -0.630332 1.161891-0.633879 H -0.343293 1.022242 1.092121 C 2.751345 0.264676-1.193040 H 3.815413 0.346594-0.983264 H 2.608915-0.375117-2.060441 C 2.045183 1.619710-1.298015 H 2.783169 2.399687-1.471561 H 1.350681 1.631531-2.136024 C 2.234847 1.689498 1.178764 H 3.138259 2.279532 1.035957 H 1.760877 2.032634 2.095606 C 2.571939 0.200642 1.303561 H 3.632239-0.000987 1.434288 H 2.015417-0.306017 2.088903 N 2.160475-0.497198 0.000968 C 2.632825-1.800460 0.000763 N 3.022271-2.876300-0.000321 Cl -0.229991 6.203873 0.015741 Cl 0.679450 3.600065 0.000305 HF= -1341.893601219189 CN-Quin_I-Cl Br C 0.633770-0.512239-0.106656 C 1.290977 1.898309-0.003135 C 0.126012 0.915929 0.115396 H 0.420048-0.899391-1.100312 H 0.281702-1.225178 0.634693 H -0.628690 1.152565-0.631201 H -0.338706 1.015671 1.094555 C 2.752948 0.256432-1.194035 H 3.817262 0.339611-0.986190 H 2.609597-0.384264-2.060563 C 2.046002 1.611035-1.300794 H 2.783431 2.390935-1.476670 H 1.350175 1.621028-2.137663 C 2.239783 1.684952 1.176134 H 3.142789 2.274839 1.030434 H 1.767467 2.029620 2.093206 C 2.576838 0.196272 1.302810 H 3.637295-0.004447 1.433169 H 2.021148-0.308733 2.089748 N 2.164213-0.503844 0.001796 C 2.637416-1.807032 0.003071 S9

Cl 0.692339 3.564404-0.001092 Br -0.323925 6.378737-0.001845 HF= -3363.760087364140 H-Quin_I-Cl NC C 0.616030-0.434412-0.115404 C 1.347936 1.946857 0.092168 C 0.145424 1.001371 0.162125 H 0.343077-0.780329-1.110250 H 0.249759-1.151971 0.615407 H -0.597093 1.301674-0.573097 H -0.319314 1.077447 1.143435 C 2.703360 0.297795-1.208789 H 3.780399 0.313571-1.054714 H 2.488877-0.273144-2.109399 C 2.086005 1.704470-1.227146 H 2.864471 2.452878-1.353549 H 1.390175 1.816481-2.056461 C 2.294074 1.625315 1.251204 H 3.208315 2.206599 1.146121 H 1.831039 1.912474 2.192124 C 2.596097 0.118431 1.250292 H 3.658023-0.103133 1.330097 H 2.068918-0.415235 2.038434 N 2.118631-0.464208-0.051410 N -0.100953 6.148569 0.228095 C -0.859176 6.244800-0.657707 Cl 0.794974 3.633370 0.176496 H 2.427401-1.429174-0.108200 HF= -882.269187833551 H-Quin_I-Br F C 0.652043-0.512573-0.078768 C 1.290277 1.911722-0.000216 C 0.127229 0.925936 0.081302 H 0.406648-0.947468-1.046165 H 0.309826-1.188342 0.703097 H -0.597789 1.142324-0.700999 H -0.384399 1.041692 1.035836 C 2.724801 0.235516-1.193348 H 3.801436 0.277914-1.037619 H 2.523390-0.389442-2.061645 C 2.076804 1.629581-1.278022 H 2.847357 2.386071-1.413734 H 1.411316 1.689499-2.138157 C 2.209014 1.677744 1.196655 H 3.098418 2.299348 1.102438 H 1.704812 1.974021 2.114505 C 2.596313 0.189479 1.272366 H 3.668891 0.024602 1.358824 H 2.097005-0.336991 2.083982 N 2.153984-0.480477 0.000162 H 2.498351-1.434328 0.000301 Br 0.604218 3.810926-0.000558 F -0.113593 5.796089-0.000916 N 3.027536-2.882610 0.003364 Br -0.303887 6.364913 0.020695 Cl 0.680597 3.588874-0.002365 HF= -3455.945628811099 CN-Quin_I-Cl NC C 0.557477-0.314107-0.098812 C 1.449000 2.023835-0.032362 C 0.193345 1.159191 0.102212 H 0.306202-0.692146-1.087181 H 0.135778-0.977278 0.652241 H -0.537481 1.458482-0.645399 H -0.256475 1.319927 1.080065 C 2.742883 0.224890-1.193157 H 3.810011 0.204870-0.984087 H 2.537622-0.411619-2.050144 C 2.173543 1.640721-1.323842 H 2.984441 2.341005-1.510280 H 1.483289 1.705831-2.162790 C 2.372243 1.735750 1.153042 H 3.328779 2.232395 1.001172 H 1.933495 2.138832 2.062832 C 2.559859 0.223435 1.303261 H 3.594943-0.079483 1.439489 H 1.955678-0.210943 2.096407 N 2.081358-0.454039 0.012683 C 2.425658-1.796794 0.036914 N 2.710610-2.904649 0.056784 N 0.212740 6.220711-0.038634 C -0.865446 6.321711 0.404324 Cl 0.990121 3.742608-0.054885 HF= -974.454510137623 CN-Quin_I-Br F C 0.620087-0.487046-0.095538 C 1.283867 1.932458 0.000579 C 0.120795 0.950671 0.100112 H 0.398901-0.895772-1.079257 H 0.278446-1.186798 0.664001 H -0.621974 1.177109-0.662721 H -0.365973 1.054071 1.068820 C 2.735467 0.275158-1.203586 H 3.805060 0.330401-1.012257 H 2.562392-0.362831-2.067462 C 2.053088 1.647138-1.285206 H 2.810243 2.413296-1.442047 H 1.373854 1.682236-2.135754 C 2.215896 1.704386 1.186281 H 3.115028 2.307542 1.068777 H 1.729377 2.022030 2.106758 C 2.581145 0.218138 1.297581 H 3.646792 0.025686 1.400727 H 2.048371-0.304086 2.089491 Br 0.596135 3.841697 0.001743 N 2.152555-0.480266-0.000787 C 2.621590-1.783147-0.001568 N 3.009095-2.859876-0.002252 S10

