O,O -Disubstituted N,N -Dihydroxynaphthalenediimides (DHNDI): First principles-designed organic building blocks for materials science

, -Disubstituted N,N -Dihydroxynaphthalenediimides (DHNDI): First principles-designed organic building blocks for materials science Eric Assen B. Kantchev [a] *, Huei Shuan Tan, [a] Tyler B. Norsten [a] * Michael B. Sullivan [b] a Institute of Materials Research and Engineering, A*STAR, 3 Research Link, Singapore 117602 b Institute of High Performance Computing, A*STAR, 1 Fusionopolis Way #16-16, The Connexis, Singapore 138632 kantcheveab@imre.a-star.edu.sg; norstent@imre.a-star.edu.sg Contents Page 1. DFT computational studies S2 2. Experimental materials and methods S25 3. Synthetic procedures S26 4. NMR Spectra S29 5. Additional surface characterization for compd. 12 S32 6. Solid state UV and TFT device characterization S32 7. References S33 S 1

1. DFT computational studies 1.1. Computational methodology All computations were performed on Gaussian 09 (AM64L -G09RevA.02) 1 and Gaussview 5.1W as GUI using default M06 DFT functional and DGTZVP basis set in gas phase or implicit solvent (dichloromethane) by SMD treatment. ptimizations were performed from structures built in Gaussview via pre-optimization at HF/3-21g at M06/DGTZVP first in gas phase, then in implicit solvent with cutoff values for Maximum Force = 0.0001500, RMS Force = 0.0001000, Maximum Displacement = 0.001800, RMS Displacement = 0.001200. All optimized structures were confirmed to reside in their respective PEHS minima by having only positive vibrational frequencies. 1.2. Table 1-SI (extended version of Table 1 in the manuscript) Table 1-SI. Computational (DFT) characterization of -functionalized DHNDI derivatives at M06/DGTZVP levels of theory in gas phase and in CH 2 Cl 2 under the dispersion-corrected polarized continuum implicit solvation model (SMD). Gas phase CH 2Cl 2 G G A B C (kcal HM/LUM (kcal HM/LUM D1, D2, mol - D1, D2, (ev) mol -1 ) (ev) 1 ) 3a a 180.0 180.0 0.00-7.53/-3.48 180.0 180.0 0.00-7.20/-3.18 3b CH 2 CH 2 CH 3 179.8 62.6 0.55-7.53/-3.48 180.0 63.5 0.50-7.20/-3.18 3c -62.4 62.4 1.93-7.53/-3.48-62.7 62.7 1.67-7.19/-3.17 4a a 180.0 180.0 0.00-7.71/-3.65 180.0 180.0 0.00-7.35/-3.32 4b CH 2 CH 3 178.7 67.3 1.51-7.72/-3.65 177.4 67.1 2.57-7.35/-3.31 4c -68.7 68.7 3.89-7.72/-3.65-66.1 66.1 5.33-7.34/-3.30 5a a 180.0 180.0 0.00-7.81/3.72 179.9-179.9 0.00-7.46/-3.42 5b C= CH 3 180.0 0.0 6.44-8.03/-3.95 179.2-0.8 2.82-7.52/-3.49 5c 0.0 0.0 13.0-8.25/-4.18 0.9 0.9 7.68-7.57/-3.54 6a a 178.4-178.4 0.00-8.28/-4.19 177.6-177.5 0.00-7.65/-3.62 6b C= CF 3 180.0 0.3 6.33-8.33/-4.24 180.0 0.0 5.82-7.66/-3.63 6c 0.0 0.0 13.4-8.38/-4.29 0.0 0.0 13.3-7.69/-3.65 7a a 179.5 179.3 0.00-7.56/-3.51 178.8 178.8 0.00-7.37/-3.36 7b C= N(CH 3) 2 179.8 35.0 12.1-7.54/-3.76 178.2 33.3 9.25-7.39/-3.43 7c 35.6 35.6 24.0-7.66/-4.00 33.0 33.0 18.7-7.41/-3.51 8a a 115.5-115.6 0.00-8.01/-3.94 116.1-116.1 0.00-7.53/-3.51 =S= CH 3 8b 115.8 115.8 0.17-8.01/-3.94 116.3-116.3-0.23-7.54/-3.51 a Chosen as the reference structure. S 2

1.3. Structure plots, Cartesian coordinates SCF convergence and thermochemistry data for all structures in Table 1 at SMD (CH 2 Cl 2 )/M06/DGDZVP level of theory Structure 1(gas phase) 1 6 0-2.871914 1.251313 0.000034 2 6 0-1.393353 1.232622-0.000052 3 6 0-0.705955-0.000006-0.000064 4 6 0-1.393350-1.232637-0.000059 5 6 0-2.871904-1.251320-0.000168 6 6 0-0.699288 2.418430-0.000049 7 6 0 0.705955-0.000005-0.000060 8 6 0 1.393352 1.232622-0.000044 9 6 0 0.699288 2.418430-0.000044 10 6 0 2.871914 1.251313 0.000047 11 6 0 2.871904-1.251320-0.000146 12 6 0 1.393350-1.232637-0.000049 13 6 0 0.699289-2.418447-0.000003 14 6 0-0.699289-2.418447-0.000009 15 1 0-1.258291-3.345010-0.000014 16 1 0 1.258292-3.345010-0.000003 17 1 0-1.258293 3.344993-0.000023 18 1 0 1.258293 3.344993-0.000015 19 8 0-3.537516-2.263283 0.000126 20 8 0-3.537506 2.263291 0.000064 21 8 0 3.537517-2.263282 0.000179 22 8 0 3.537506 2.263292 0.000116 23 7 0 3.475059 0.000003 0.000027 24 7 0-3.475059 0.000003-0.000007 25 1 0-4.488478-0.000028 0.000084 26 1 0 4.488478-0.000027 0.000142 SCF Done: E(RM06) = -947.304529824 A.U. after 1 cycles Convg = 0.1868D-08 -V/T = 2.0046 0.179958 (Hartree/Particle) Thermal correction to Energy= 0.193665 Thermal correction to Enthalpy= 0.194609 Thermal correction to Gibbs Free Energy= 0.139346 Sum of electronic and zero-point Energies= -947.124572 Sum of electronic and thermal Energies= -947.110865 Sum of electronic and thermal Enthalpies= -947.109921 Sum of electronic and thermal Free Energies= -947.165183 Structure 2 (gas phase) S 3

1 6 0-2.860275-1.232790 0.000028 2 6 0-1.391113-1.222133-0.000028 3 6 0-0.704812 0.010937-0.000006 4 6 0-1.397115 1.240308 0.000052 5 6 0-2.877732 1.278575 0.000078 6 6 0-0.699654-2.410393-0.000087 7 6 0 0.704812 0.010937-0.000039 8 6 0 1.391113-1.222133-0.000085 9 6 0 0.699653-2.410393-0.000110 10 6 0 2.860275-1.232790-0.000078 11 6 0 2.877732 1.278575-0.000123 12 6 0 1.397116 1.240308-0.000025 13 6 0 0.699814 2.424742 0.000045 14 6 0-0.699814 2.424742 0.000083 15 1 0-1.255986 3.353272 0.000129 16 1 0 1.255987 3.353272 0.000049 17 1 0-1.255541-3.338919-0.000099 18 1 0 1.255541-3.338919-0.000142 19 8 0-3.535515 2.288202 0.000165 20 8 0-3.559132-2.232906-0.000056 21 8 0 3.535515 2.288202 0.000052 22 8 0 3.559132-2.232907-0.000087 23 7 0 3.469786 0.009336 0.000029 24 7 0-3.469786 0.009336-0.000021 25 8 0-4.840737-0.010353-0.000005 26 1 0-5.019036-0.974721 0.000087 27 8 0 4.840738-0.010352 0.000131 28 1 0 5.019038-0.974720 0.000095 SCF Done: E(RM06) = -1097.61057351 A.U. after 1 cycles Convg = 0.5202D-08 -V/T = 2.0046 0.187366 (Hartree/Particle) Thermal correction to Energy= 0.203256 Thermal correction to Enthalpy= 0.204200 Thermal correction to Gibbs Free Energy= 0.144525 Sum of electronic and zero-point Energies= -1097.423208 Sum of electronic and thermal Energies= -1097.407317 Sum of electronic and thermal Enthalpies= -1097.406373 Sum of electronic and thermal Free Energies= -1097.466049 Structure 3a S 4

