S 1 SUPPORTING INFORMATION Polarisation Effects on the Solvation Properties of Alcohols Stefan Henkel, Maria Cristina Misuraca, Pavle Troselj, Jonathan Davidson, Christopher A. Hunter* Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, UK Contents BINDING ISOTHERMS EXPERIMENTAL AND PREDICTED ASSOCIATION CONSTANTS SPECIATION OF ALCOHOL AGGREGATES H-BOND PARAMETERS FOR ALCOHOL MONOMERS AND DIMERS OPTIMIZED GEOMETRIES S 2 BINDING ISOTHERMS for formation of 1:1 complexes of phenols 1-5 with phosphine oxide 6 in n-octane at 298 K. Figure S1. Fit of the experimental shifts of the UV-vis signals of 2-methoxyphenol upon titration with tri-n-butyl phosphine oxide. Figure S2. Fit of the experimental shifts of the 1H NMR signals of the methyl protons of 2-methoxyphenol upon titration with tri-n- butyl phosphine oxide. Figure S3. Fit of the experimental shifts of the UV-vis signals of 2,6-dimethoxyphenol upon titration with tri-n-butyl phosphine oxide. Figure S4. Fit of the experimental shifts of the UV-vis signals of phenol upon titration with tri-n-butyl phosphine oxide. Figure S5. Fit of the experimental shifts of the UV-vis signals of 4-methoxyphenol upon titration with tri-n-butyl phosphine oxide. Figure S6. Fit of the experimental shifts of the 1H NMR signals of the aromatic protons of 4-methoxyphenol upon titration with tri- n-butyl phosphine oxide. Figure S7. Fit of the experimental shifts of the UV-vis signals of 2-ethylphenol upon titration with tri-n-butyl phosphine oxide. S 3 EXPERIMENTAL AND PREDICTED ASSOCIATION CONSTANTS of donors 12-14 and acceptors 5-11 the as a function of concentration of 1-octanol (S2) in n-octane (S1) at 298 K. H- bond donors 13 14 15 H - b on d ac ce pt or s 6 7 8 9 10 S 4 H- bond donors 13 14 15 H - b on d ac ce pt or s 11 12 S 5 SPECIATION OF ALCOHOL AGGREGATES for 1-octanol A1 and 3-ethyl-3-pentanol A9 in tetrachloromethane based on literature data. Figure S8. Left: A: Apparent dipole moment of 1-octanol in tetrachloromethane.[1] B: Population of monomeric 1-octanol in tetrachloromethane measured by IR spectroscopy.[2-4] Right: A: Apparent dipole moment of 3-ethyl-3-pentanol in tetrachloromethane.[5] B: Population of monomeric 3-ethyl-3-pentanol in tetrachloromethane measured by IR spectroscopy.[4] Black lines correspond to fits of the experimental data with Kn = 3 M-1, αc = 13 and K4 = 75 M-3 for 1-octanol and Kn = 0.7 M-1, αc = 3.4 and K4 = 0.4 M-3 for 3-ethyl-3-pentanol. The grey lines show the populations of linear aggregates (solid line) and cyclic tetramer (dashed line). References [1] Campbell, C.; Brink, G.; Glasser, L., J. Phys. Chem. 1975, 79, 660. [2] Fletcher, A. N., J. Phys. Chem. 1969, 73, 2217. [3] Brink, G.; Drought, Z.; Glasser, L., S. Afr. J. Chem. 1986, 39, 163-168. [4] Nodland, E., Appl. Spectrosc. 