HF= -3003.362360661516 H-Quin_I-Br Cl C 0.661065-0.534477-0.085499 C 1.299144 1.883944 0.000617 C 0.133315 0.900433 0.089048 H 0.417992-0.957221-1.058499 H 0.313466-1.217232 0.687258 H -0.598780 1.120549-0.684884 H -0.367842 1.011485 1.049273 C 2.737128 0.216700-1.189698 H 3.811759 0.270272-1.025927 H 2.548387-0.407820-2.060610 C 2.079136 1.604503-1.283030 H 2.842665 2.365745-1.427435 H 1.406986 1.654446-2.138157 C 2.223603 1.655760 1.195498 H 3.115379 2.271767 1.091649 H 1.726047 1.959849 2.113835 C 2.598828 0.165462 1.274361 H 3.669417-0.003541 1.371351 H 2.089503-0.354890 2.083282 N 2.162450-0.502784-0.000482 H 2.507420-1.456772-0.000938 Br 0.625380 3.753665 0.000659 Cl -0.296093 6.322996-0.002358 HF= -3363.761410237322 H-Quin_I-Br Br C 0.663724-0.541227-0.087224 C 1.303150 1.875341-0.000296 C 0.135979 0.893558 0.087386 H 0.421768-0.963058-1.060843 H 0.314115-1.223889 0.684610 H -0.595354 1.114236-0.687007 H -0.365482 1.004982 1.047340 C 2.741809 0.209130-1.188054 H 3.816122 0.262886-1.022616 H 2.554463-0.415113-2.059372 C 2.084180 1.596998-1.283420 H 2.848031 2.358013-1.426940 H 1.413014 1.646649-2.139254 C 2.226308 1.648992 1.195826 H 3.118769 2.263873 1.091734 H 1.728457 1.954356 2.113489 C 2.599363 0.158236 1.275809 H 3.669523-0.011481 1.375437 H 2.087698-0.360829 2.084010 N 2.164950-0.510027 0.000308 H 2.509622-1.464214 0.000523 Br -0.362535 6.483428-0.001362 Br 0.628676 3.742001-0.000762 HF= -5477.812491768400 F -0.110046 5.800229 0.003046 HF= -3095.551392516421 CN-Quin_I-Br Cl C 0.628918-0.507132-0.097196 C 1.292663 1.906887-0.000248 C 0.127239 0.927478 0.109492 H 0.407589-0.907034-1.084298 H 0.283171-1.210951 0.656262 H -0.623014 1.155710-0.644826 H -0.348546 1.028683 1.083533 C 2.744374 0.255006-1.200800 H 3.812425 0.319929-1.005003 H 2.580511-0.383420-2.065762 C 2.053814 1.621520-1.291971 H 2.804863 2.390925-1.459001 H 1.367874 1.646659-2.137085 C 2.232113 1.686187 1.182232 H 3.133188 2.283549 1.053382 H 1.753804 2.012613 2.103439 C 2.585834 0.198212 1.298182 H 3.649745 0.002545 1.409629 H 2.045697-0.316612 2.089694 Br 0.615013 3.786835-0.000467 N 2.160425-0.500963 0.000133 C 2.630137-1.804572 0.000297 N 3.017899-2.881074 0.000403 Cl -0.295547 6.311437-0.000546 HF= -3455.948468305230 CN-Quin_I-Br Br C 0.632965-0.514650-0.102820 C 1.293501 1.897874-0.001958 C 0.128410 0.918233 0.108643 H 0.417241-0.910153-1.092886 H 0.284155-1.222614 0.645209 H -0.623234 1.147216-0.643991 H -0.345610 1.017423 1.083720 C 2.751181 0.250755-1.196541 H 3.817377 0.324139-0.994091 H 2.597297-0.389209-2.062146 C 2.053235 1.612800-1.294746 H 2.800226 2.384857-1.467366 H 1.364319 1.629657-2.137598 C 2.234862 1.680522 1.179707 H 3.138731 2.272262 1.044972 H 1.761124 2.013980 2.100661 C 2.581657 0.191642 1.301487 H 3.643891-0.006660 1.423033 H 2.033285-0.318958 2.090133 Br 0.617458 3.777334-0.000110 N 2.163634-0.506994 0.001419 C 2.634545-1.810460 0.001871 N 3.022759-2.886804 0.001474 Br -0.342817 6.470229 0.011403 HF= -5569.999267471236 S11

H-Quin_I-Br NC C 0.658027-0.522378-0.089150 C 1.294327 1.897810-0.000208 C 0.129584 0.910760 0.092093 H 0.417176-0.939078-1.065207 H 0.307109-1.208963 0.678472 H -0.606941 1.131523-0.677239 H -0.366586 1.019199 1.055163 C 2.736376 0.229443-1.186648 H 3.809844 0.288369-1.017756 H 2.555084-0.395851-2.058382 C 2.073285 1.613874-1.285507 H 2.834069 2.376616-1.435475 H 1.399093 1.657561-2.139320 C 2.223008 1.668529 1.193378 H 3.117192 2.280063 1.084199 H 1.730531 1.977834 2.112537 C 2.590957 0.177204 1.276197 H 3.660139 0.004628 1.380330 H 2.074869-0.339053 2.083332 N 2.158863-0.491051 0.000232 N -0.219329 6.076431-0.000689 C -0.619356 7.173870-0.000361 H 2.504043-1.445018 0.000377 Br 0.624127 3.749249-0.000509 HF= -2996.321686265665 CN-Quin_I-Br NC C 0.628403-0.500200-0.104337 C 1.287188 1.916447-0.000108 C 0.123850 0.931589 0.110370 H 0.411309-0.892841-1.095217 H 0.278459-1.209050 0.642221 H -0.629908 1.160281-0.640079 H -0.348614 1.028051 1.086463 C 2.746756 0.265959-1.196190 H 3.812991 0.337538-0.993300 H 2.592983-0.371907-2.063235 C 2.049628 1.628122-1.292719 H 2.797124 2.399882-1.463776 H 1.362883 1.646974-2.137290 C 2.229211 1.693193 1.182355 H 3.132094 2.287196 1.050994 H 1.754086 2.022683 2.103938 C 2.576886 0.204563 1.300485 H 3.639304 0.006833 1.420733 H 2.029559-0.307801 2.088560 Br 0.614379 3.775375-0.000023 N 2.158850-0.493245 0.000011 C 2.630173-1.796470 0.000025 N 3.019187-2.872470 0.000008 N -0.212413 6.058989 0.000389 C -0.603692 7.159548-0.000371 HF= -3088.508183591101 Table S3. Atom coordinates of (+/-)CAXB dimers with Quinu_II corresponding to optimized geometries with CP-correction at ωb97xd/aug-cc-pvtz level of theory. H-Quin_II-Cl F C 0.636788-0.387224 0.087521 C 1.290645 1.909782 0.189945 C 0.197972 0.849659 0.063150 H 0.142867-1.340613 0.022625 H -0.833999 1.148865-0.035703 C 2.725335 0.346665-0.911265 H 3.411401-0.192155-1.540647 C 2.275447 1.579665-0.930469 H 2.544150 2.335918-1.651676 C 2.033680 1.541313 1.472874 H 2.151336 2.273736 2.256437 C 2.482329 0.308158 1.504877 H 3.031450-0.252115 2.240858 N 2.132815-0.422059 0.237594 H 2.476755-1.374396 0.256958 F -0.033356 5.576491 0.116097 Cl 0.668268 3.633352 0.155100 HF= -885.554214513291 CN-Quin_II-Cl F C 0.605276-0.361957 0.053396 C 1.283288 1.932491 0.192525 C 0.189113 0.880038 0.052313 H 0.125561-1.321739-0.023974 H -0.843022 1.184046-0.038579 C 2.722761 0.397679-0.954843 H 3.404513-0.145472-1.585322 C 2.262280 1.623779-0.934938 H 2.528042 2.393479-1.644114 C 2.027772 1.547316 1.466050 H 2.146982 2.269258 2.260141 C 2.483208 0.319593 1.497345 H 3.033902-0.266049 2.212227 N 2.129966-0.416649 0.200562 C 2.599187-1.719000 0.204796 N 2.986630-2.794829 0.208136 Cl 0.657151 3.669573 0.187102 F -0.030300 5.574976 0.181612 S12