1 6 0 2.858835-1.238790 0.293837 2 6 0 1.390408-1.225440 0.136081 3 6 0 0.701779 0.000043 0.070424 4 6 0 1.390414 1.225525 0.136053 5 6 0 2.858849 1.238871 0.293731 6 6 0 0.696129-2.411051 0.067799 7 6 0-0.701790 0.000045-0.070565 8 6 0-1.390424-1.225437-0.136212 9 6 0-0.696149-2.411049-0.067911 10 6 0-2.858850-1.238784-0.293962 11 6 0-2.858861 1.238877-0.293848 12 6 0-1.390425 1.225528-0.136179 13 6 0-0.696146 2.411138-0.067887 14 6 0 0.696136 2.411137 0.067783 15 1 0 1.238429 3.345829 0.120937 16 1 0-1.238440 3.345832-0.121022 17 1 0 1.238419-3.345744 0.120973 18 1 0-1.238443-3.345741-0.121069 19 8 0 3.497975 2.273834 0.345067 20 8 0 3.497969-2.273751 0.345095 21 8 0-3.498001 2.273838-0.345035 22 8 0-3.498004-2.273741-0.345063 23 6 0 4.950002 0.000033 0.579339 24 1 0 5.202348 0.883986 1.163283 25 1 0 5.202294-0.883789 1.163503 26 7 0-3.493024 0.000048-0.394985 27 7 0 3.493003 0.000040 0.394922 28 6 0-5.700401-0.000182 0.738613 29 1 0-5.405551-0.879396 1.318813 30 1 0-5.405623 0.878868 1.319096 31 6 0-7.198750-0.000206 0.507473 32 1 0-7.746870-0.000379 1.450470 33 1 0-7.509837 0.881896-0.057683 34 1 0-7.509766-0.882151-0.057967 35 6 0-4.950041 0.000045-0.579252 36 1 0-5.202450 0.884007-1.163156 37 1 0-5.202396-0.883769-1.163401 38 6 0 5.700508-0.000172-0.738444 39 1 0 5.405797 0.878886-1.318946 40 1 0 5.405728-0.879376-1.318694 41 6 0 7.198830-0.000198-0.507132 42 1 0 7.747060-0.000355-1.450065 43 1 0 7.509850 0.881895 0.058076 44 1 0 7.509781-0.882152 0.058330 SCF Done: E(RM06) = -1183.09244514 A.U. after 1 cycles Convg = 0.7148D-08 -V/T = 2.0050 SMD-CDS (non-electrostatic) energy (kcal/mol) = -7.96 0.349386 (Hartree/Particle) Thermal correction to Energy= 0.371148 Thermal correction to Enthalpy= 0.372093 Thermal correction to Gibbs Free Energy= 0.299024 Sum of electronic and zero-point Energies= -1182.743059 Sum of electronic and thermal Energies= -1182.721297 Sum of electronic and thermal Enthalpies= -1182.720353 Sum of electronic and thermal Free Energies= -1182.793421 Structure 3b S 5

1 6 0 2.912535 1.301117-0.402148 2 6 0 1.450151 1.269427-0.199176 3 6 0 0.776815 0.035367-0.143103 4 6 0 1.475580-1.178959-0.269873 5 6 0 2.939920-1.174708-0.468347 6 6 0 0.746377 2.445114-0.079923 7 6 0-0.622113 0.016047 0.037416 8 6 0-1.321003 1.231481 0.155015 9 6 0-0.641175 2.426077 0.097596 10 6 0-2.785831 1.225018 0.342243 11 6 0-2.759929-1.251778 0.279897 12 6 0-1.296065-1.218409 0.086554 13 6 0-0.592256-2.393278-0.040573 14 6 0 0.795132-2.373558-0.219322 15 1 0 1.345132-3.299823-0.320054 16 1 0-1.122457-3.335537-0.001621 17 1 0 1.276187 3.387228-0.126341 18 1 0-1.191646 3.353004 0.189654 19 8 0 3.575005-2.204033-0.603670 20 8 0 3.532350 2.345234-0.493529 21 8 0-3.386279-2.294993 0.322569 22 8 0-3.434224 2.251363 0.434541 23 6 0 5.022891 0.117166-0.725632 24 1 0 5.298813-0.841399-1.159541 25 1 0 5.209037 0.899881-1.459144 26 7 0-3.405346-0.022880 0.421400 27 7 0 3.567560 0.073234-0.501740 28 6 0-5.625594-0.028289-0.682886 29 1 0-5.346539 0.864349-1.250397 30 1 0-5.327514-0.893470-1.282186 31 6 0-7.121205-0.049402-0.436038 32 1 0-7.679201-0.039245-1.373123 33 1 0-7.416433-0.944589 0.116874 34 1 0-7.436225 0.818955 0.147809 35 6 0-4.859494-0.042988 0.625868 36 1 0-5.094845-0.939411 1.197727 37 1 0-5.113382 0.828145 1.227997 38 6 0 5.811841 0.379911 0.544721 39 1 0 6.860475 0.483269 0.252951 40 1 0 5.512983 1.344861 0.961257 41 6 0 5.673341-0.709222 1.590879 42 1 0 4.637074-0.825759 1.917627 43 1 0 6.011759-1.674803 1.208317 44 1 0 6.266972-0.475516 2.476286 SCF Done: E(RM06) = -1183.09160218 A.U. after 1 cycles Convg = 0.4480D-08 -V/T = 2.0050 SMD-CDS (non-electrostatic) energy (kcal/mol) = -7.89 0.349406 (Hartree/Particle) S 6

Thermal correction to Energy= 0.371049 Thermal correction to Enthalpy= 0.371994 Thermal correction to Gibbs Free Energy= 0.298980 Sum of electronic and zero-point Energies= -1182.742196 Sum of electronic and thermal Energies= -1182.720553 Sum of electronic and thermal Enthalpies= -1182.719609 Sum of electronic and thermal Free Energies= -1182.792622 Structure 3c 1 6 0-2.808360 1.318570 0.399846 2 6 0-1.353295 1.264158 0.152780 3 6 0-0.695903 0.020926 0.111965 4 6 0-1.403515-1.181003 0.294975 5 6 0-2.862953-1.154856 0.524074 6 6 0-0.641599 2.426860-0.030068 7 6 0 0.695853-0.020582-0.111881 8 6 0 1.403471 1.181347-0.294863 9 6 0 0.738644 2.385184-0.254851 10 6 0 2.862922 1.155208-0.523883 11 6 0 2.808275-1.318233-0.399950 12 6 0 1.353234-1.263817-0.152756 13 6 0 0.641540-2.426520 0.030092 14 6 0-0.738694-2.384841 0.254930 15 1 0-1.296943-3.300948 0.396156 16 1 0 1.158998-3.376038-0.004591 17 1 0-1.159064 3.376376 0.004569 18 1 0 1.296895 3.301291-0.396066 19 8 0-3.507310-2.173257 0.692478 20 8 0-3.413630 2.371558 0.483426 21 8 0 3.413553-2.371220-0.483490 22 8 0 3.507210 2.173597-0.692620 23 6 0-4.927697 0.166495 0.779226 24 1 0-5.210557-0.783023 1.228220 25 1 0-5.097001 0.960780 1.504473 26 7 0 3.475478-0.100749-0.539447 27 7 0-3.475537 0.101084 0.539448 28 6 0 5.726385-0.422390 0.486462 29 1 0 5.430168-1.384173 0.911700 30 1 0 6.772711-0.529027 0.187706 31 6 0 5.595669 0.673437 1.526737 32 1 0 6.189644 0.442231 2.412441 33 1 0 5.936730 1.635446 1.137814 34 1 0 4.560142 0.795896 1.853974 35 6 0 4.927607-0.166227-0.779411 36 1 0 5.096644-0.960015-1.505260 37 1 0 5.210626 0.783554-1.227751 38 6 0-5.726364 0.421414-0.486956 39 1 0-6.772765 0.527997-0.188442 40 1 0-5.430359 1.382910-0.912987 41 6 0-5.595142-0.675311-1.526216 S 7