2000, 54, 1339. [5] Kunst, M.; Vanduijn, D.; Bordewijk, P., Ber. Bunsen Phys. Chem. 1976, 80, 839. S 6 H-BOND PARAMETERS FOR ALCOHOL MONOMERS AND DIMERS calculated from the molecular electrostatic potential. Table S1. H-bond parameters for alcohols A1-A10 calculated for the surface site interaction points at the B3LYP/6-31G(d) level of theory. Monomer Dimer α β α β 1-Octanol A1 2.8 5.3 3.5 7.4 1-Decanol A2 2.8 5.3 3.5 7.4 2-Heptanol A3 2.7 5.3 3.3 6.9 5-Nonanol A4 2.7 5.1 3.3 5.8 2,4-Dimethyl- 4-heptanol A5 2.7 4.9 3.2 5.3 Menthol A6 2.7 5.1 3.5 5.9 4-Penty- cyclohexanol A7 2.7 5.3 3.3 6.5 2-Methyl- 2-hexanol A8 2.6 5.3 3.2 6.4 3-Ethyl- 3-pentanol A9 2.7 5.1 3.3 6.7 1,1,1-Trifluoro- 2-octanol A10 3.2 3.5 4.0 5.7 S 7 OPTIMIZED GEOMETRIES of monomer and dimers of alcohols A1-A10 and methanol. Geometry optimizations, frequency calculations and calculations of the electrostatic potential were carried out using the B3LYP function and the 6-31G* basis set as implemented in Gaussian 03. (Gaussian 03, Revision E.01; Frisch, M. J. T., G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, Jr., J. A.; Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian, Inc.: Pittsburgh PA, 2003.) Methanol Monomer C -0.511 0.316 0.000 H -0.154 -0.693 0.000 H -0.154 0.820 -0.874 H -1.581 0.316 0.000 O -0.034 0.990 1.168 H -0.352 1.896 1.167 Dimer H 0.372 2.995 -0.092 O 1.123 2.648 -0.612 H -1.817 3.861 0.944 O -1.316 3.061 0.724 C 2.000 1.971 0.292 H 2.835 1.578 -0.248 H 2.347 2.659 1.035 H 1.473 1.169 0.767 C -2.123 2.242 -0.127 H -2.360 2.782 -1.020 H -1.585 1.352 -0.380 H -3.026 1.980 0.382 Trimer H 0.372 2.995 -0.092 O 1.123 2.648 -0.612 C 2.000 1.971 0.292 H 2.835 1.578 -0.248 H 2.347 2.659 1.035 H 1.473 1.169 0.767 H -1.826 3.874 0.889 O -1.340 3.038 0.744 H -2.745 6.240 1.302 O -2.393 5.642 0.625 C -2.146 2.209 -0.097 H -1.640 1.284 -0.276 H -3.083 2.017 0.383 H -2.317 2.707 -1.029 C -1.256 6.264 0.020 H -0.512 6.448 0.767 H -0.854 5.617 -0.732 H -1.551 7.190 -0.426 Cyclic tetramer C 0.121 2.783 1.138 H -0.764 3.418 1.183 H 0.995 3.436 1.059 H 0.190 2.235 2.083 O -0.002 1.928 0.024 H 0.777 1.322 -0.008 C -2.791 0.123 -1.135 H -3.425 -0.762 -1.181 H -2.250 0.199 -2.084 H -3.445 0.996 -1.046 O -1.928 -0.005 -0.028 H -1.322 0.773 0.005 C 2.788 -0.122 -1.136 H 3.423 0.763 -1.182 H 2.242 -0.192 -2.082 H 3.442 -0.995 -1.056 O 1.932 0.002 -0.024 H 1.326 -0.776 0.008 C -0.125 -2.780 1.140 H 0.760 -3.413 1.197 H -0.997 -3.435 1.057 H -0.203 -2.227 2.081 O 0.006 -1.931 0.022 H -0.772 -1.325 -0.018 S 8 1-Octanol A1 Monomer C -3.764 0.450 0.000 H -3.796 1.104 0.913 H -3.796 1.104 -0.913 C -2.512 -0.409 0.000 C -1.272 0.458 0.000 H -2.521 -1.074 -0.902 H -2.521 -1.074 0.902 H -1.277 1.125 -0.902 C -0.016 -0.387 0.000 H -1.277 1.124 0.903 H -0.012 -1.053 -0.903 H -0.011 -1.053 0.902 C 1.226 0.477 0.000 H 1.221 1.144 -0.903 C 2.482 -0.367 0.000 H 1.221 1.144 0.902 H 2.488 -1.034 -0.903 H 2.488 -1.034 0.902 C 3.727 0.496 0.000 H 3.719 1.162 -0.903 C 4.980 -0.341 0.000 H 3.718 1.163 0.902 H 5.018 -0.995 -0.904 H 5.017 -0.995 0.905 H 5.884 0.314 0.000 O -4.875 -0.433 0.000 H -5.665 0.119 -0.001 Dimer H 0.372741 2.996967 -0.091911 O 1.122719 2.648454 -0.611509 C 1.992181 1.976722 0.284767 C 3.123377 1.342321 -0.516714 H 1.457628 1.194302 0.851784 H 2.416195 2.673288 1.030060 H -1.817467 3.860282 0.944951 O -1.315777 3.060691 0.723950 C -2.125856 2.238958 -0.130491 H -1.442903 1.471132 -0.504812 H -2.473665 2.816095 -1.000691 C -3.306019 1.614610 0.609439 H 