HF= -977.739223165184 H-Quin_II-Cl Cl C 0.648490-0.417565 0.086015 C 1.303896 1.873715 0.189089 C 0.206163 0.817280 0.059045 H 0.152842-1.369788 0.020016 H -0.825042 1.116597-0.043212 C 2.739898 0.315709-0.906572 H 3.428161-0.221495-1.534645 C 2.292495 1.548783-0.931257 H 2.563176 2.304474-1.651738 C 2.042513 1.511891 1.478007 H 2.157445 2.244771 2.261017 C 2.489348 0.278772 1.508554 H 3.036026-0.279057 2.247952 N 2.143707-0.451691 0.240775 H 2.487744-1.404317 0.261852 Cl 0.693405 3.563167 0.152043 Cl -0.226384 6.103796 0.097336 HF= -1245.956315639832 H-Quin_II-Cl Br C 0.652229-0.427314 0.086030 C 1.307717 1.862486 0.188933 C 0.209080 0.807124 0.058539 H 0.156490-1.379484 0.020002 H -0.822168 1.106009-0.044225 C 2.743909 0.306163-0.905811 H 3.432613-0.230739-1.533653 C 2.296667 1.539174-0.931482 H 2.567632 2.294619-1.652070 C 2.045545 1.502721 1.478801 H 2.160082 2.235653 2.261780 C 2.492331 0.269684 1.509205 H 3.038801-0.287589 2.249171 N 2.147350-0.461033 0.241433 H 2.491602-1.413680 0.262863 Br -0.283836 6.261718 0.093320 Cl 0.697840 3.549529 0.151440 HF= -3360.007803577025 H-Quin_II-Cl NC C 0.638591-0.392257 0.090657 C 1.295609 1.900474 0.180456 C 0.196477 0.842295 0.058061 H 0.140993-1.343738 0.030609 H -0.834878 1.140568-0.043629 C 2.728346 0.333671-0.909752 H 3.414869-0.206543-1.536966 C 2.282766 1.567017-0.940777 H 2.553607 2.317519-1.666296 C 2.037435 1.542845 1.470565 H 2.155310 2.278499 2.250253 C 2.482680 0.309508 1.505620 CN-Quin_II-Cl Cl C 0.616566-0.390220 0.054913 C 1.294906 1.899511 0.188470 C 0.196088 0.849742 0.048766 H 0.134621-1.348984-0.020755 H -0.835583 1.153157-0.045141 C 2.734826 0.366433-0.950638 H 3.418365-0.176024-1.579726 C 2.276669 1.592938-0.939061 H 2.543655 2.360269-1.649807 C 2.036589 1.523515 1.468065 H 2.153952 2.247645 2.259956 C 2.490368 0.295766 1.499913 H 3.039689-0.285253 2.219560 N 2.140160-0.443967 0.205344 C 2.609954-1.747216 0.214514 N 2.997431-2.822877 0.221937 Cl -0.217365 6.091445 0.161302 Cl 0.681416 3.600652 0.176824 HF= -1338.138957477688 CN-Quin_II-Cl Br C 0.786974-0.347108-0.245647 C 1.451095 1.944236-0.094330 C 0.357558 0.889730-0.238551 H 0.310714-1.308199-0.327900 H -0.676612 1.186759-0.324950 C 2.895177 0.432810-1.254054 H 3.579446-0.098911-1.891504 C 2.429249 1.656133-1.229649 H 2.687886 2.431514-1.934713 C 2.200965 1.563196 1.178813 H 2.317367 2.280655 1.976884 C 2.662819 0.338240 1.196699 H 3.219406-0.245300 1.908724 N 2.311512-0.392051-0.102843 C 2.790104-1.692372-0.107714 N 3.184729-2.765433-0.111852 Br -0.146511 6.288464-0.076482 Cl 0.826986 3.640034-0.087796 HF= -3452.189983580693 CN-Quin_II-Cl NC C 0.609808-0.372659 0.050677 C 1.285956 1.920165 0.173730 C 0.187882 0.866516 0.035807 H 0.127002-1.331176-0.021422 H -0.843740 1.167368-0.063690 C 2.730905 0.378367-0.950792 H 3.417044-0.166271-1.575012 C 2.273432 1.604955-0.949072 H 2.544068 2.366903-1.663812 C 2.024216 1.549057 1.459089 H 2.139418 2.276297 2.248086 C 2.477425 0.321535 1.498248 S13

H 3.030223-0.244114 2.247380 N 2.133822-0.426993 0.242545 N -0.148999 5.899510 0.079826 C -0.563623 6.991878 0.071868 Cl 0.692845 3.573461 0.136518 H 2.476962-1.379823 0.267879 HF= -878.516356683716 H-Quin_II-Br F C 0.832772-0.350598-0.247973 C 1.449138 1.957704-0.097228 C 0.375595 0.880514-0.237185 H 0.353800-1.310440-0.330549 H -0.665259 1.154768-0.317917 C 2.896827 0.440255-1.251647 H 3.584139-0.072636-1.901323 C 2.426023 1.666198-1.234458 H 2.681138 2.437051-1.945672 C 2.213248 1.566293 1.165733 H 2.334054 2.274057 1.971708 C 2.682605 0.339741 1.164276 H 3.249055-0.229862 1.879971 N 2.330386-0.365571-0.115753 H 2.689510-1.312290-0.123323 Br 0.727424 3.859471-0.081220 F -0.000959 5.777338-0.064470 HF= -2999.617786618594 H-Quin_II-Br Cl C 0.650420-0.426195 0.087263 C 1.307188 1.867715 0.189387 C 0.211943 0.810874 0.060554 H 0.154280-1.378454 0.021826 H -0.822100 1.101799-0.041615 C 2.741444 0.303615-0.906205 H 3.428621-0.235726-1.534018 C 2.294084 1.537591-0.928821 H 2.571748 2.286295-1.654535 C 2.045899 1.501590 1.475190 H 2.167450 2.227814 2.263949 C 2.492246 0.267508 1.508067 H 3.038696-0.291972 2.246712 N 2.145334-0.463290 0.241157 H 2.487975-1.416230 0.262230 Cl -0.261776 6.230694 0.094953 Br 0.629485 3.752496 0.148178 HF= -3360.012774893482 H-Quin_II-Br Br C 0.850420-0.389050-0.252831 C 1.464252 1.912013-0.095437 C 0.386999 0.839010-0.238971 H 0.372059-1.348794-0.338357 H -0.653851 1.111971-0.319018 H 3.024112-0.254095 2.224081 N 2.132272-0.425282 0.207053 C 2.602264-1.728493 0.225390 N 2.989865-2.803973 0.240451 N -0.139291 5.876577 0.122748 C -0.530099 6.977708 0.122695 Cl 0.680261 3.599850 0.150610 HF= -970.698209882487 CN-Quin_II-Br F C 0.775344-0.320074-0.230863 C 1.437492 1.982962-0.098683 C 0.352466 0.920306-0.228448 H 0.301784-1.283409-0.303511 H -0.685762 1.206707-0.310747 C 2.877753 0.452602-1.258049 H 3.557303-0.086992-1.894132 C 2.408393 1.675902-1.233015 H 2.669564 2.439960-1.950466 C 2.196443 1.598956 1.166144 H 2.323914 2.314502 1.965190 C 2.660976 0.373926 1.195248 H 3.221971-0.208461 1.904937 Br 0.730693 3.905260-0.099332 N 2.301089-0.365182-0.097531 C 2.778736-1.664063-0.097052 N 3.173344-2.737347-0.096728 F 0.031830 5.806019-0.099835 HF= -3091.803829008000 CN-Quin_II-Br Cl C 0.786465-0.347328-0.223859 C 1.447147 1.950670-0.094474 C 0.358486 0.890869-0.217152 H 0.312421-1.310612-0.293948 H -0.680432 1.176054-0.291079 C 2.878751 0.430083-1.266229 H 3.554555-0.105990-1.909239 C 2.409108 1.652799-1.238842 H 2.662756 2.418348-1.957005 C 2.215583 1.572876 1.166492 H 2.347511 2.288141 1.964709 C 2.681273 0.348551 1.187844 H 3.248861-0.232022 1.893767 Br 0.745502 3.848192-0.087944 N 2.312855-0.389707-0.102480 C 2.793147-1.688538-0.107004 N 3.189560-2.761045-0.110785 Cl -0.150216 6.270234-0.079642 HF= -3452.196909737466 CN-Quin_II-Br Br C 0.789512-0.356391-0.215406 C 1.450619 1.940163-0.094149 C 0.360626 0.881454-0.208560 H 0.315329-1.319968-0.280941 H -0.678852 1.166032-0.276989 S14