42 1 0-4.559520-0.797716-1.853183 43 1 0-5.935900-1.637083-1.136430 44 1 0-6.189079-0.445137-2.412216 SCF Done: E(RM06) = -1183.09090294 A.U. after 1 cycles Convg = 0.7315D-08 -V/T = 2.0050 SMD-CDS (non-electrostatic) energy (kcal/mol) = -7.91 0.350249 (Hartree/Particle) Thermal correction to Energy= 0.371567 Thermal correction to Enthalpy= 0.372511 Thermal correction to Gibbs Free Energy= 0.300171 Sum of electronic and zero-point Energies= -1182.740654 Sum of electronic and thermal Energies= -1182.719336 Sum of electronic and thermal Enthalpies= -1182.718392 Sum of electronic and thermal Free Energies= -1182.790732 Structure 4a 1 6 0 2.859927-1.259031 0.253607 2 6 0 1.389974-1.230774 0.116351 3 6 0 0.703199 0.000004 0.059940 4 6 0 1.389972 1.230783 0.116340 5 6 0 2.859929 1.259043 0.253554 6 6 0 0.696694-2.416461 0.058540 7 6 0-0.703231 0.000002-0.060406 8 6 0-1.390007-1.230777-0.116778 9 6 0-0.696730-2.416463-0.058891 10 6 0-2.859958-1.259038-0.254032 11 6 0-2.859966 1.259036-0.253983 12 6 0-1.390010 1.230779-0.116771 13 6 0-0.696736 2.416466-0.058888 14 6 0 0.696689 2.416468 0.058533 15 1 0 1.239525 3.351221 0.104955 16 1 0-1.239579 3.351218-0.105260 17 1 0 1.239532-3.351213 0.104970 18 1 0-1.239570-3.351216-0.105271 19 8 0 3.517981 2.274463 0.310499 20 8 0 3.517987-2.274449 0.310485 21 8 0-3.518068 2.274453-0.310374 22 8 0-3.518064-2.274456-0.310354 23 7 0-3.469483-0.000002-0.316527 24 7 0 3.469428 0.000007 0.316325 25 8 0-4.817322 0.000002-0.546401 26 6 0-5.545543-0.000004 0.704057 27 1 0-5.263099-0.890893 1.271395 28 1 0-5.263109 0.890890 1.271395 29 6 0-7.003130-0.000013 0.352210 30 1 0-7.599801-0.000014 1.264716 31 1 0-7.265794 0.886433-0.226531 32 1 0-7.265783-0.886464-0.226528 33 8 0 4.817180 0.000011 0.546703 34 6 0 5.545855-0.000015-0.703487 S 8

35 1 0 5.263632 0.890869-1.270943 36 1 0 5.263622-0.890916-1.270912 37 6 0 7.003309-0.000018-0.351091 38 1 0 7.265747-0.886458 0.227760 39 1 0 7.600318-0.000034-1.263376 40 1 0 7.265757 0.886438 0.227733 SCF Done: E(RM06) = -1254.79868239 A.U. after 2 cycles Convg = 0.2465D-08 -V/T = 2.0048 SMD-CDS (non-electrostatic) energy (kcal/mol) = -6.44 0.298204 (Hartree/Particle) Thermal correction to Energy= 0.320145 Thermal correction to Enthalpy= 0.321089 Thermal correction to Gibbs Free Energy= 0.246146 Sum of electronic and zero-point Energies= -1254.500478 Sum of electronic and thermal Energies= -1254.478537 Sum of electronic and thermal Enthalpies= -1254.477593 Sum of electronic and thermal Free Energies= -1254.552536 Structure 4b 1 6 0 2.906574 1.328219-0.380947 2 6 0 1.442581 1.282784-0.192813 3 6 0 0.769993 0.044674-0.143522 4 6 0 1.467127-1.174882-0.259670 5 6 0 2.933969-1.186432-0.437395 6 6 0 0.740189 2.459364-0.083919 7 6 0-0.632142 0.026506 0.017892 8 6 0-1.328595 1.247671 0.128636 9 6 0-0.648648 2.441591 0.079413 10 6 0-2.794882 1.256995 0.305518 11 6 0-2.769150-1.260490 0.236793 12 6 0-1.304137-1.212828 0.059677 13 6 0-0.601217-2.388301-0.056764 14 6 0 0.787642-2.369344-0.218129 15 1 0 1.338897-3.295651-0.311149 16 1 0-1.132963-3.329940-0.022910 17 1 0 1.271563 3.400840-0.125447 18 1 0-1.198942 3.369051 0.167282 19 8 0 3.584634-2.195364-0.590041 20 8 0 3.541889 2.354146-0.489917 21 8 0-3.415165-2.284068 0.285306 22 8 0-3.460492 2.263578 0.409022 23 7 0-3.390178-0.010192 0.347014 24 7 0 3.541226 0.078745-0.412097 25 8 0-4.732709-0.033613 0.605626 26 6 0-5.487844-0.034406-0.628858 27 1 0-5.265944 0.886066-1.175857 28 1 0-5.173017-0.892414-1.228591 S 9

29 6 0-6.934917-0.123563-0.246976 30 1 0-7.551680-0.124432-1.146027 31 1 0-7.136001-1.042027 0.305851 32 1 0-7.230446 0.727251 0.368108 33 8 0 4.883737 0.098516-0.691535 34 6 0 5.670378 0.351022 0.497285 35 1 0 5.359362 1.306634 0.925299 36 1 0 6.676142 0.473904 0.095226 37 6 0 5.610476-0.764785 1.502088 38 1 0 5.914960-1.712722 1.058608 39 1 0 6.283437-0.534585 2.329927 40 1 0 4.607783-0.880166 1.917714 SCF Done: E(RM06) = -1254.79714744 A.U. after 1 cycles Convg = 0.3771D-08 -V/T = 2.0048 SMD-CDS (non-electrostatic) energy (kcal/mol) = -6.37 0.299217 (Hartree/Particle) Thermal correction to Energy= 0.320618 Thermal correction to Enthalpy= 0.321563 Thermal correction to Gibbs Free Energy= 0.248713 Sum of electronic and zero-point Energies= -1254.497931 Sum of electronic and thermal Energies= -1254.476529 Sum of electronic and thermal Enthalpies= -1254.475585 Sum of electronic and thermal Free Energies= -1254.548434 Structure 4c 1 6 0 2.800304 1.353727-0.380338 2 6 0 1.345310 1.275919-0.141683 3 6 0 0.697351 0.024514-0.105523 4 6 0 1.410027-1.178121-0.283997 5 6 0 2.871244-1.158424-0.500201 6 6 0 0.627795 2.435042 0.035664 7 6 0-0.697251-0.024504 0.105021 8 6 0-1.409912 1.178127 0.283568 9 6 0-0.753018 2.385713 0.251253 10 6 0-2.871095 1.158426 0.499970 11 6 0-2.800185-1.353721 0.380017 12 6 0-1.345208-1.275909 0.141231 13 6 0-0.627687-2.435032-0.036096 14 6 0 0.753131-2.385705-0.251669 15 1 0 1.317196-3.298579-0.390538 16 1 0-1.140484-3.387207-0.005127 17 1 0 1.140603 3.387213 0.004760 18 1 0-1.317071 3.298581 0.390207 19 8 0 3.536553-2.151290-0.691001 20 8 0 3.413322 2.393828-0.484812 21 8 0-3.413151-2.393824 0.484768 S 10

22 8 0-3.536353 2.151278 0.691023 23 7 0-3.455480-0.117419 0.462346 24 7 0 3.455612 0.117426-0.462512 25 8 0-4.792455-0.167175 0.763805 26 6 0-5.592740-0.417948-0.416847 27 1 0-5.281371-1.369395-0.853995 28 1 0-6.592658-0.548897-0.002959 29 6 0-5.551160 0.702944-1.416846 30 1 0-6.227692 0.469602-2.240829 31 1 0-5.861458 1.646194-0.967382 32 1 0-4.552542 0.829250-1.839387 33 8 0 4.792731 0.167201-0.763323 34 6 0 5.592274 0.418017 0.417817 35 1 0 5.280282 1.369280 0.854922 36 1 0 6.592411 0.549384 0.004589 37 6 0 5.550405-0.703069 1.417591 38 1 0 5.861590-1.646071 0.968230 39 1 0 6.226114-0.469542 2.242195 40 1 0 4.551469-0.829980 1.839218 SCF Done: E(RM06) = -1254.79563900 A.U. after 1 cycles Convg = 0.5475D-08 -V/T = 2.0048 SMD-CDS (non-electrostatic) energy (kcal/mol) = -6.32 0.300626 (Hartree/Particle) Thermal correction to Energy= 0.321411 Thermal correction to Enthalpy= 0.322355 Thermal correction to Gibbs Free Energy= 0.251602 Sum of electronic and zero-point Energies= -1254.495013 Sum of electronic and thermal Energies= -1254.474228 Sum of electronic and thermal Enthalpies= -1254.473284 Sum of electronic and thermal Free Energies= -1254.544037 Structure 5a 1 6 0 2.846875-1.263975-0.343477 2 6 0 1.383290-1.232888-0.163554 3 6 0 0.700743 0.000120-0.086021 4 6 0 1.382876 1.233365-0.163489 5 6 0 2.846459 1.264985-0.343445 6 6 0 0.694725-2.419435-0.080721 7 6 0-0.700744-0.000120 0.086019 8 6 0-1.382873-1.233366 0.163516 9 6 0-0.693912-2.419670 0.080563 10 6 0-2.846443-1.264987 0.343592 11 6 0-2.846894 1.263975 0.343315 12 6 0-1.383293 1.232889 0.163522 13 6 0-0.694727 2.419435 0.080707 14 6 0 0.693915 2.419671-0.080547 15 1 0 1.234812 3.354585-0.142573 16 1 0-1.235932 3.354167 0.142815 17 1 0 1.235929-3.354165-0.142853 S 11