2.682285 0.667406 -1.262828 C 4.127960 0.580246 0.355024 H 3.635526 2.134396 -1.079552 H 3.601082 -0.202201 0.921866 H 4.554049 1.262389 1.105982 C 5.268597 -0.061339 -0.445994 H 4.844284 -0.740527 -1.200216 C 6.269353 -0.831805 0.424527 H 5.801224 0.719884 -1.008230 H 5.734908 -1.612726 0.986166 H 6.691811 -0.152321 1.179898 C 7.412074 -1.474556 -0.372026 H 6.991363 -2.153443 -1.128948 C 8.409202 -2.247405 0.500700 H 7.949745 -0.694430 -0.931639 H 7.872130 -3.027995 1.058403 H 8.828746 -1.569122 1.257517 C 9.549216 -2.885045 -0.300107 H 9.164026 -3.594807 -1.042700 H 10.242132 -3.429261 0.351998 H 10.127732 -2.125155 -0.840007 C -4.133949 0.675664 -0.278322 H -3.952939 2.414834 1.001004 H -2.921225 1.069993 1.481479 H -4.499927 1.228086 -1.156382 C -5.324653 0.041525 0.452647 H -3.482852 -0.119601 -0.669488 H -5.978418 0.836813 0.840373 H -4.958626 -0.506694 1.333072 C -6.147343 -0.906284 -0.429605 H -6.511162 -0.357924 -1.311284 C -7.338862 -1.541238 0.298691 H -5.492407 -1.701153 -0.816223 H -7.995835 -0.746855 0.683560 H -6.975961 -2.088157 1.181749 C -8.159680 -2.492240 -0.581962 H -8.521056 -1.946193 -1.465031 C -9.349014 -3.120328 0.151817 H -7.503885 -3.287325 -0.964444 H -10.043190 -2.351428 0.512958 H -9.016693 -3.699634 1.022118 H -9.911922 -3.795868 -0.502384 S 9 1-Decanol A2 Monomer C -3.764 0.450 0.000 H -3.796 1.104 0.913 H -3.796 1.104 -0.913 C -2.512 -0.409 0.000 C -1.272 0.458 0.000 H -2.521 -1.074 -0.902 H -2.521 -1.074 0.902 H -1.277 1.125 -0.902 C -0.016 -0.387 0.000 H -1.277 1.124 0.903 H -0.012 -1.053 -0.903 H -0.011 -1.053 0.902 C 1.226 0.477 0.000 H 1.221 1.144 -0.903 C 2.482 -0.367 0.000 H 1.221 1.144 0.902 H 2.488 -1.034 -0.903 H 2.488 -1.034 0.902 C 3.727 0.496 0.000 H 3.719 1.162 -0.903 C 4.980 -0.341 0.000 H 3.718 1.163 0.902 H 5.018 -0.995 -0.904 H 5.017 -0.995 0.905 O -4.875 -0.433 0.000 H -5.665 0.119 -0.001 C 6.227 0.563 0.000 H 6.220 1.180 0.874 H 6.220 1.180 -0.874 C 7.495 -0.312 0.000 H 7.502 -0.930 -0.873 H 8.361 0.316 0.000 H 7.502 -0.930 0.874 Dimer H 0.372067 3.023060 -0.088831 O 1.122230 2.674763 -0.608316 C 1.990854 2.001517 0.287648 C 3.119731 1.363830 -0.514504 H 1.454905 1.220753 0.855604 H 2.417212 2.697526 1.032128 H -1.821145 3.882311 0.945853 O -1.317317 3.083938 0.725337 C -2.124822 2.259957 -0.129421 H -1.439586 1.494081 -0.503552 H -2.473959 2.836160 -0.999702 C -3.303460 1.632247 0.610073 H 2.676171 0.689569 -1.259743 C 4.123269 0.599668 0.356627 H 3.633318 2.154242 -1.078372 H 3.594797 -0.180542 0.925073 H 4.552587 1.281262 1.106235 C 5.260632 -0.046438 -0.445452 H 4.832854 -0.724536 -1.198692 C 6.259610 -0.820124 0.424255 H 5.795338 0.732509 -1.008878 H 5.722765 -1.598085 0.987666 H 6.686311 -0.141715 1.178155 C 7.398091 -1.468879 -0.373898 H 6.971952 -2.145262 -1.129834 C 8.391766 -2.246458 0.498650 H 7.938133 -0.691224 -0.934397 H 7.850843 -3.024144 1.058471 H 8.816565 -1.570053 1.255412 C 9.532379 -2.896032 -0.295414 H 9.109338 -3.572607 -1.053105 H 10.075809 -2.119137 -0.853995 C -4.127798 0.690193 -0.277774 H -3.953166 2.430584 1.000880 H -2.917465 1.089251 1.482590 H -4.494764 1.240901 -1.156498 C -5.317112 0.052752 0.452574 H -3.473903 -0.103295 -0.667896 H -5.974090 0.846190 0.838668 H -4.950149 -0.493168 1.334050 C -6.135373 -0.899052 -0.429546 H -6.500156 -0.353129 -1.312305 C -7.325407 -1.537443 0.298497 H -5.477116 -1.691981 -0.814443 H -7.985310 -0.744467 0.680860 H -6.960626 -2.080456 1.183040 C -8.140583 -2.493592 -0.581965 H -8.503835 -1.951059 -1.467523 C -9.331814 -3.131241 0.144398 H -7.480502 -3.287087 -0.962898 H -9.993789 -2.338260 0.523614 H -8.969707 -3.672707 1.031197 C 10.523144 -3.674445 0.579611 H 10.944985 -2.998372 1.337112 H 9.980409 -4.451774 1.136377 C 11.661116 -4.318839 -0.218679 H 12.349459 -4.866852 0.435062 H 11.273414 -5.026596 -0.961871 H 12.245183 -3.562461 -0.757522 C -10.145317 -4.089804 -0.734852 H -10.505866 -3.549335 -1.621708 H -9.484732 -4.883769 -1.111493 C -11.334639 -4.719885 -0.002733 H -11.892288 -5.400918 -0.655813 H -11.003001 -5.293681 0.871503 H -12.033441 -3.952361 0.352405 S 10 2-Heptanol A3 Monomer C -3.764 0.450 0.000 H -3.796 1.104 0.913 C -2.512 -0.409 0.000 C -1.272 0.458 0.000 H -2.521 -1.074 -0.902 H -2.521 -1.074 0.902 H -1.277 1.125 -0.902 C -0.016 -0.387 0.000 H -1.277 1.124 0.903 H -0.012 -1.053 -0.903 H -0.011 -1.053 0.902 O -4.875 -0.433 0.000 H -5.665 0.119 -0.001 C 1.248 0.492 0.000 H 1.254 1.109 -0.875 H 1.252 1.112 0.873 C 2.499 -0.406 0.003 H 2.495 -1.026 -0.870 H 3.377 0.205 0.002 H 2.493 -1.022 0.878 C -3.808 1.346 -1.251 H -3.179 2.199 -1.102 H -3.462 0.793 -2.099 H -4.813 1.670 -1.423 Dimer H 0.373 2.997 -0.092 O 1.123 2.648 -0.612 C 1.992 1.977 0.285 C 3.123 1.342 -0.517 H 1.458 1.194 0.852 H -1.817 3.860 0.945 O -1.316 3.061 0.724 C -2.126 2.239 -0.130 H -1.443 1.471 -0.505 C -3.306 1.615 0.609 H 2.682 0.667 -1.263 C 4.128 0.580 0.355 H 3.636 2.134 -1.080 H 3.601 -0.202 0.922 H 4.554 1.262 1.106 C 5.269 -0.061 -0.446 H 4.844 -0.741 -1.200 C 6.269 -0.832 0.425 H 5.801 0.720 -1.008 H 5.735 -1.613 0.986 H 6.692 -0.152 1.180 C -4.134 0.676 -0.278 H -3.953 2.415 1.001 H -2.921 1.070 1.481 H -4.500 1.228 -1.156 C -5.325 0.042 0.453 H -3.483 -0.120 -0.669 H -5.978 0.837 0.840 H -4.959 -0.507 1.333 C -6.147 -0.906 -0.430 H -6.511 -0.358 -1.311 H -5.492 -1.701 -0.816 C -7.343 -1.544 0.302 H -8.002 -0.774 0.646 H -7.869 -2.189 -0.370 H -6.990 -2.111 1.137 C 7.416 -1.477 -0.375 H 8.071 -1.994 0.295 H 7.012 -2.169 -1.084 H 7.963 -0.716 -0.892 C 2.583 2.948 1.324 H 2.950 2.393 2.163 H 3.388 3.497 0.881 H 1.824 3.627 1.650 C -2.613 3.046 -1.348 H -2.827 2.378 -2.156 H -3.499 3.586 -1.087 H -1.850 3.734 -1.647 S 11 5-Nonanol A4 Monomer C -3.764 0.450 0.000 H -3.796 1.104 0.913 H -3.796 1.104 -0.913 C -2.512 -0.409 0.000 C -1.272 0.458 0.000 H -2.521 -1.074 -0.902 H -2.521 -1.074 0.902 H -1.277 1.125 -0.902 C -0.016 -0.387 0.000 H -1.277 1.124 0.903 H -0.012 -1.053 -0.903 C 1.226 0.477 0.000 H 1.221 1.144 -0.903 C 2.482 -0.367 0.000 H 1.221 1.144 0.902 H 2.488 -1.034 -0.903 H 2.488 -1.034 0.902 C 3.727 0.496 0.000 H 3.719 1.162 -0.903 C 4.980 -0.341 0.000 H 3.718 1.163 0.902 H 5.018 -0.995 -0.904 H 5.017 -0.995 0.905 H 5.884 0.314 0.000 O -0.010 -1.236 1.150 H 0.002 -2.155 0.871 C -4.970 -0.508 0.000 H -5.876 0.059 -0.039 H -4.914 -1.151 -0.853 H -4.956 -1.098 0.893 Dimer H 0.309234 2.434278 0.106119 O 1.124640 2.441793 -0.435009 C 2.121692 1.666554 0.226875 C 1.606806 0.241264 0.497179 H 2.369222 2.132354 1.199384 H -1.801004 3.325769 0.615759 O -1.484754 2.412108 0.717416 C -2.280785 1.581095 -0.161512 H -1.833113 0.586208 -0.045588 C -3.733190 1.538468 0.326333 H 0.642204 0.331195 1.018916 C 2.534307 -0.647469 1.337095 H 1.393961 -0.239965 -0.468290 H 2.809764 -0.117636 2.261673 H 3.474460 -0.828221 0.798277 C 1.905176 -1.998959 1.702856 H 0.970562 -1.824659 2.254823 H 1.619641 -2.526262 0.781398 C -3.891612 1.019404 1.760937 H -4.318500 0.909492 -0.357366 H -4.160618 2.551605 0.245937 H -3.486126 -0.001768 1.820053 C -5.345833 1.014531 2.248722 H -3.276414 1.629020 2.434325 H -5.957577 0.405540 1.567628 H -5.752115 2.034687 2.189996 C 3.371058 1.706957 -0.656244 H 4.152077 1.082101 -0.202971 H 3.118256 1.248825 -1.623640 C -2.106629 2.038078 -1.616381 H -2.548695 3.041389 -1.730449 H -1.029302 2.143774 -1.793667 C 3.919177 3.121186 -0.883774 H 3.127526 3.742833 -1.318281 H 4.168428 3.573910 0.088258 C 5.159062 3.151747 -1.786191 H 5.945911 2.519242 -1.349645 H 4.911230 2.699382 -2.757199 C 5.707648 4.564989 -2.008594 H 5.997117 5.031329 -1.058503 H 6.590859 4.556858 -2.658067 H 4.955125 5.211737 -2.476454 C 2.831268 -2.891239 2.535520 H 3.108940 -2.403397 3.478106 H 2.352618 -3.845749 2.783202 H 3.758960 -3.114619 1.994187 C -2.704372 1.094871 -2.670364 H -2.311371 0.079232 -2.512803 H -3.793929 1.024185 -2.547729 C -2.393090 1.535814 -4.107304 H -2.778878 2.553103 -4.264716 H -1.304023 1.600552 -4.236401 C -2.980890 0.597073 -5.165571 H -2.741175 0.938174 -6.179070 H -2.587026 -0.420818 -5.055250 H -4.073428 0.539304 -5.083533 C -5.497424 0.487960 3.679385 H -6.544987 0.499166 4.001275 H -5.134255 -0.543807 3.762536 H -4.923817 1.097433 4.388396 S 12 2,4-Dimethyl-4-heptanol A5 Monomer C -2.512 -0.409 0.000 C -1.272 0.458 0.000 H -2.521 -1.074 0.902 H -1.277 1.125 -0.902 C -0.016 -0.387 0.000 H -1.277 1.124 0.903 H -0.012 -1.053 -0.903 C 1.226 0.477 0.000 H 1.221 1.144 -0.903 C 2.482 -0.367 0.000 H 1.221 1.144 0.902 H 2.488 -1.034 0.902 O -0.010 -1.236 1.150 H 0.002 -2.155 0.871 C -3.782 0.462 0.000 H -3.790 1.080 -0.874 H -4.647 -0.168 0.000 H -3.791 1.080 0.874 C 3.748 0.510 0.000 H 4.615 -0.116 0.000 H 3.753 1.128 -0.874 H 3.753 1.128 0.874 C 2.490 -1.282 -1.239 H 1.953 -2.181 -1.021 H 2.024 -0.777 -2.058 H 3.500 -1.524 -1.497 C -2.524 -1.323 -1.240 H -2.066 -0.815 -2.062 H -1.981 -2.220 -1.027 H -3.535 -1.569 -1.491 Dimer C 2.267690 2.208619 0.532389 H 2.338816 2.640858 1.543342 C 3.501955 2.625373 -0.272650 H 4.402503 2.268674 0.247489 C 3.639874 4.138477 -0.534914 H 3.469029 2.101924 -1.239200 H 2.736499 4.457222 -1.069198 O 1.128704 2.755563 -0.134502 H 0.331810 2.578073 0.404680 C 4.853312 4.410116 -1.436455 H 4.937001 5.476357 -1.679825 H 5.788121 4.108862 -0.944412 H 4.782515 3.856045 -2.380482 C 3.732596 4.957223 0.760971 H 2.827008 4.856244 1.368353 H 4.588398 4.639560 1.372551 H 3.864159 6.023358 0.539406 C -1.834043 4.026894 -1.592254 C -1.988329 2.521517 -1.292806 H -1.116194 4.443167 -0.869543 H -2.732100 2.094145 -1.981644 C -2.399361 2.159866 0.142454 H -1.031390 2.027375 -1.501715 H -3.378995 2.602472 0.370992 C -2.467816 0.646116 0.350889 H -3.168872 0.233845 -0.389451 C -2.879036 0.177315 1.760896 H -1.480255 0.229187 0.108374 H -2.185808 0.639236 2.475628 O -1.443031 2.667863 1.104656 H -1.507954 3.635878 1.105039 C -1.215695 4.223595 -2.984030 H -1.859312 3.796929 -3.764810 H -1.079887 5.287972 -3.209532 H -0.236605 3.736474 -3.045470 C -2.732826 -1.347783 1.870526 H -2.980031 -1.697968 2.879757 H -3.403765 -1.860377 1.168268 H -1.708632 -1.669320 1.646254 C -4.304788 0.610385 2.134600 H -4.413873 1.700405 2.152888 H -5.038847 0.210737 1.421825 H -4.575317 0.239339 3.130154 C -3.157804 4.797776 -1.468567 H -3.900697 4.413072 -2.179566 H -3.596632 4.726426 -0.465773 H -3.012708 5.862561 -1.685628 C 3.226258 -0.095701 1.385656 H 4.175956 0.086688 0.862200 C 2.947739 -1.605341 1.316876 H 2.007549 -1.854478 1.826734 H 2.864186 -1.949675 0.279151 H 3.748472 -2.179459 1.798480 C 3.397181 0.352122 2.846100 H 4.169835 -0.241867 3.348969 H 3.687313 1.405471 2.925286 H 2.461609 0.221409 3.406154 C 2.112842 0.680573 0.653671 H 2.000860 0.282582 -0.364794 H 1.158810 0.482030 1.167561 S 13 Menthol A6 Monomer C -3.323 -1.241 0.000 C -1.808 -1.241 0.000 C -1.256 0.170 0.000 C -1.806 0.975 1.161 C -3.321 0.975 1.160 C -3.874 -0.435 1.159 H -0.137 0.136 0.063 H -1.433 -1.791 -0.902 H -3.696 -0.808 -0.965 H -3.699 -2.295 0.064 H -1.430 2.029 1.099 H -3.696 1.525 2.062 H -3.608 -0.941 2.124 H -4.992 -0.400 1.094 H -1.525 0.676 -0.965 C -1.297 -1.990 1.245 H -1.667 -2.994 1.234 H -0.227 -2.004 1.238 H -1.641 -1.492 2.127 C -3.831 1.726 -0.084 H -3.493 1.224 -0.967 C -3.289 3.167 -0.073 H -2.361 3.203 -0.605 H -3.995 3.818 -0.544 H -3.133 3.482 0.938 C -5.371 1.757 -0.069 H -5.716 1.846 0.940 H -5.716 2.593 -0.640 H -5.750 0.852 -0.497 O -1.331 0.420 2.390 H -0.765 1.058 2.832 Dimer C 4.103936 1.743444 -1.996220 C 2.973847 0.751234 -2.351339 C 2.176599 0.378587 -1.079725 C 1.734242 1.567120 -0.212511 C 2.917794 2.509692 0.143185 C 3.600204 2.941000 -1.174587 H 1.284149 -0.200205 -1.348838 H 3.449246 -0.172763 -2.712755 H 4.883759 1.212732 -1.430908 H 4.585664 2.099780 -2.916849 H 1.296394 1.161392 0.710468 H 2.474887 3.411379 0.598422 H 2.860112 3.496166 -1.761608 H 4.421963 3.638291 -0.978121 H 2.797975 -0.277845 -0.454881 C 2.081083 1.264385 -3.494186 H 2.681359 1.463033 -4.391423 H 1.325423 0.514199 -3.757597 H 1.548285 2.176698 -3.217229 C 3.881028 1.915266 1.212873 H 4.219341 0.925745 0.874276 C 3.179976 1.724305 2.570996 H 2.326613 1.041637 2.517002 H 3.878254 1.316790 3.311771 H 2.813381 2.684912 2.957218 C 5.136487 2.781346 1.417557 H 4.865491 3.814039 1.675510 H 5.745546 2.385651 2.239125 H 5.771061 2.815518 0.526812 O 0.720200 2.283340 -0.921926 H 0.263241 2.869357 -0.285063 C -4.057536 2.254883 1.891188 C -3.085257 1.529659 0.934343 C -2.672596 2.467662 -0.224993 C -2.250047 3.882777 0.188571 C -3.261804 4.570634 1.137454 C -3.527834 3.628184 2.333373 H -1.857363 2.020995 -0.805448 H -3.632237 0.691572 0.479096 H -5.029050 2.380882 1.392705 H -4.245707 1.628358 2.772905 H -2.119179 4.479218 -0.723059 