C 2.912700 0.409714-1.253783 H 3.601530-0.097835-1.905829 C 2.441111 1.634662-1.236170 H 2.693700 2.408639-1.944305 C 2.227538 1.527090 1.169989 H 2.345797 2.233369 1.977132 C 2.698233 0.301757 1.161753 H 3.265817-0.266860 1.877140 N 2.347941-0.400486-0.120365 H 2.709518-1.346688-0.130565 Br 0.748914 3.782928-0.074372 Cl -0.253185 6.400553-0.043038 HF= -5474.063069724588 H-Quin_II-Br NC C 0.644514-0.405425 0.085857 C 1.296732 1.891710 0.182611 C 0.203463 0.830355 0.054370 H 0.149010-1.357977 0.022035 H -0.830999 1.117759-0.051080 C 2.736349 0.324329-0.904766 H 3.425803-0.214932-1.529922 C 2.287915 1.557538-0.932855 H 2.567170 2.303187-1.660763 C 2.034104 1.528277 1.471909 H 2.153623 2.255689 2.259573 C 2.481688 0.295006 1.508548 H 3.027162-0.260570 2.250660 N 2.138814-0.439877 0.243258 N -0.180733 5.979760 0.078928 C -0.578931 7.077386 0.053692 H 2.482767-1.392228 0.267945 Br 0.623639 3.754875 0.134814 HF= -2992.572297960366 C 2.875308 0.419974-1.271381 H 3.547627-0.116896-1.917436 C 2.405543 1.642607-1.243895 H 2.654676 2.406908-1.964986 C 2.226005 1.567060 1.163414 H 2.362267 2.283845 1.959558 C 2.692174 0.342935 1.183913 H 3.264133-0.235988 1.887717 Br 0.747077 3.839760-0.087221 N 2.316573-0.397884-0.102863 C 2.797478-1.696731-0.107735 N 3.194304-2.769072-0.111773 Br -0.207067 6.413768-0.078139 HF= -5566.246844683572 CN-Quin_II-Br NC C 0.782085-0.335786 0.243691 C 1.431116 1.966034 0.088504 C 0.348414 0.900180 0.233368 H 0.311326-1.299492 0.327303 H -0.690760 1.180158 0.318813 C 2.655071 0.355945-1.197283 H 3.215433-0.226753-1.907066 C 2.185785 1.578728-1.180149 H 2.305692 2.286823-1.986256 C 2.410384 1.677502 1.222983 H 2.671767 2.447818 1.932828 C 2.884108 0.456641 1.252377 H 3.570336-0.070880 1.891244 Br 0.731134 3.837657 0.076834 N 2.306441-0.373736 0.102734 C 2.791501-1.670867 0.110742 N 3.191743-2.741883 0.117432 N -0.078362 6.001523 0.062963 C -0.487991 7.095181 0.055232 HF= -3084.755525127899 Table S4. Atom coordinates of partially charged dimers with Quinu_I corresponding to optimized geometries with CP-correction at ωb97xd/aug-cc-pvtz level of theory. (+)CAXB H-Quin_I-Cl ClH C 0.691557-0.607011-0.123811 C 1.343546 1.793890-0.249504 C 0.157967 0.835077-0.117995 H 0.524862-1.108986-1.074061 H 0.265387-1.214446 0.670403 H -0.532955 0.975598-0.945452 H -0.383727 1.045162 0.802328 C 2.858394 0.018636-1.119697 H 3.911941 0.119336-0.869334 CN-Quin_I-Cl BrH C 0.697794-0.643615-0.121241 C 1.272670 1.783704-0.149440 C 0.131506 0.775624 0.000652 H 0.532958-1.090896-1.098496 H 0.329058-1.321861 0.643437 H -0.611884 0.931458-0.777485 H -0.360245 0.915265 0.961359 C 2.829935 0.121712-1.167530 H 3.881487 0.261166-0.928740 S15

H 2.761264-0.701329-1.928214 C 2.199683 1.369673-1.444427 H 2.966270 2.115653-1.638352 H 1.578606 1.296251-2.335104 C 2.190049 1.718670 1.022707 H 3.104247 2.294298 0.891069 H 1.647925 2.149092 1.860840 C 2.508921 0.242154 1.311404 H 3.559276 0.077383 1.537122 H 1.910391-0.162894 2.124093 N 2.179742-0.566410 0.087318 Cl -0.178960 6.890588 0.836039 Cl 0.753431 3.459221-0.487271 H -0.437189 8.041442 0.335393 H 2.516512-1.515454 0.222867 HF= -1250.160486300842 H-Quin_I-Cl BrH C 0.730969-0.646971-0.086647 C 1.283959 1.781956-0.111335 C 0.143783 0.769687 0.021166 H 0.540252-1.105555-1.054156 H 0.365867-1.312816 0.691067 H -0.589690 0.924920-0.766123 H -0.361809 0.909762 0.974676 C 2.821777 0.115571-1.144422 H 3.882135 0.242816-0.938988 H 2.710330-0.563864-1.985532 C 2.100781 1.456271-1.363911 H 2.831074 2.240027-1.548768 H 1.442502 1.407944-2.229296 C 2.190866 1.674455 1.116282 H 3.073856 2.295098 0.976495 H 1.670809 2.036057 1.999699 C 2.581371 0.199534 1.308680 H 3.647086 0.066780 1.476123 H 2.040545-0.272185 2.125935 N 2.224680-0.557652 0.059734 Br -0.480914 7.090758 0.370040 Cl 0.618811 3.431648-0.231491 H -1.614089 7.469549-0.395306 H 2.603206-1.498054 0.129135 HF= -3364.202340567266 H-Quin_I-Br FH C 0.725560-0.642135-0.101223 C 1.275069 1.788474-0.015116 C 0.139475 0.767199 0.089227 H 0.506545-1.056550-1.082622 H 0.384797-1.344033 0.655618 H -0.611291 0.956422-0.673886 H -0.348148 0.856296 1.058103 C 2.784091 0.179974-1.178520 H 3.850162 0.295842-0.997240 H 2.646449-0.452009-2.052179 H 2.746811-0.574487-1.997702 C 2.082211 1.439874-1.401069 H 2.803391 2.226561-1.608968 H 1.418556 1.362606-2.260127 C 2.185096 1.689266 1.074539 H 3.078854 2.289664 0.916518 H 1.676124 2.077822 1.953215 C 2.551952 0.219971 1.313080 H 3.610543 0.066634 1.504118 H 1.978435-0.243372 2.112293 N 2.217890-0.577271 0.049230 C 2.733836-1.862965 0.158535 N 3.158546-2.921301 0.248344 Br -0.402467 7.072088 0.502184 Cl 0.612200 3.431471-0.285258 H -1.537669 7.480769-0.244670 HF= -3456.380816287105 CN-Quin_I-Br FH C 0.694286-0.640482-0.112205 C 1.257433 1.791572-0.034087 C 0.125210 0.769614 0.090275 H 0.497964-1.046437-1.101612 H 0.355456-1.353243 0.634726 H -0.636530 0.955242-0.663097 H -0.347901 0.857695 1.066333 C 2.786529 0.190654-1.189597 H 3.845944 0.318008-0.980645 H 2.673015-0.459099-2.053187 C 2.032324 1.519924-1.325171 H 2.749683 2.315247-1.512260 H 1.345639 1.488640-2.168885 C 2.205143 1.633626 1.156898 H 3.089966 2.250070 1.010687 H 1.721330 1.963585 2.072935 C 2.592771 0.156320 1.300132 H 3.658735 0.002914 1.444815 H 2.052373-0.355329 2.093031 Br 0.528401 3.584225-0.062363 N 2.218371-0.573881 0.008396 C 2.742019-1.860769 0.031289 N 3.173558-2.919991 0.049690 F -0.696244 6.532230 0.107431 H -1.069880 7.372766 0.120788 HF= -3096.020552289480 CN-Quin_I-Br ClH C 0.693533-0.633592-0.104076 C 1.258730 1.797253-0.024196 C 0.126237 0.776546 0.104510 H 0.490465-1.037647-1.092883 H 0.358876-1.347322 0.643787 H -0.639296 0.963863-0.644601 H -0.341462 0.862650 1.083358 C 2.779433 0.198869-1.192936 H 3.840131 0.325408-0.990172 H 2.660282-0.448645-2.057431 S16