18 1 0-1.234807-3.354584 0.142616 19 8 0 3.519718 2.268825-0.379181 20 8 0 3.520576-2.267544-0.378730 21 8 0-3.520571 2.267552 0.378747 22 8 0-3.519724-2.268817 0.379165 23 7 0-3.432224-0.000596 0.488889 24 7 0 3.432226 0.000606-0.488881 25 8 0-4.783028-0.000741 0.736101 26 6 0-6.980258 0.001802-0.054727 27 1 0-7.204781-0.871182 0.559023 28 1 0-7.205064 0.888197 0.539644 29 1 0-7.593268-0.007539-0.950977 30 6 0-5.546330-0.000569-0.428296 31 8 0-5.050261-0.001469-1.515716 32 8 0 4.783026 0.000780-0.736099 33 6 0 5.546334 0.000564 0.428303 34 8 0 5.050261 0.001552 1.515720 35 6 0 6.980258-0.001909 0.054724 36 1 0 7.205069-0.888620-0.539181 37 1 0 7.204761 0.870749-0.559491 38 1 0 7.593278 0.007885 0.950962 SCF Done: E(RM06) = -1402.87742883 A.U. after 1 cycles Convg = 0.7384D-08 -V/T = 2.0047 SMD-CDS (non-electrostatic) energy (kcal/mol) = -5.50 0.259867 (Hartree/Particle) Thermal correction to Energy= 0.281385 Thermal correction to Enthalpy= 0.282329 Thermal correction to Gibbs Free Energy= 0.208355 Sum of electronic and zero-point Energies= -1402.617562 Sum of electronic and thermal Energies= -1402.596044 Sum of electronic and thermal Enthalpies= -1402.595100 Sum of electronic and thermal Free Energies= -1402.669074 Structure 5b 1 6 0-2.833623-1.263220 0.347488 2 6 0-1.369837-1.229534 0.166593 3 6 0-0.689098 0.004675 0.093384 4 6 0-1.373298 1.236544 0.172543 5 6 0-2.837204 1.265436 0.353734 6 6 0-0.680882-2.414980 0.072837 7 6 0 0.711989 0.006985-0.082516 8 6 0 1.394548-1.224955-0.172382 9 6 0 0.706698-2.412803-0.096125 10 6 0 2.855050-1.255665-0.368521 11 6 0 2.851724 1.277136-0.365472 12 6 0 1.391328 1.241117-0.167124 13 6 0 0.700081 2.426582-0.085419 14 6 0-0.687450 2.424241 0.084217 S 12

15 1 0-1.230252 3.358105 0.145404 16 1 0 1.238317 3.362400-0.156302 17 1 0-1.221244-3.350534 0.129460 18 1 0 1.247648-3.346778-0.170719 19 8 0-3.511279 2.268358 0.392387 20 8 0-3.505021-2.268221 0.380850 21 8 0 3.512514 2.284178-0.468578 22 8 0 3.520500-2.260294-0.468355 23 7 0 3.460618 0.011445-0.413196 24 7 0-3.421141-0.000145 0.495392 25 8 0 4.784825 0.013465-0.789273 26 6 0 5.217979-0.032505 1.637760 27 1 0 4.686679 0.892851 1.865995 28 1 0 4.535698-0.864632 1.809251 29 1 0 6.071141-0.122191 2.303809 30 6 0 5.721638-0.017735 0.241769 31 8 0 6.863838-0.023359-0.111830 32 8 0-4.772413-0.002944 0.739535 33 6 0-5.532579-0.005626-0.427715 34 8 0-5.032652 0.001754-1.513205 35 6 0-6.967408-0.026108-0.059097 36 1 0-7.192487-0.951064 0.474147 37 1 0-7.194913 0.803260 0.610743 38 1 0-7.577348 0.038487-0.955122 SCF Done: E(RM06) = -1402.87079984 A.U. after 1 cycles Convg = 0.3553D-08 -V/T = 2.0047 SMD-CDS (non-electrostatic) energy (kcal/mol) = -5.35 0.260261 (Hartree/Particle) Thermal correction to Energy= 0.283277 Thermal correction to Enthalpy= 0.284221 Thermal correction to Gibbs Free Energy= 0.206221 Sum of electronic and zero-point Energies= -1402.610539 Sum of electronic and thermal Energies= -1402.587523 Sum of electronic and thermal Enthalpies= -1402.586579 Sum of electronic and thermal Free Energies= -1402.664578 Structure 5c 1 6 0-2.842125-1.256333 0.372265 2 6 0-1.381421-1.223334 0.174862 3 6 0-0.700361 0.009687 0.089299 4 6 0-1.381645 1.242580 0.174911 5 6 0-2.842454 1.276046 0.373741 6 6 0-0.693306-2.410219 0.088207 7 6 0 0.700377 0.009673-0.089341 8 6 0 1.381420-1.223358-0.174876 9 6 0 0.693291-2.410230-0.088187 10 6 0 2.842130-1.256387-0.372336 S 13

11 6 0 2.842471 1.275996-0.373940 12 6 0 1.381672 1.242553-0.175084 13 6 0 0.693306 2.429285-0.088567 14 6 0-0.693278 2.429297 0.088252 15 1 0-1.233159 3.364256 0.157733 16 1 0 1.233186 3.364235-0.158180 17 1 0-1.233331-3.345119 0.157381 18 1 0 1.233305-3.345136-0.157344 19 8 0-3.503823 2.282177 0.479809 20 8 0-3.505203-2.262347 0.471753 21 8 0 3.503870 2.282084-0.480124 22 8 0 3.505118-2.262417-0.472212 23 7 0 3.449769 0.009513-0.417635 24 7 0-3.449704 0.009596 0.417923 25 8 0 4.774477 0.008794-0.791469 26 6 0 5.203568-0.034586 1.636703 27 1 0 4.674341 0.892656 1.862100 28 1 0 4.518672-0.864467 1.808808 29 1 0 6.055238-0.125254 2.304527 30 6 0 5.709749-0.024007 0.241667 31 8 0 6.852243-0.033869-0.110439 32 8 0-4.774410 0.008942 0.791730 33 6 0-5.709746-0.024005-0.241350 34 8 0-6.852224-0.033831 0.110817 35 6 0-5.203688-0.034833-1.636430 36 1 0-4.674368 0.892282-1.862114 37 1 0-4.519035-0.864928-1.808465 38 1 0-6.055446-0.125491-2.304155 SCF Done: E(RM06) = -1402.86420090 A.U. after 1 cycles Convg = 0.4245D-08 -V/T = 2.0047 SMD-CDS (non-electrostatic) energy (kcal/mol) = -5.20 0.260494 (Hartree/Particle) Thermal correction to Energy= 0.283252 Thermal correction to Enthalpy= 0.284196 Thermal correction to Gibbs Free Energy= 0.207369 Sum of electronic and zero-point Energies= -1402.603707 Sum of electronic and thermal Energies= -1402.580949 Sum of electronic and thermal Enthalpies= -1402.580005 Sum of electronic and thermal Free Energies= -1402.656832 Structure 6a 1 6 0 2.856083-1.249280-0.322869 2 6 0 1.391444-1.224106-0.158092 3 6 0 0.701305 0.005570-0.082326 4 6 0 1.371982 1.246128-0.156805 5 6 0 2.835571 1.295304-0.327238 6 6 0 0.713520-2.416874-0.079358 7 6 0-0.701316-0.005430 0.082326 8 6 0-1.371993-1.245987 0.156816 9 6 0-0.675741-2.427789 0.073895 S 14

10 6 0-2.835576-1.295158 0.327317 11 6 0-2.856104 1.249421 0.322788 12 6 0-1.391459 1.224246 0.158070 13 6 0-0.713536 2.417015 0.079336 14 6 0 0.675725 2.427929-0.073908 15 1 0 1.213898 3.364236-0.131801 16 1 0-1.266183 3.344688 0.139453 17 1 0 1.266166-3.344547-0.139483 18 1 0-1.213915-3.364095 0.131779 19 8 0 3.508465 2.296431-0.349183 20 8 0 3.546584-2.238662-0.336697 21 8 0-3.546581 2.238816 0.336811 22 8 0-3.508509-2.296265 0.348987 23 7 0-3.425005-0.027379 0.476007 24 7 0 3.425004 0.027527-0.475930 25 8 0-4.784357-0.035403 0.708872 26 6 0-7.002137 0.013324-0.055416 27 6 0-5.508823-0.040884-0.442073 28 8 0-5.085340-0.064183-1.550190 29 8 0 4.784352 0.035533-0.708814 30 6 0 5.508842 0.040473 0.442123 31 8 0 5.085383 0.063357 1.550257 32 6 0 7.002153-0.013469 0.055407 33 9 0-7.746943-0.114336-1.138386 34 9 0-7.304008-0.958930 0.797665 35 9 0-7.269481 1.182437 0.519880 36 9 0 7.269504-1.182104-0.520804 37 9 0 7.304008 0.959480-0.796917 38 9 0 7.746968 0.113353 1.138473 SCF Done: E(RM06) = -1998.34160139 A.U. after 9 cycles Convg = 0.9974D-08 -V/T = 2.0043 SMD-CDS (non-electrostatic) energy (kcal/mol) = -3.11 0.215440 (Hartree/Particle) Thermal correction to Energy= 0.242244 Thermal correction to Enthalpy= 0.243189 Thermal correction to Gibbs Free Energy= 0.154037 Sum of electronic and zero-point Energies= -1998.126161 Sum of electronic and thermal Energies= -1998.099357 Sum of electronic and thermal Enthalpies= -1998.098413 Sum of electronic and thermal Free Energies= -1998.187564 Structure 6b 1 6 0 3.029639-1.271310-0.784551 2 6 0 1.584517-1.233749-0.502689 3 6 0 0.912292 0.000674-0.370190 4 6 0 1.584211 1.235361-0.501714 5 6 0 3.029323 1.273488-0.783535 S 15

6 6 0 0.902372-2.421627-0.390581 7 6 0-0.477175 0.000416-0.116737 8 6 0-1.151573-1.235496-0.004832 9 6 0-0.472395-2.422410-0.140409 10 6 0-2.601522-1.272271 0.255502 11 6 0-2.601756 1.272326 0.256834 12 6 0-1.151836 1.236086-0.003731 13 6 0-0.472934 2.423265-0.138343 14 6 0 0.901813 2.422995-0.388611 15 1 0 1.436110 3.357515-0.495789 16 1 0-1.009919 3.358299-0.050030 17 1 0 1.436866-3.355946-0.498513 18 1 0-1.009193-3.357637-0.053006 19 8 0 3.678663 2.268104-0.989148 20 8 0 3.679347-2.265619-0.990499 21 8 0-3.284689 2.265663 0.318358 22 8 0-3.284221-2.265814 0.316294 23 7 0-3.169381-0.000124 0.441015 24 7 0 3.646556 0.001162-0.768576 25 8 0-4.509222-0.000424 0.769763 26 6 0-6.772835-0.000609 0.182169 27 6 0-5.315480 0.000141-0.323090 28 8 0-4.977010 0.000732-1.460437 29 8 0 4.946460 0.001518-1.251722 30 6 0 5.955519 0.000221-0.340676 31 8 0 7.080537 0.001103-0.720188 32 6 0 5.599546-0.001729 1.172312 33 9 0-7.605278-0.000172-0.842007 34 9 0-6.997759-1.080400 0.925516 35 9 0-6.998424 1.078009 0.927006 36 9 0 4.899225 1.078922 1.507679 37 9 0 4.898147-1.082645 1.504451 38 9 0 6.723714-0.003295 1.864924 SCF Done: E(RM06) = -1998.33232965 A.U. after 1 cycles Convg = 0.6422D-08 -V/T = 2.0043 SMD-CDS (non-electrostatic) energy (kcal/mol) = -3.05 0.215308 (Hartree/Particle) Thermal correction to Energy= 0.242028 Thermal correction to Enthalpy= 0.242972 Thermal correction to Gibbs Free Energy= 0.154045 Sum of electronic and zero-point Energies= -1998.117022 Sum of electronic and thermal Energies= -1998.090301 Sum of electronic and thermal Enthalpies= -1998.089357 Sum of electronic and thermal Free Energies= -1998.178285 Structure 6c 1 6 0-1.433926 10.143496 2.478841 S 16

2 6 0-0.701630 10.106047 1.201310 3 6 0-0.353752 8.871287 0.611495 4 6 0-0.701419 7.636385 1.201139 5 6 0-1.433887 7.598623 2.478570 6 6 0-0.353672 11.293880 0.603407 7 6 0 0.352649 8.871430-0.610945 8 6 0 0.700308 10.106333-1.200591 9 6 0 0.352158 11.294026-0.602503 10 6 0 1.432752 10.144096-2.478032 11 6 0 1.432871 7.599221-2.478271 12 6 0 0.700550 7.636671-1.200751 13 6 0 0.352602 6.448839-0.602839 14 6 0-0.353251 6.448693 0.603059 15 1 0-0.627677 5.514084 1.073902 16 1 0 0.627122 5.514346-1.073861 17 1 0-0.628170 12.228372 1.074445 18 1 0 0.626586 12.228633-1.073349 19 8 0-1.833234 6.604263 3.030568 20 8 0-1.833589 11.137723 3.030849 21 8 0 1.832659 6.605005-3.030204 22 8 0 1.832087 11.138459-3.030036 23 7 0 1.610113 8.871736-3.068339 24 7 0-1.611185 8.870979 3.068900 25 8 0 2.451646 8.872025-4.170239 26 6 0 0.317319 8.871859-5.495469 27 6 0 1.869666 8.872477-5.399740 28 8 0 2.556863 8.873266-6.367839 29 8 0-2.452651 8.870715 4.170850 30 6 0-1.870561 8.870501 5.400296 31 8 0-2.557660 8.869929 6.368464 32 6 0-0.318208 8.870261 5.495853 33 9 0-0.019803 8.871705-6.771947 34 9 0-0.205426 7.791057-4.921167 35 9 0-0.206421 9.952205-4.921210 36 9 0 0.204806 7.789560 4.921598 37 9 0 0.205118 9.950707 4.921414 38 9 0 0.019059 8.870308 6.772293 SCF Done: E(RM06) = -1998.32339213 A.U. after 1 cycles Convg = 0.5436D-08 -V/T = 2.0043 SMD-CDS (non-electrostatic) energy (kcal/mol) = -3.24 0.215142 (Hartree/Particle) Thermal correction to Energy= 0.240827 Thermal correction to Enthalpy= 0.241771 Thermal correction to Gibbs Free Energy= 0.157042 Sum of electronic and zero-point Energies= -1998.108250 Sum of electronic and thermal Energies= -1998.082565 Sum of electronic and thermal Enthalpies= -1998.081621 Sum of electronic and thermal Free Energies= -1998.166350 Structure 7a S 17

1 6 0-2.845001-1.253660 0.359573 2 6 0-1.382255-1.222277 0.171038 3 6 0-0.700268 0.010438 0.090269 4 6 0-1.382639 1.242835 0.173382 5 6 0-2.845142 1.273308 0.365115 6 6 0-0.693432-2.408414 0.083976 7 6 0 0.700276 0.010691-0.090323 8 6 0 1.382665-1.221772-0.171506 9 6 0 0.694232-2.408165-0.084803 10 6 0 2.845435-1.252596-0.359919 11 6 0 2.844700 1.274373-0.365098 12 6 0 1.382242 1.243339-0.173047 13 6 0 0.693321 2.429402-0.085526 14 6 0-0.694094 2.429155 0.086311 15 1 0-1.235110 3.363717 0.152934 16 1 0 1.234029 3.364157-0.151946 17 1 0-1.234527-3.343044 0.148792 18 1 0 1.235634-3.342603-0.149845 19 8 0-3.515131 2.279025 0.414927 20 8 0-3.514849-2.259821 0.401146 21 8 0 3.514474 2.280294-0.413574 22 8 0 3.515591-2.258531-0.402070 23 7 0 3.432266 0.010822-0.508581 24 7 0-3.432273 0.009523 0.508366 25 8 0 4.774390 0.008715-0.762342 26 6 0 5.530830 0.019375 0.423798 27 8 0 5.006504 0.014651 1.511780 28 8 0-4.774375 0.006902 0.762254 29 6 0-5.530884 0.019489-0.423810 30 8 0-5.006640 0.016198-1.511835 31 7 0-6.834429 0.042569-0.120219 32 7 0 6.834406 0.042338 0.120340 33 6 0-7.806093-0.085626-1.191582 34 1 0-7.305387-0.018487-2.152730 35 1 0-8.321632-1.046410-1.123508 36 1 0-8.544223 0.714153-1.117586 37 6 0-7.343305-0.042573 1.241429 38 1 0-7.343001-1.072712 1.604970 39 1 0-6.759412 0.575100 1.918723 40 1 0-8.367517 0.326397 1.241825 41 6 0 7.805941-0.087394 1.191637 42 1 0 8.321579-1.048015 1.122124 43 1 0 8.544008 0.712582 1.118983 44 1 0 7.305131-0.021824 2.152841 45 6 0 7.343505-0.041783-1.241284 46 1 0 8.367551 0.327654-1.241333 47 1 0 7.343712-1.071736-1.605369 48 1 0 6.759449 0.575977-1.918310 SCF Done: E(RM06) = -1592.14554650 A.U. after 2 cycles Convg = 0.2574D-08 -V/T = 2.0048 SMD-CDS (non-electrostatic) energy (kcal/mol) = -6.08 0.352084 (Hartree/Particle) Thermal correction to Energy= 0.380391 Thermal correction to Enthalpy= 0.381335 Thermal correction to Gibbs Free Energy= 0.292057 Sum of electronic and zero-point Energies= -1591.793462 S 18