C 2.059300 1.531563-1.304596 H 2.787807 2.321391-1.469397 H 1.379567 1.528384-2.154585 C 2.213767 1.614419 1.181611 H 3.091865 2.245140 1.056750 H 1.718294 1.920513 2.099443 C 2.615390 0.132228 1.280475 H 3.686115-0.004612 1.408396 H 2.100898-0.385298 2.087037 Br 0.547759 3.584268-0.028659 N 2.222202-0.557071 0.004414 F -0.778793 6.544539 0.049972 H -1.143497 7.389071 0.061530 H 2.602802-1.499044 0.012234 HF= -3003.841679887101 H-Quin_I-Br ClH C 0.726217-0.638585-0.097989 C 1.270373 1.792494-0.011185 C 0.137018 0.769347 0.094638 H 0.505346-1.053055-1.078914 H 0.389003-1.341410 0.659548 H -0.615417 0.957054-0.667221 H -0.348982 0.856295 1.064535 C 2.779985 0.189548-1.180073 H 3.846224 0.307747-1.001441 H 2.641477-0.441681-2.054103 C 2.051687 1.539666-1.303020 H 2.778132 2.331181-1.468837 H 1.369910 1.535738-2.151350 C 2.212186 1.620269 1.183191 H 3.088332 2.253410 1.056945 H 1.718230 1.923863 2.102695 C 2.617829 0.138922 1.279386 H 3.689215 0.004836 1.404439 H 2.106809-0.380581 2.086875 Br 0.540181 3.589304-0.021094 N 2.222885-0.549985 0.003666 Cl -0.415306 7.066975-0.017002 H -1.680376 7.218966 0.117982 H 2.605749-1.491110 0.009528 HF= -3364.204727149613 H-Quin_I-Br BrH C 0.713195-0.623467-0.118482 C 1.283380 1.799407 0.017415 C 0.139293 0.786614 0.104541 H 0.483307-1.016269-1.106243 H 0.372234-1.337359 0.626910 H -0.612363 0.998564-0.651651 H -0.344057 0.858449 1.076989 C 2.771489 0.206745-1.191685 H 3.839444 0.310486-1.014437 H 2.623441-0.403516-2.078938 C 2.056480 1.566448-1.283002 C 2.024915 1.528832-1.320999 H 2.741543 2.324074-1.511240 H 1.332832 1.499439-2.160351 C 2.213646 1.636717 1.160513 H 3.097937 2.252925 1.010121 H 1.735961 1.964721 2.080478 C 2.601353 0.158758 1.297807 H 3.668133 0.004723 1.435580 H 2.065778-0.354257 2.093087 Br 0.532245 3.593465-0.044339 N 2.218280-0.568114 0.006843 C 2.741080-1.855565 0.023334 N 3.171603-2.915273 0.036515 Cl -0.361502 7.032859 0.021272 H -1.625400 7.194631 0.157662 HF= -3456.383392207976 CN-Quin_I-Br BrH C 0.684005-0.617708-0.130949 C 1.275871 1.803005 0.025554 C 0.131931 0.791707 0.121008 H 0.475688-0.989258-1.131338 H 0.342191-1.349792 0.595618 H -0.630282 1.011298-0.622628 H -0.336330 0.852188 1.101497 C 2.779513 0.226691-1.193576 H 3.841232 0.335940-0.986207 H 2.654419-0.390750-2.078959 C 2.038668 1.567623-1.279685 H 2.763478 2.360928-1.445515 H 1.345923 1.571207-2.118966 C 2.228354 1.593872 1.204588 H 3.119381 2.205006 1.074673 H 1.753439 1.896658 2.134569 C 2.600186 0.107966 1.294188 H 3.665222-0.061476 1.427200 H 2.058557-0.424414 2.072415 Br 0.570809 3.608073 0.061093 N 2.209467-0.572406-0.019263 C 2.717829-1.865533-0.044895 N 3.136261-2.929945-0.066151 Br -0.400455 7.172729-0.103210 H -1.396775 7.355442 0.890919 HF= -5570.424578708228 CN-Quin_I-Br NCH C 0.657300-0.558574-0.114213 C 1.313150 1.851695-0.035434 C 0.142813 0.872716 0.086100 H 0.450779-0.956391-1.104858 H 0.288203-1.258499 0.630633 H -0.609417 1.087598-0.669059 H -0.329338 0.979100 1.060882 C 2.786019 0.189681-1.181257 H 3.848041 0.278028-0.965371 H 2.654062-0.457364-2.044311 C 2.081982 1.545162-1.322926 S17

H 2.790260 2.353912-1.435306 H 1.370983 1.587024-2.128058 C 2.227609 1.591084 1.204087 H 3.109844 2.217805 1.088684 H 1.739862 1.879225 2.131838 C 2.618364 0.103965 1.266553 H 3.688811-0.043482 1.384406 H 2.105069-0.427613 2.064662 Br 0.573949 3.604828 0.049953 N 2.211142-0.552605-0.022060 Br -0.437041 7.187846-0.081414 H -1.433980 7.358354 0.914097 H 2.583977-1.497626-0.038480 HF= -5478.245933446557 H-Quin_I-Br NCH C 0.675975-0.563707-0.094926 C 1.321991 1.845399-0.032634 C 0.146460 0.870318 0.077835 H 0.446128-0.979145-1.073430 H 0.303773-1.244089 0.666889 C -0.593550 1.081673-0.689974 H -0.340810 0.988890 1.043819 C 2.772433 0.162659-1.168067 H 3.840908 0.239304-0.980005 H 2.616503-0.474607-2.034880 C 2.101034 1.539096-1.314776 H 2.859292 2.298679-1.487542 H 1.424827 1.550510-2.167603 C 2.248477 1.644783 1.169958 H 3.153518 2.235324 1.040533 H 1.763832 1.984262 2.081833 C 2.587186 0.149008 1.289873 H 3.650594-0.030371 1.426564 H 2.046514-0.337776 2.098453 Br 0.672238 3.669837-0.067825 N 2.174199-0.537841 0.018986 N -0.383595 6.596647-0.027655 C -0.814882 7.651231 0.053257 H -1.220655 8.635540 0.130785 H 2.516063-1.494238 0.039362 HF= -2996.806859724688 H 2.828099 2.313378-1.510939 H 1.397123 1.536165-2.168739 C 2.250657 1.655967 1.158470 H 3.160761 2.234799 1.013329 H 1.778706 2.008479 2.072330 C 2.577861 0.165060 1.307348 H 3.636052-0.030422 1.458540 H 2.012382-0.323588 2.097223 Br 0.658354 3.672678-0.067577 N 2.182293-0.551164 0.014162 C 2.654588-1.857506 0.040590 N 3.043311-2.933139 0.062209 N -0.367038 6.559717-0.020474 C -0.789910 7.617475 0.061756 H -1.187971 8.605029 0.140427 HF= -3088.986199625324 ( _ )CAXB Quin_I-Cl F C 0.697429-0.494437-0.056013 C 1.282549 1.933050-0.001072 C 0.121162 0.941026 0.068035 H 0.402587-0.952492-1.002149 H 0.324012-1.138555 0.742488 H -0.587928 1.158170-0.730734 H -0.406078 1.079290 1.012926 C 2.682235 0.219474-1.161422 H 3.768631 0.260638-1.061409 H 2.462536-0.368345-2.054835 C 2.083389 1.646888-1.272236 Quin_I-Br F C 0.691933-0.496128-0.042349 C 1.282667 1.942355-0.000300 C 0.117285 0.947569 0.057405 H 0.385225-0.978960-0.981680 H 0.325583-1.127758 0.780312 H -0.584148 1.155513-0.761809 H -0.433040 1.093598 0.997299 C 2.671671 0.211564-1.172556 H 3.768501 0.230065-1.093428 H 2.421162-0.377057-2.067544 C 2.094695 1.654712-1.269192 S18

H 2.863498 2.399941-1.383513 H 1.422631 1.737488-2.135490 C 2.191619 1.687564 1.203919 H 3.066661 2.334409 1.126813 H 1.664669 1.967835 2.115951 C 2.590910 0.187730 1.217079 H 3.671978 0.068630 1.311333 H 2.136606-0.327443 2.065799 N 2.159943-0.501029 0.000129 Cl 0.673705 3.626360-0.001882 F -0.172418 5.977158-0.002440 HF= -888.816913115264 Quin_I-Br Cl C 0.713862-0.528749-0.053781 C 1.291089 1.896494-0.001252 C 0.129922 0.904961 0.070122 H 0.418438-0.987756-0.998866 H 0.343436-1.172065 0.746223 H -0.582453 1.113020-0.727792 H -0.397037 1.038370 1.015586 C 2.693818 0.191799-1.162510 H 3.779828 0.238321-1.064610 H 2.474189-0.395776-2.055617 C 2.090014 1.618320-1.275043 H 2.870135 2.370289-1.390853 H 1.429461 1.703137-2.138724 C 2.201708 1.660882 1.204109 H 3.075866 2.308465 1.126978 H 1.678164 1.935476 2.119519 C 2.606398 0.161196 1.215624 H 3.687892 0.048232 1.308005 H 2.155595-0.354054 2.065696 Br 0.623140 3.736954-0.002184 N 2.175484-0.527958 0.000039 Cl -0.446796 6.748505-0.001893 HF= -3363.287234823616 H 2.896481 2.399029-1.367362 H 1.442915 1.766171-2.146953 C 2.185724 1.687320 1.212624 H 3.062807 2.347066 1.154920 H 1.646238 1.950043 2.132628 C 2.604006 0.187094 1.212893 H 3.696266 0.078067 1.283982 H 2.170149-0.342163 2.073882 Br 0.613555 3.810673 0.000063 N 2.158941-0.507516-0.000662 F -0.189109 6.034186 0.001129 HF= -3002.702755852096 Quin_I-Br Br C 0.714721-0.536342-0.073040 C 1.298524 1.884910-0.000144 C 0.132450 0.898402 0.050422 H 0.428415-0.990474-1.023112 H 0.333636-1.181366 0.720346 H -0.568100 1.112850-0.756040 H -0.406246 1.028592 0.989544 C 2.708639 0.185037-1.155574 H 3.793701 0.226503-1.047032 H 2.494976-0.395296-2.054649 C 2.112311 1.615327-1.265881 H 2.897026 2.364743-1.364996 H 1.463849 1.709428-2.137568 C 2.192548 1.641927 1.215663 H 3.068407 2.288756 1.154359 H 1.657170 1.910377 2.125932 C 2.595005 0.141246 1.221142 H 3.675328 0.027054 1.323347 H 2.135359-0.378307 2.063673 Br 0.634439 3.725211 0.002204 N 2.175311-0.538993-0.002946 Br -0.534584 6.980099 0.010484 HF= -5477.342004022005 Quin_I-Br NC C 0.715565-0.543201-0.062393 C 1.297842 1.887737-0.001894 C 0.129630 0.895987 0.040931 H 0.424179-1.017812-1.009779 H 0.338303-1.180920 0.749302 H -0.563844 1.105850-0.783356 H -0.427013 1.035389 0.977177 C 2.708493 0.177613-1.159958 H 3.802804 0.206942-1.062845 H 2.477415-0.407760-2.061084 C 2.122862 1.616965-1.265881 H 2.919291 2.366981-1.353709 H 1.478059 1.723530-2.148419 C 2.187395 1.643902 1.223026 H 3.062951 2.304952 1.172281 H 1.637086 1.905032 2.136040 C 2.605663 0.143444 1.223756 H 3.695976 0.038186 1.313399 H 2.157977-0.386284 2.076312 S19

Br 0.630490 3.730135-0.003854 N 2.180598-0.545253 0.001224 N -0.364589 6.472215-0.002265 C -0.785816 7.574553 0.001860 HF= -2995.687485439764 Table S5. Atom coordinates of partially charged dimers with Quinu_II corresponding to optimized geometries with CP-correction at ωb97xd/aug-cc-pvtz level of theory. (+)CAXB H-Quin_II-Cl FH C 0.754762-0.610503 0.085107 C 1.209906 1.720830 0.034118 C 0.201153 0.571292-0.039706 H 0.337926-1.602267 0.079390 H -0.850925 0.757784-0.181409 C 2.796085 0.231598-0.920171 H 3.543998-0.281317-1.498875 C 2.249022 1.416145-1.048481 H 2.479657 2.132834-1.819768 C 1.943646 1.527116 1.364155 H 1.980337 2.312322 2.101667 C 2.492342 0.342665 1.484819 H 3.065582-0.106971 2.276347 N 2.241873-0.502451 0.267789 Cl 0.473951 3.312782-0.126981 F -0.546860 6.267209 0.604574 H -0.909193 7.112659 0.615401 H 2.667077-1.418766 0.363499 HF= -886.035505299163 H-Quin_II-Cl ClH C 0.772564-0.647733 0.021820 C 1.198030 1.688753 0.020128 C 0.208758 0.528033-0.113496 H 0.370162-1.644787-0.015739 H -0.838523 0.702562-0.299031 C 2.846490 0.234318-0.878195 H 3.629216-0.259899-1.426361 C 2.289333 1.412871-1.017726 H 2.545699 2.142001-1.768968 C 1.872812 1.489368 1.380134 H 1.865860 2.265585 2.127953 C 2.431012 0.310449 1.511306 H 2.972538-0.141922 2.323365 N 2.248289-0.522217 0.273696 Cl -0.173252 6.836279 0.693399 CN-Quin_II-Cl FH C 0.681643-0.566901 0.035511 C 1.179157 1.763565 0.025809 C 0.159122 0.628132-0.072687 H 0.266687-1.559852 0.012985 H -0.890651 0.827773-0.218750 C 2.764642 0.279296-0.955182 H 3.510052-0.243869-1.529015 C 2.221184 1.465763-1.053467 H 2.464505 2.191927-1.812828 C 1.900704 1.543173 1.356427 H 1.940888 2.317935 2.105708 C 2.441548 0.357996 1.480032 H 3.005967-0.121280 2.261266 N 2.194930-0.493309 0.234155 C 2.763307-1.755576 0.350537 N 3.231207-2.794271 0.445636 Cl 0.463506 3.364503-0.115555 F -0.350440 6.337658 0.622439 H -0.675216 7.198272 0.642699 HF= -978.209698580113 CN-Quin_II-Cl ClH C 0.718005-0.647818-0.010294 C 1.163713 1.692313 0.001523 C 0.172367 0.535478-0.131896 H 0.326193-1.649707-0.048849 H -0.876592 0.712372-0.309492 C 2.812176 0.248021-0.932040 H 3.589065-0.255350-1.481387 C 2.245786 1.422400-1.045298 H 2.497515 2.155946-1.794792 C 1.847108 1.485362 1.354080 H 1.846666 2.258103 2.106515 C 2.409727 0.311868 1.491586 H 2.958995-0.157125 2.289728 N 2.222039-0.540843 0.236490 C 2.814654-1.790575 0.368253 S20