Sum of electronic and thermal Energies= -1591.765155 Sum of electronic and thermal Enthalpies= -1591.764211 Sum of electronic and thermal Free Energies= -1591.853490 Structure 7b 1 6 0 3.012424-0.992195-0.748363 2 6 0 1.565736-1.033474-0.472464 3 6 0 0.842295 0.161895-0.283716 4 6 0 1.465579 1.424226-0.367394 5 6 0 2.911003 1.527833-0.644107 6 6 0 0.931945-2.252148-0.408953 7 6 0-0.542774 0.093568-0.020006 8 6 0-1.166508-1.169895 0.047423 9 6 0-0.439763-2.319990-0.148378 10 6 0-2.612564-1.272058 0.323211 11 6 0-2.718973 1.250283 0.422247 12 6 0-1.268038 1.290820 0.155809 13 6 0-0.636807 2.508698 0.068417 14 6 0 0.734814 2.575805-0.194323 15 1 0 1.229888 3.535084-0.265966 16 1 0-1.211614 3.415607 0.201718 17 1 0 1.504462-3.157504-0.561234 18 1 0-0.938475-3.278721-0.096755 19 8 0 3.509126 2.570599-0.779007 20 8 0 3.701393-1.962674-0.963335 21 8 0-3.427695 2.223836 0.532929 22 8 0-3.235080-2.307817 0.364784 23 7 0-3.243854-0.042092 0.552940 24 7 0 3.578506 0.294687-0.711835 25 8 0-4.576202-0.111491 0.846232 26 6 0-5.362917-0.102625-0.321878 27 8 0-4.864250-0.068638-1.421302 28 8 0 4.901882 0.374886-1.090050 29 6 0 5.834579-0.259435-0.246412 30 8 0 6.798882-0.728119-0.797852 31 7 0 5.567233-0.272781 1.071577 32 7 0-6.658500-0.133666 0.011405 33 6 0 6.416956-1.118804 1.896861 34 1 0 6.688429-2.019763 1.352341 35 1 0 7.328891-0.596755 2.198291 36 1 0 5.859132-1.400869 2.789178 37 6 0 4.816478 0.752756 1.783840 38 1 0 4.705304 1.650147 1.180848 39 1 0 3.834496 0.393347 2.102688 40 1 0 5.384138 1.032766 2.671961 41 6 0-7.650866-0.288031-1.037412 42 1 0-8.164488-1.246088-0.930341 43 1 0-8.387705 0.514047-0.973454 44 1 0-7.168615-0.250403-2.009440 S 19

45 6 0-7.134588-0.227959 1.384024 46 1 0-8.166628 0.118265 1.406225 47 1 0-7.103710-1.257094 1.749056 48 1 0-6.549710 0.404635 2.046532 SCF Done: E(RM06) = -1592.13209087 A.U. after 1 cycles Convg = 0.2882D-08 -V/T = 2.0048 SMD-CDS (non-electrostatic) energy (kcal/mol) = -6.10 0.352621 (Hartree/Particle) Thermal correction to Energy= 0.380537 Thermal correction to Enthalpy= 0.381481 Thermal correction to Gibbs Free Energy= 0.293348 Sum of electronic and zero-point Energies= -1591.779470 Sum of electronic and thermal Energies= -1591.751554 Sum of electronic and thermal Enthalpies= -1591.750609 Sum of electronic and thermal Free Energies= -1591.838743 Structure 7c 1 6 0-2.777103-1.024303 0.710817 2 6 0-1.348706-0.996019 0.345497 3 6 0-0.683984 0.235332 0.171647 4 6 0-1.349247 1.466433 0.345562 5 6 0-2.781859 1.499571 0.696440 6 6 0-0.676575-2.183176 0.174199 7 6 0 0.684445 0.235405-0.172684 8 6 0 1.349174-0.995872-0.347011 9 6 0 0.677050-2.183099-0.176187 10 6 0 2.777613-1.024018-0.712205 11 6 0 2.782311 1.499832-0.697010 12 6 0 1.349709 1.466573-0.346108 13 6 0 0.677144 2.653320-0.174325 14 6 0-0.676673 2.653247 0.174272 15 1 0-1.205178 3.587379 0.310722 16 1 0 1.205639 3.587508-0.310425 17 1 0-1.204082-3.117682 0.312103 18 1 0 1.204579-3.117544-0.314427 19 8 0-3.414414 2.511263 0.894273 20 8 0-3.412997-2.029762 0.928692 21 8 0 3.415045 2.511624-0.893735 22 8 0 3.413631-2.029416-0.929968 23 7 0 3.393947 0.237927-0.758051 24 7 0-3.393415 0.237634 0.757452 25 8 0 4.697087 0.252982-1.206203 26 6 0 5.649667-0.406013-0.403793 S 20

27 8 0 6.564253-0.916388-1.001186 28 8 0-4.696186 0.252519 1.206694 29 6 0-5.649619-0.406056 0.404995 30 8 0-6.563779-0.916352 1.003131 31 7 0-5.457597-0.392885-0.925174 32 7 0 5.456239-0.393296 0.926198 33 6 0-6.313346-1.265916-1.715317 34 1 0-6.545357-2.167726-1.154501 35 1 0-7.246575-0.767720-1.990219 36 1 0-5.778865-1.542611-2.623668 37 6 0-4.762727 0.649680-1.667743 38 1 0-4.646295 1.550064-1.070190 39 1 0-3.788176 0.313056-2.031605 40 1 0-5.375535 0.916083-2.529661 41 6 0 6.310983-1.266834 1.716882 42 1 0 7.244097-0.768999 1.992816 43 1 0 5.775558-1.543648 2.624643 44 1 0 6.543251-2.168536 1.156000 45 6 0 4.761160 0.649358 1.668468 46 1 0 5.373362 0.915252 2.530967 47 1 0 4.645610 1.549981 1.071115 48 1 0 3.786128 0.313064 2.031400 SCF Done: E(RM06) = -1592.11868136 A.U. after 1 cycles Convg = 0.6109D-08 -V/T = 2.0048 SMD-CDS (non-electrostatic) energy (kcal/mol) = -6.18 0.352758 (Hartree/Particle) Thermal correction to Energy= 0.380265 Thermal correction to Enthalpy= 0.381209 Thermal correction to Gibbs Free Energy= 0.295013 Sum of electronic and zero-point Energies= -1591.765923 Sum of electronic and thermal Energies= -1591.738416 Sum of electronic and thermal Enthalpies= -1591.737472 Sum of electronic and thermal Free Energies= -1591.823668 Structure 8a 1 6 0-2.798785-1.328063 0.466905 2 6 0-1.346515-1.262070 0.223876 3 6 0-0.695849-0.014621 0.117749 4 6 0-1.398981 1.203392 0.231063 5 6 0-2.851439 1.205507 0.476908 6 6 0-0.637992-2.433923 0.106690 7 6 0 0.696033 0.015225-0.118273 8 6 0 1.399169-1.202792-0.231536 9 6 0 0.740909-2.404418-0.119441 10 6 0 2.851645-1.204904-0.477247 S 21

11 6 0 2.798987 1.328669-0.467369 12 6 0 1.346707 1.262674-0.224366 13 6 0 0.638186 2.434526-0.107147 14 6 0-0.740715 2.405017 0.118993 15 1 0-1.298003 3.327911 0.209013 16 1 0 1.156141 3.380464-0.192391 17 1 0-1.155942-3.379860 0.191976 18 1 0 1.298205-3.327314-0.209398 19 8 0-3.540461 2.196980 0.552104 20 8 0-3.447021-2.343854 0.535386 21 8 0 3.447274 2.344449-0.535566 22 8 0 3.540757-2.196337-0.552133 23 7 0 3.415648 0.071939-0.623353 24 7 0-3.415441-0.071343 0.623037 25 8 0 4.735721 0.105685-0.971413 26 6 0 6.621270-1.415179 0.098849 27 1 0 5.902974-2.216550 0.250078 28 1 0 7.016602-1.420335-0.914993 29 1 0 7.431461-1.459407 0.825470 30 8 0 4.986589 0.112722 1.547910 31 8 0-4.735411-0.105155 0.971525 32 8 0-4.987377-0.113654-1.547714 33 6 0-6.622564 1.413863-0.098831 34 1 0-7.017625 1.419289 0.915115 35 1 0-5.904907 2.215671-0.250750 36 1 0-7.432971 1.457120-0.825254 37 16 0-5.802541-0.130214-0.353506 38 16 0 5.802294 0.129341 0.354077 39 8 0-6.708701-1.217741-0.075216 40 8 0 6.709403 1.216330 0.076780 SCF Done: E(RM06) = -2273.31685333 A.U. after 1 cycles Convg = 0.7233D-08 -V/T = 2.0047 SMD-CDS (non-electrostatic) energy (kcal/mol) = -4.37 0.262125 (Hartree/Particle) Thermal correction to Energy= 0.287260 Thermal correction to Enthalpy= 0.288204 Thermal correction to Gibbs Free Energy= 0.207390 Sum of electronic and zero-point Energies= -2273.054728 Sum of electronic and thermal Energies= -2273.029593 Sum of electronic and thermal Enthalpies= -2273.028649 Sum of electronic and thermal Free Energies= -2273.109463 Structure 8b 1 6 0-2.825029-1.214528 0.476857 2 6 0-1.372882-1.180999 0.229664 3 6 0-0.695992 0.052145 0.118203 S 22

4 6 0-1.373293 1.285051 0.227007 5 6 0-2.826253 1.319696 0.470764 6 6 0-0.689177-2.367892 0.114330 7 6 0 0.696090 0.052215-0.118636 8 6 0 1.373099-1.180862-0.230123 9 6 0 0.689513-2.367823-0.114793 10 6 0 2.825253-1.214246-0.477301 11 6 0 2.826250 1.319983-0.471045 12 6 0 1.373283 1.285189-0.227349 13 6 0 0.689644 2.472047-0.112619 14 6 0-0.689762 2.471978 0.112357 15 1 0-1.227376 3.406774 0.199142 16 1 0 1.227177 3.406897-0.199326 17 1 0-1.226164-3.302782 0.203500 18 1 0 1.226592-3.302660-0.203963 19 8 0-3.496185 2.321015 0.541419 20 8 0-3.492687-2.220762 0.551113 21 8 0 3.496130 2.321359-0.541376 22 8 0 3.493080-2.220392-0.551223 23 7 0 3.415912 0.049766-0.625980 24 7 0-3.415778 0.049421 0.625739 25 8 0 4.736733 0.054371-0.972472 26 6 0 6.592881-1.498912 0.101150 27 1 0 5.859635-2.286873 0.250361 28 1 0 6.990886-1.510968-0.911598 29 1 0 7.400377-1.558197 0.829727 30 8 0 4.982532 0.057258 1.547074 31 8 0-4.736509 0.053931 0.972585 32 8 0-6.728009 1.130755-0.079152 33 6 0-6.593240-1.498763-0.101015 34 1 0-5.860175-2.286790-0.250743 35 1 0-6.990925-1.511114 0.911855 36 1 0-7.400979-1.557653-0.829355 37 16 0-5.801328 0.059958-0.354651 38 16 0 5.801147 0.059851 0.355084 39 8 0-4.983081 0.057668-1.546895 40 8 0 6.728072 1.130603 0.080231 SCF Done: E(RM06) = -2273.31676152 A.U. after 1 cycles Convg = 0.3107D-08 -V/T = 2.0047 SMD-CDS (non-electrostatic) energy (kcal/mol) = -4.36 0.261885 (Hartree/Particle) Thermal correction to Energy= 0.287098 Thermal correction to Enthalpy= 0.288043 Thermal correction to Gibbs Free Energy= 0.206937 Sum of electronic and zero-point Energies= -2273.054876 Sum of electronic and thermal Energies= -2273.029663 Sum of electronic and thermal Enthalpies= -2273.028719 Sum of electronic and thermal Free Energies= -2273.109824 Structure 11 (B3LYP/DGDZVP) S 23

1 6 0-2.866847-1.268222 0.392528 2 6 0-1.392174-1.237540 0.192225 3 6 0-0.705268 0.001290 0.098226 4 6 0-1.392212 1.240125 0.192003 5 6 0-2.866946 1.270830 0.391992 6 6 0-0.698352-2.434390 0.095237 7 6 0 0.705268 0.001279-0.098230 8 6 0 1.392156-1.237561-0.192223 9 6 0 0.698317-2.434401-0.095227 10 6 0 2.866829-1.268267-0.392526 11 6 0 2.866966 1.270786-0.392002 12 6 0 1.392231 1.240104-0.192013 13 6 0 0.698382 2.436943-0.095071 14 6 0-0.698345 2.436954 0.095055 15 1 0-1.249698 3.369425 0.168337 16 1 0 1.249748 3.369405-0.168357 17 1 0-1.249714-3.366842 0.168680 18 1 0 1.249665-3.366861-0.168665 19 8 0-3.528905 2.291424 0.452650 20 8 0-3.528714-2.288825 0.453865 21 8 0 3.528939 2.291369-0.452666 22 8 0 3.528682-2.288880-0.453853 23 7 0 3.462845 0.001270-0.523082 24 7 0-3.462844 0.001324 0.523080 25 8 0 4.829515 0.001169-0.750407 26 6 0 7.075094-0.002092 0.106102 27 6 0 5.585455-0.001633 0.439008 28 8 0 5.061018-0.002908 1.521394 29 8 0-4.829514 0.001245 0.750407 30 6 0-5.585457-0.001546-0.439006 31 8 0-5.061021-0.002877-1.521392 32 6 0-7.075094-0.002112-0.106098 33 6 0-7.406008-1.264547 0.725969 34 1 0-7.141508-2.178984 0.185548 35 1 0-6.875512-1.269379 1.681086 36 1 0-8.482229-1.287522 0.927856 37 6 0-7.409799 1.273638 0.704003 38 1 0-7.151278 2.179301 0.146202 39 1 0-8.485534 1.295104 0.908622 40 1 0-6.876461 1.298132 1.657238 41 6 0 7.406111-1.264543-0.725899 42 1 0 7.141686-2.178973-0.185429 43 1 0 6.875615-1.269469-1.681014 44 1 0 8.482334-1.287439-0.927784 45 6 0 7.409696 1.273643-0.704065 46 1 0 7.151098 2.179314-0.146313 47 1 0 8.485430 1.295188-0.908681 48 1 0 6.876359 1.298043-1.657303 49 6 0 7.860941-0.014575 1.429191 50 1 0 8.934675-0.014352 1.214227 51 1 0 7.631590 0.864129 2.038499 52 1 0 7.629088-0.902967 2.023406 53 6 0-7.860942-0.014728-1.429185 54 1 0-7.629015-0.903130-2.023356 55 1 0-8.934676-0.014587-1.214219 56 1 0-7.631667 0.863965-2.038536 SCF Done: E(RB3LYP) = -1639.31382838 A.U. after 1 cycles Convg = 0.9417D-08 -V/T = 2.0141 S 24