Cl 0.446830 3.273422-0.158329 H -1.321951 7.402896 0.648490 H 2.681256-1.434057 0.377827 HF= -1246.398216629074 H-Quin_II-Cl BrH C 0.926395-0.553026-0.230323 C 1.396623 1.774861-0.256058 C 0.381260 0.632996-0.352725 H 0.503579-1.542096-0.250334 H -0.667846 0.826332-0.506692 C 2.985837 0.284421-1.201733 H 3.738257-0.228280-1.774815 C 2.447657 1.473265-1.327836 H 2.692709 2.194192-2.090706 C 2.111344 1.566866 1.081839 H 2.143676 2.345572 1.826379 C 2.650994 0.378002 1.199964 H 3.210479-0.081511 1.995692 N 2.411569-0.455781-0.027123 Br -0.151802 7.050783 0.201203 Cl 0.672401 3.374326-0.415698 H -1.554656 7.224494 0.074111 H 2.829921-1.375520 0.066751 HF= -3360.439210742607 H-Quin_II-Cl NCH C 0.656164-0.454282 0.084140 C 1.322543 1.827028 0.160670 C 0.211064 0.778686 0.055140 H 0.151682-1.402821 0.030152 H -0.823282 1.068281-0.035029 C 2.730137 0.263568-0.948970 H 3.404480-0.277576-1.588946 C 2.290671 1.498462-0.980235 H 2.558484 2.239718-1.715434 C 2.083566 1.479059 1.443343 H 2.221490 2.209895 2.223509 C 2.522866 0.244114 1.468591 H 3.081773-0.306266 2.204756 N 2.152136-0.493574 0.213273 N -0.280190 6.371044 0.120879 C -0.693412 7.435751 0.145924 Cl 0.732412 3.485440 0.125125 H -1.081970 8.429923 0.170230 H 2.493600-1.448720 0.234841 HF= -879.000488884976 H-Quin_II-Br FH C 0.901003-0.517743-0.209338 C 1.410996 1.803456-0.135513 C 0.372863 0.682205-0.240271 H 0.459423-1.497333-0.262306 H -0.680060 0.893747-0.331934 N 3.302649-2.818678 0.476522 Cl -0.072298 6.819765 0.767046 Cl 0.415085 3.277744-0.161430 H -1.219614 7.391242 0.748495 HF= -1338.572155505001 CN-Quin_II-Cl BrH C 0.860187-0.504602-0.255312 C 1.418299 1.809820-0.171057 C 0.366933 0.706922-0.300299 H 0.419325-1.484711-0.315952 H -0.679767 0.938359-0.418932 C 2.945632 0.331913-1.248346 H 3.665273-0.184609-1.859923 C 2.431998 1.535112-1.283073 H 2.679629 2.287056-2.015525 C 2.159253 1.513196 1.133359 H 2.235562 2.253518 1.913956 C 2.670613 0.310234 1.193876 H 3.238845-0.217054 1.940726 N 2.377845-0.478178-0.082921 C 2.914966-1.758590-0.033425 N 3.356945-2.812099 0.006965 Br -0.191316 7.004474 0.137602 Cl 0.740788 3.434769-0.229964 H -1.564694 7.077061-0.213069 HF= -3452.613082852719 CN-Quin_II-Cl NCH C 0.633762-0.437163 0.052838 C 1.325633 1.843455 0.145201 C 0.213113 0.801576 0.017122 H 0.138754-1.390729-0.010408 H -0.818589 1.095923-0.093630 C 2.758083 0.282527-0.950881 H 3.441056-0.272798-1.570184 C 2.314162 1.513505-0.975056 H 2.599244 2.254563-1.704932 C 2.058316 1.494318 1.441733 H 2.183042 2.225504 2.224715 C 2.498810 0.263169 1.493278 H 3.041110-0.300824 2.232383 N 2.152107-0.499687 0.214646 C 2.613889-1.809088 0.253430 N 2.994020-2.886758 0.285250 N -0.265006 6.329895 0.117287 C -0.686149 7.390442 0.167953 Cl 0.741919 3.502486 0.099924 H -1.082428 8.380841 0.216845 HF= -971.175198119922 CN-Quin_II-Br FH C 0.856796-0.514106-0.220919 C 1.386192 1.808863-0.124815 C 0.347327 0.691692-0.237473 H 0.426733-1.499028-0.281043 H -0.706313 0.904975-0.324558 S21

C 2.922074 0.337151-1.240450 H 3.632974-0.156387-1.879571 C 2.401197 1.540154-1.274181 H 2.623995 2.292065-2.013577 C 2.191363 1.509080 1.149033 H 2.282240 2.243658 1.932517 C 2.713623 0.306686 1.175842 H 3.307260-0.203328 1.914032 Br 0.645567 3.562364-0.175487 N 2.395453-0.456172-0.078582 F -0.578159 6.391735-0.022849 H -0.958661 7.229435-0.009103 H 2.800701-1.386074-0.055420 HF= -3000.079498999162 H-Quin_II-Br ClH C 0.899807-0.511809-0.208471 C 1.417801 1.806302-0.117819 C 0.374753 0.689860-0.222796 H 0.454671-1.489529-0.266447 H -0.678534 0.904513-0.302000 C 2.912912 0.346708-1.251912 H 3.615953-0.142589-1.902913 C 2.395425 1.551476-1.269085 H 2.613212 2.309305-2.003966 C 2.210139 1.498262 1.156186 H 2.311929 2.225146 1.945531 C 2.728808 0.294032 1.165887 H 3.328863-0.224472 1.892935 Br 0.660060 3.571220-0.134866 N 2.395756-0.455964-0.092096 Cl -0.265907 6.968452-0.019386 H -1.532078 7.117565-0.150301 H 2.798339-1.387331-0.081737 HF= -3360.442154541793 H-Quin_II-Br BrH C 0.916520-0.538658-0.209879 C 1.460484 1.772913-0.108669 C 0.404817 0.668865-0.218911 H 0.460871-1.511231-0.272418 H -0.646023 0.895553-0.297314 C 2.939262 0.301767-1.249353 H 3.636528-0.192840-1.902540 C 2.435102 1.512203-1.261221 H 2.661147 2.270624-1.992986 C 2.249384 1.450344 1.163896 H 2.359335 2.172535 1.956457 C 2.754359 0.240276 1.168182 H 3.348533-0.288402 1.892725 Br 0.723614 3.547461-0.118159 N 2.413076-0.500083-0.093029 Br -0.312364 7.051965-0.038997 H -1.724619 6.971184-0.156780 H 2.805067-1.435997-0.086796 C 2.901622 0.360502-1.262180 H 3.610078-0.139371-1.900034 C 2.372029 1.557532-1.267319 H 2.593192 2.316828-2.000618 C 2.168583 1.504070 1.153790 H 2.262194 2.232421 1.943677 C 2.696578 0.306957 1.185568 H 3.293227-0.221891 1.908738 Br 0.623712 3.568495-0.147001 N 2.377741-0.470298-0.091255 C 2.932247-1.743820-0.072775 N 3.388967-2.791689-0.058003 F -0.492219 6.387261-0.035920 H -0.888985 7.217629-0.021615 HF= -3092.253990324521 CN-Quin_II-Br ClH C 0.857014-0.503486-0.230848 C 1.407865 1.813020-0.124203 C 0.358470 0.706972-0.244952 H 0.418077-1.484167-0.296405 H -0.692964 0.929494-0.335255 C 2.913519 0.355693-1.261473 H 3.619579-0.148481-1.898663 C 2.395208 1.557641-1.264419 H 2.626426 2.317235-1.994345 C 2.182713 1.497302 1.156213 H 2.280792 2.221777 1.949160 C 2.699248 0.295141 1.185260 H 3.288699-0.241654 1.908535 Br 0.663909 3.583207-0.142288 N 2.377818-0.474396-0.095388 C 2.920118-1.753345-0.079811 N 3.366482-2.805702-0.067650 Cl -0.226314 6.963089-0.003784 H -1.491731 7.119854-0.134982 HF= -3452.616418551303 CN-Quin_II-Br BrH C 0.875423-0.525823-0.213683 C 1.454803 1.784095-0.115257 C 0.391086 0.690460-0.223453 H 0.424678-1.501486-0.273520 H -0.658626 0.925229-0.302256 C 2.930027 0.308129-1.268423 H 3.622380-0.205207-1.913271 C 2.425686 1.515996-1.266657 H 2.657112 2.272116-2.000112 C 2.240282 1.460126 1.156517 H 2.355763 2.183811 1.947856 C 2.742883 0.251948 1.180669 H 3.334109-0.291319 1.897629 Br 0.731421 3.563773-0.126634 N 2.398104-0.514574-0.095401 C 2.925292-1.799884-0.084851 N 3.359124-2.857511-0.076776 Br -0.292054 7.041628-0.022672 S22