0.430031 (Hartree/Particle) Thermal correction to Energy= 0.460471 Thermal correction to Enthalpy= 0.461415 Thermal correction to Gibbs Free Energy= 0.366628 Sum of electronic and zero-point Energies= -1638.883797 Sum of electronic and thermal Energies= -1638.853357 Sum of electronic and thermal Enthalpies= -1638.852413 Sum of electronic and thermal Free Energies= -1638.947201 1.4. HM and LUM contour plots for selected structures 2. Experimental materials and methods. All solvents and reagents used in the synthetic schemes were used as received except where noted. 1 H and 13 C spectra were recorded on a Bruker 400 MHz spectrometer. Chemical shifts were referenced to tetramethylsilane (0.00 ppm). Low and high resolution mass spectra data was acquired at the National University of Singapore Mass Spectrometry Laboratory. Cyclic voltammetry measurements of compounds 10 13 were carried out under nitrogen atmosphere using an AUTLAB model PGSTAT30 workstation with 0.1 M tetra-n-butylammonium hexafluorophosphate as supporting S 25

electrolyte in freshly distilled and degassed CH 2 Cl 2 using platinum foil working electrode, a gold counter electrode and a silver/silver chloride reference electrode. Fc/Fc+ was used as internal reference for all measurements. The scan rate was 50mV s -1. All solutions for cyclic voltammetry were thoroughly purged with N 2 before the CV measurements. UV-Vis data were recorded on a Shimadzu UV-Vis-NIR 3101 PC scanning spectrophotometer. The thin film samples for XRD measurements were deposited on the TS-modified Si 2 /Si substrate by thermal evaporation with LED heating source in a alumina crucible. Prior to deposition, 11 and 12 were purified via sublimation. Thin films (~67 nm of 11 and ~ 65 nm of 12) were evaporated at 120 and 115 C, respectively, under a base pressure of 1.7 10-7 mbar; at substrate temperature of 60 C, and deposition rates of 0.5 Å/s. The thin films morphology was characterized in tapping mode by using multimode Atomic Force Microscopy. The AFM scans were performed both in ambient condition using scan size of 5 m and a scan rate of 1Hz. The crystallinity of 11 and 12 was determined by using XRD patterns and were obtained on an Analytical X PERT PR system using Cu Kα source (λ=1.5418 Å) in air over 2θ range of 2 to 30. 3. Synthetic procedures 2,7-Dihydroxybenzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone (DHNDI) (2): Naphthalene[1,8:4,5]tetracarboxylic acid dianhydride (9) (6.71 g, 25 mmol) and NH 2 H HCl (3.47 g, 50 mmol) were suspended into freshly-distilled, amine-free DMF (50 ml) and n-bu 3 N (12 ml, 9.30 g, 50 mmol) were syringed in over 10 min with vigorous stirring, whereupon the yellow suspension thickened and changed color to offwhite. The mixture was heated with stirring at 140 C for 1 h in an open flask. During that time, the initial off-white precipitate dissolved and then bright yellow, fine-crystalline precipitate of 2 appeared. The mixture was cooled to room temperature, diluted with CH 3 CN (50 ml), filtered and the filter cake washed with CH 3 CN (4 15 ml), followed by copious amounts of diethyl ether. The powder was transferred into a pre-weighed roundbottomed flask and was heated under high vacuum at 100 C for 2 h with frequent S 26

shaking and turning of the solid around to ensure all solvents have been completely removed. The known compound 2 2 (6.63 g, 89 %) was isolated as a bright yellow solid. 1,3,6,8-Tetraoxobenzo[lmn][3,8]phenanthroline-2,7(1H,3H,6H,8H)-diyl di-n-hexanoate (, -Di-n-hexanoylDHNDI) (10) : Compound 2 (0.447 g, 1.5 mmol) and DMAP (0.009 g, 5 mol%, 0.075 mmol) were suspended in dry CHCl 3 (15 ml) and n-hexanoyl chloride (0.47 ml, 0.444 g, 3.3 mmol) and n-bu 3 N (0.79 ml, 0.614 g, 3.3 mmol) were added via syringe in succession. The mixture was stirred in ambient temperature over 18 h, the volatiles were removed in vacuum and the residue was suspended in CH 3 CN (10 ml). The precipitate was filtered, washed with CH 3 CN (3 2 ml) and dried thoroughly with a stream of air. Compound 10 (550 mg, 74 %) was obtained as a white solid. 1 H NMR (CDCl 3 ): 8.83 (s, 4H), 2.76 (t, 4H, J = 7.6 Hz), 1.86 (m, 4H), 1.53-1.37 (m, 8H), 0.98 (t, 3H, J = 7.2 Hz); 13 C NMR (CDCl 3 ): 169.9, 158.3, 132.2, 127.5, 127.0, 31.5, 31.4, 24.8, 22.6, 14.3; HRMS (ESI): m/z 494.1685 (M - ); Calcd for C 26 H 26 N 2 8 : 494.1685. 1,3,6,8-Tetraoxobenzo[lmn][3,8]phenanthroline-2,7(1H,3H,6H,8H)-diyl dipivalate (, -DipivaloylDHNDI) (11) : Following the procedure for 10, from 2 (0.596 g, 2.0 mmol), DMAP (0.012 g, 5 mol%, 0.050 mmol), CHCl 3 (20 ml), pivaloyl chloride (0.62 ml, 0.603 g, 5.0 mmol) and n-bu 3 N (1.20 ml, 0.927 g, 5.0 mmol) compound 11 (722 mg, 77 %) was obtained as a white solid. 1 H NMR (CDCl 3 ): 8.81 (s, 4H), 1.51 (s, 18H); 13 C NMR (CDCl 3 ): 174.4, 158.5, 132.0, 127.6, 127.0, 39.0, 27.5; HRMS (ESI): m/z 466.1373 (M - ); Calcd for C 24 H 22 N 2 8 : 466.1382. S 27

2,7-Bis(n-hexyloxy)benzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone (, - Di-n-hexylDHNDI) (12): Under Ar, 2 (0.596 g, 2.0 mmol) and PPh 3 (1.31 g, 5.0 mmol) were suspended in dry, air-free DMF (5.7 ml). 1-Hexanol (0.63 ml, 0.511 g, 5.0 mmol) and 50 vol% solution of DEAD in toluene (2.30 ml, 0.871 g DEAD, 5.0 mmol) was added drop-wise via syringe over 10 min. Addition of DEAd resulted in dark-brown mixture, which turned gray within 30 min. The misture was stirred for 3 h, the volatiles were removed in vacuo and the residue was suspended in CH 3 CN (10 ml). The precipitate was filtered, washed with CH 3 CN (3 2 ml) and dried thoroughly with a stream of air. Compound 12 (741 mg, 79 %) was obtained as a white solid. 1 H NMR (CDCl 3 ): 8.80 (s, 4H), 4.27 (t, 4H, J = 6.8 Hz), 1.87 (m, 4H), 1.54 (m, 4H), 1.37 (m, 8H), 0.92 (t, 3H, J = 6.4 Hz); 13 C NMR (CDCl 3 ): 160.0, 131.8, 127.7, 126.6, 79.9, 32.0, 28.5, 25.8, 22.9, 14.4; HRMS (ESI): m/z 466.2109 (M - ); Calcd for C 26 H 30 N 2 6 : 466.2109. S 28

4. NMR spectra N N 10 N N 10 S 29

N N 11 N N 11 S 30

N N 12 N N 12 S 31

5. Additional surface characterization of compound 12 Figure 1-SI. XRD intensity graph and AFM height (left inset) and phase (right inset) images of a spin cast film (CHCl 3 ) 12 on TS-modified Si/Si 2 substrate. 6. Solid State UV & TFT Device Characterization Figure 2-SI. UV-Vis spectra of an evaporated film (thickness ~ 40nm) of DHNDI 11 on quartz substrate. The thin film transistor properties of 11 as a channel semiconductor was evaluated using a bottom-gate, top-contact TFTs configuration. Heavily p-doped silicon wafer with a layer of ~200 nm (17.25 nf cm -2 ) Si 2 on the surface was used as the substrate. Sublimed grade of 11 was thermally evaporated at 100-150 C ( thickness ~50-70 nm) on a octyltrichlorosilane (TS-8) pretreated substrate under a base pressure of 8.5 10-7 mbar with substrate temperature maintained at room temperature, and the deposition rates was S 32

controlled at 0.5 /s. A pair of Au electrodes was then thermally evaporated to act as source and drain. The TFT devices were then characterized using a Keithley SCS-4200 probe station under an ambient environment with relative humidity level of 65 % in the dark. Figure 3-SI. The top schematic shows the typical bottom gate top contact device structure used in device evaluation. (Left) utput characteristics and (right) transfer characteristics of the TFT devices measured under ambient which show no obvious transistors signal. Four devices were evaluated all showing similar characteristics as described above. Devices were also measured under nitrogen atmosphere and the same experiment was repeated for compound 12 with similar results. Spin coated devices of 11 and 12 were also prepared and showed similar output and transfer characteristics as described above. 7. References 1. Gaussian 09, Revision A.02, Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao,.; Nakai, H.; Vreven, T.; Montgomery, Jr., J. A.; Peralta, J. E.; gliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, N. J.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev,.; Austin, A. J.; Cammi, R.; Pomelli, C.; chterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, Ö.; Foresman, J. B.; rtiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian, Inc., Wallingford CT, 2009. 2. Zhong, C.-J.; Kwan, W. S. V.; Miller, L. L. Chem. Mater. 1992, 4, 1423-1428. S 33