HF= -5474.483359481988 H-Quin_II-Br NCH C 0.835462-0.415931 0.229897 C 1.465680 1.875476 0.114713 C 0.372238 0.810946 0.247332 H 0.345546-1.370846 0.303033 H -0.667083 1.079186 0.346287 C 2.674801 0.290117-1.185105 H 3.233585-0.262049-1.920087 C 2.217434 1.518984-1.171438 H 2.339614 2.236438-1.966516 C 2.452230 1.574766 1.247772 H 2.721807 2.324707 1.973493 C 2.909476 0.345770 1.228140 H 3.599162-0.176459 1.867588 Br 0.797185 3.675983 0.134535 N 2.329773-0.435498 0.083581 N -0.236491 6.485469 0.096899 C -0.661408 7.543200 0.029424 H -1.061461 8.531107-0.035597 H 2.684848-1.385746 0.070969 HF= -2993.045829787923 H -1.704409 6.956831-0.138624 HF= -5566.657617818579 CN-Quin_II-Br NCH C 0.811601-0.402543 0.240663 C 1.470044 1.887717 0.115659 C 0.372792 0.830710 0.252403 H 0.329512-1.361844 0.316171 H -0.665835 1.104375 0.351017 C 2.677205 0.300195-1.196033 H 3.234210-0.268246-1.920662 C 2.218631 1.525781-1.168440 H 2.343633 2.240972-1.966026 C 2.454580 1.588784 1.248155 H 2.727709 2.340833 1.971355 C 2.916265 0.363892 1.248399 H 3.602618-0.171074 1.881771 Br 0.807202 3.690162 0.129520 N 2.331255-0.446162 0.091778 C 2.811903-1.749122 0.078743 N 3.207626-2.821587 0.068326 N -0.230573 6.466342 0.087867 C -0.665850 7.519884 0.023167 H -1.075580 8.504176-0.039260 HF= -3085.220905882006 ( _ )CAXB Quin_II-Cl F C 0.680681-0.366107 0.053711 C 1.286213 1.921512 0.193089 C 0.192780 0.859336 0.044263 H 0.141050-1.296709-0.035305 H -0.841287 1.150467-0.055320 C 2.697833 0.356783-0.893144 H 3.392378-0.130152-1.560703 C 2.275250 1.605548-0.932462 H 2.552539 2.366813-1.644797 C 2.029715 1.525136 1.471667 H 2.151775 2.238344 2.271901 C 2.459641 0.278803 1.436373 H 3.008348-0.255621 2.196977 N 2.141299-0.453267 0.201271 Cl 0.683330 3.605494 0.188589 F -0.125052 5.873982 0.185393 HF= -885.078331693163 Quin_II-Cl Cl C 0.698863-0.412773 0.074231 C 1.299891 1.869207 0.187046 C 0.202865 0.808699 0.057735 H 0.162474-1.345923-0.001081 H -0.832518 1.095634-0.034605 C 2.704282 0.309617-0.898591 H 3.394142-0.180737-1.567751 C 2.278376 1.556238-0.948108 H 2.545172 2.312731-1.668700 C 2.055340 1.496754 1.465495 Quin_II-Br F C 0.820841-0.242600-0.226610 C 1.412097 2.053587-0.098026 C 0.327083 0.981176-0.231567 H 0.284775-1.176393-0.307744 H -0.713034 1.256366-0.319524 C 2.820265 0.490086-1.199428 H 3.509543 0.006606-1.875487 C 2.388979 1.736728-1.233754 H 2.659315 2.492438-1.955531 C 2.174908 1.658446 1.169391 H 2.308458 2.366802 1.972918 C 2.612386 0.414107 1.131691 H 3.173848-0.116116 1.886416 Br 0.733981 3.907313-0.096458 N 2.283505-0.322983-0.097564 F -0.061434 6.065309-0.092208 HF= -2999.134846783508 Quin_II-Br Cl C 0.862865-0.355974-0.217501 C 1.451471 1.931971-0.095690 C 0.361227 0.863784-0.221687 H 0.330064-1.291378-0.293816 H -0.678916 1.137696-0.303251 C 2.854039 0.382298-1.204555 H 3.540388-0.099618-1.883790 C 2.421351 1.627530-1.240893 H 2.682697 2.384707-1.963237 C 2.221606 1.551095 1.171799 S23

H 2.181385 2.218029 2.257118 C 2.488402 0.252027 1.434294 H 3.046063-0.273260 2.194101 N 2.160459-0.490165 0.208697 Cl -0.375727 6.582517 0.164932 Cl 0.695454 3.538031 0.173171 HF= -1245.497803114834 Quin_II-Cl Br C 0.874318-0.377647-0.246402 C 1.452837 1.906027-0.095397 C 0.365836 0.838682-0.248963 H 0.347880-1.314741-0.339595 H -0.671566 1.116573-0.345312 C 2.880448 0.378637-1.192230 H 3.580639-0.094574-1.862884 C 2.443377 1.621784-1.227360 H 2.708539 2.391161-1.934694 C 2.201226 1.524203 1.184382 H 2.314316 2.235228 1.987056 C 2.646398 0.284366 1.137715 H 3.203516-0.246601 1.893841 N 2.335315-0.442092-0.101378 Br -0.302716 6.870538-0.065999 Cl 0.833669 3.568657-0.090079 HF= -3359.552997378743 Quin_II-Cl NC C 0.718668-0.439709 0.047864 C 1.273843 1.853993 0.147275 C 0.200960 0.771840-0.001104 H 0.201850-1.383494-0.031143 H -0.836507 1.036624-0.128950 C 2.740859 0.306994-0.870749 H 3.460869-0.179202-1.510512 C 2.293932 1.544558-0.951715 H 2.570469 2.296088-1.673784 C 1.994676 1.513408 1.454516 H 2.082039 2.247430 2.239529 C 2.451165 0.276811 1.454714 H 2.993250-0.227456 2.239520 N 2.176133-0.487374 0.229651 N -0.301886 6.288474 0.090024 C -0.523097 7.426295 0.239860 Cl 0.643448 3.510534 0.094027 HF= -878.062425414779 H 2.356277 2.262273 1.971536 C 2.661556 0.308664 1.128612 H 3.229787-0.218592 1.879526 Br 0.780376 3.756734-0.092847 N 2.325922-0.428378-0.097866 Cl -0.270085 6.648347-0.085422 HF= -3359.546898251190 Quin_II-Br Br C 0.868086-0.355586-0.208184 C 1.443999 1.934066-0.095323 C 0.358039 0.860555-0.210868 H 0.340582-1.294343-0.278754 H -0.684239 1.127852-0.285168 C 2.847604 0.393036-1.210940 H 3.532286-0.085837-1.893870 C 2.406918 1.635317-1.247745 H 2.658026 2.392678-1.973340 C 2.225474 1.563055 1.168086 H 2.361547 2.277011 1.964941 C 2.672089 0.323175 1.123816 H 3.249077-0.198901 1.871544 Br 0.763735 3.752667-0.091590 N 2.332178-0.417991-0.098787 Br -0.357034 6.849224-0.080164 HF= -5473.600919920586 Quin_II-Br NC C 0.873118-0.374065 0.220911 C 1.440216 1.918966 0.090218 C 0.359964 0.840799 0.222322 H 0.348953-1.313881 0.301759 H -0.682585 1.104552 0.305792 C 2.661464 0.302511-1.132577 H 3.232273-0.221774-1.883527 C 2.210686 1.540843-1.178538 H 2.337100 2.250320-1.981055 C 2.416259 1.626636 1.233863 H 2.673006 2.387783 1.953600 C 2.860364 0.385472 1.199562 H 3.553195-0.087577 1.878361 Br 0.756199 3.733123 0.083279 N 2.336173-0.433133 0.097190 N -0.209973 6.360451 0.067179 C -0.614433 7.456517 0.059779 HF= -2992.111251537924 Table S6. Atom coordinates of neutral dimers with Quinu_II corresponding to optimized geometries with CP-correction at ωb97xd/aug-cc-pvtz level of theory. Quin_II-Cl NCH C 0.803255-0.637171 0.134449 C 1.293154 1.659745 0.084378 Quin_II-Br NCH C 0.799179-0.601933 0.128250 C 1.279166 1.698514 0.102764 S24