H -2.770509 5.479578 1.528128 H -2.584338 3.495024 2.875045 H -4.220334 4.092810 3.042567 H -3.522802 2.577812 -0.911532 C -1.883224 0.919137 1.675013 H -2.221775 0.189434 2.421223 H -1.222471 0.398573 0.972208 H -1.284129 1.678794 2.184049 C -4.543172 5.066086 0.402186 H -5.007528 4.211915 -0.109655 C -4.221764 6.128391 -0.666149 H -3.582581 5.748213 -1.468695 H -5.144061 6.492246 -1.133427 H -3.717054 6.994619 -0.217602 C -5.585294 5.637787 1.379391 H -5.155886 6.446507 1.985528 H -6.435397 6.054813 0.827440 H -5.979761 4.879822 2.062536 O -0.954436 3.783397 0.832873 H -0.677413 4.681995 1.074289 S 14 4-Pentylcyclohexanol A7 Monomer H 0.372 2.995 -0.092 O 1.123 2.648 -0.612 C 2.000 1.971 0.293 C 2.107 0.512 -0.100 C 3.358 2.644 0.283 H 1.552 2.050 1.318 C 3.092 -0.227 0.783 H 2.437 0.437 -1.169 H 1.099 0.028 -0.024 C 4.342 1.906 1.167 H 3.750 2.675 -0.767 H 3.255 3.702 0.637 C 4.449 0.446 0.776 H 3.195 -1.285 0.428 H 2.698 -0.260 1.833 H 5.351 2.390 1.091 H 4.012 1.982 2.236 H 4.899 0.366 -0.249 C 5.391 -0.282 1.753 H 5.482 -1.308 1.463 H 4.991 -0.225 2.743 C 6.779 0.385 1.720 H 6.775 1.248 2.353 H 7.010 0.679 0.718 C 9.207 0.090 2.304 H 9.220 0.747 3.148 H 9.373 0.655 1.410 C 10.319 -0.965 2.457 H 11.105 -0.758 1.761 H 10.707 -0.932 3.454 H 9.917 -1.937 2.263 C 7.840 -0.613 2.220 H 7.860 -1.431 1.531 H 7.606 -0.977 3.199 Dimer H 0.767409 1.674088 -0.418660 O 1.445803 1.083554 -0.805621 H -0.672729 3.548067 -0.377708 O -0.790585 2.657738 -0.008417 C 2.245893 0.564979 0.249913 C 3.241373 -0.419753 -0.361619 C 2.986168 1.673534 1.011040 H 1.612781 0.014991 0.970905 C 4.197073 -0.999822 0.691890 H 3.812548 0.112458 -1.135475 H 2.692005 -1.220774 -0.871171 C 3.937581 1.096805 2.070475 H 3.550886 2.268335 0.279236 H 2.258156 2.350460 1.479252 C 4.947701 0.097882 1.472322 H 4.906911 -1.676940 0.202193 H 3.627138 -1.613780 1.407058 H 4.473040 1.910575 2.577371 H 3.350366 0.584016 2.848113 H 5.573440 0.650310 0.751619 C -1.882103 2.031315 -0.713813 C -1.666522 2.052175 -2.229460 C -1.992186 0.598613 -0.199683 H -2.810686 2.574174 -0.470683 C -2.782758 1.292497 -2.965542 H -0.692478 1.592433 -2.442791 H -1.619041 3.091398 -2.587631 C -3.106533 -0.164600 -0.931008 H -1.024838 0.106687 -0.365350 H -2.171985 0.610064 0.882078 C -2.924084 -0.157718 -2.461756 H -2.579960 1.309078 -4.042375 H -3.741584 1.815170 -2.821824 H -3.144457 -1.198741 -0.565586 H -4.081608 0.284445 -0.685755 H -1.979784 -0.680310 -2.685266 C 5.873199 -0.467635 2.565888 H 6.288404 0.374026 3.140319 H 5.269088 -1.049061 3.279509 C 7.035715 -1.335636 2.063440 H 6.646748 -2.217450 1.536413 H 7.618295 -0.769255 1.321240 C 7.968129 -1.801197 3.189794 H 7.383907 -2.358529 3.937455 H 8.371078 -0.922507 3.715606 C 9.131050 -2.676202 2.704311 H 8.728312 -3.554359 2.179607 H 9.716122 -2.119490 1.958352 C 10.054549 -3.137849 3.836397 H 10.873901 -3.759643 3.457595 H 10.500017 -2.282010 4.358627 H 9.505031 -3.727981 4.580241 C -4.065689 -0.926793 -3.151839 H -4.159566 -1.910942 -2.669240 H -5.016918 -0.406343 -2.960401 C -3.898605 -1.138457 -4.663383 H -3.884512 -0.169131 -5.180417 H -2.920509 -1.602910 -4.859160 C -5.003456 -2.011405 -5.273541 H -5.010777 -2.990880 -4.772206 H -5.983751 -1.557412 -5.063970 C -4.857721 -2.220068 -6.786321 H -4.858841 -1.242062 -7.288475 H -3.876203 -2.668140 -6.997140 C -5.959679 -3.101150 -7.383699 H -6.951613 -2.662813 -7.217732 H -5.829062 -3.228962 -8.464403 H -5.959992 -4.099156 -6.928140 S 15 2-methyl-2-hexanol A8 Monomer C -3.764 0.450 0.000 C -2.512 -0.409 0.000 C -1.272 0.458 0.000 H -2.521 -1.074 -0.902 H -2.521 -1.074 0.902 H -1.277 1.125 -0.902 C -0.016 -0.387 0.000 H -1.277 1.124 0.903 H -0.012 -1.053 -0.903 H -0.011 -1.053 0.902 O -4.875 -0.433 0.000 H -5.665 0.119 -0.001 C -3.808 1.346 -1.251 H -3.179 2.199 -1.102 H -3.462 0.793 -2.099 H -4.813 1.670 -1.423 C 1.248 0.492 0.000 H 1.230 1.144 0.849 H 2.116 -0.131 0.048 H 1.277 1.075 -0.897 C -3.808 1.346 1.251 H -4.801 1.722 1.387 H -3.523 0.775 2.110 H -3.131 2.166 1.127 Dimer H 0.372 2.995 -0.092 O 1.123 2.648 -0.612 H -1.817 3.861 0.944 O -1.316 3.061 0.724 C 2.000 1.971 0.292 C -2.123 2.242 -0.127 C 3.203 1.405 -0.486 H 2.855 0.717 -1.228 H 3.729 2.206 -0.961 C -2.464 3.019 -1.412 H -2.999 2.380 -2.084 H -3.070 3.866 -1.167 H -1.560 3.351 -1.879 C 2.499 2.961 1.361 H 1.668 3.316 1.934 H 3.193 2.467 2.008 H 2.983 3.787 0.884 C -1.349 0.961 -0.491 H -1.104 0.426 0.403 H -1.956 0.345 -1.121 H -0.449 1.223 -1.008 C -3.424 1.865 0.606 H -3.185 1.349 1.513 H -3.975 2.753 0.835 C 1.242 0.818 0.975 H 0.868 0.146 0.231 H 1.907 0.292 1.628 H 0.425 1.214 1.541 C 4.147 0.676 0.488 H 4.496 1.364 1.229 H 3.619 -0.124 0.965 C 5.347 0.106 -0.290 H 4.998 -0.583 -1.031 H 5.875 0.905 -0.768 C 6.292 -0.623 0.684 H 7.126 -1.019 0.143 H 6.641 0.066 1.424 H 5.764 -1.422 1.161 C -4.275 0.951 -0.295 H -3.768 0.019 -0.438 H -4.425 1.424 -1.243 C -5.639 0.697 0.373 H -5.488 0.248 1.333 H -6.157 1.626 0.491 C -6.475 -0.249 -0.509 H -5.954 -1.176 -0.631 H -7.420 -0.429 -0.043 H -6.630 0.201 -1.468 S 16 3-Ethyl-3-pentanol A9 Monomer C -0.012 -0.336 -0.023 C 0.008 0.947 -0.874 H 0.864 0.935 -1.516 H -0.881 0.997 -1.466 C -1.270 -0.343 0.866 H -1.284 -1.234 1.457 H -1.255 0.512 1.510 C 0.078 2.176 0.052 H 0.509 2.999 -0.479 H -0.908 2.436 0.374 H 0.683 1.946 0.904 C -2.527 -0.295 -0.022 H -3.359 -0.700 0.516 H -2.735 0.719 -0.291 H -2.360 -0.872 -0.908 C 2.502 -0.380 -0.024 H 2.286 -0.873 -0.949 H 2.799 0.629 -0.219 H 3.295 -0.895 0.477 C 1.245 -0.384 0.865 H 1.158 -1.270 1.458 H 1.332 0.468 1.508 O -0.031 -1.478 -0.883 H -0.047 -2.279 -0.353 Dimer C -2.524 -0.052 -0.322 C -2.165 0.167 1.159 H -1.391 -0.515 1.442 H -1.825 1.171 1.299 C -3.603 0.963 -0.745 H -3.853 0.811 -1.773 H -4.477 0.825 -0.142 C -3.411 -0.079 2.031 H -3.107 -0.348 3.021 H -4.001 0.813 2.069 H -3.991 -0.873 1.608 C -3.067 2.394 -0.551 H -3.601 3.064 -1.192 H -3.201 2.690 0.468 H -2.025 2.420 -0.796 C -1.981 -2.496 -0.096 H -1.011 -2.086 -0.290 H -2.075 -2.708 0.948 H -2.103 -3.400 -0.656 C -3.060 -1.482 -0.516 H -3.329 -1.563 -1.548 H -3.917 -1.690 0.093 O -1.357 0.132 -1.128 H -1.581 -0.001 -2.052 C 2.320 0.074 -0.025 C 3.428 -0.088 1.032 H 3.362 0.709 1.742 H 3.308 -1.024 1.535 C 2.383 -1.101 -1.020 H 1.614 -0.988 -1.754 H 3.339 -1.107 -1.502 C 4.805 -0.049 0.343 H 5.548 0.263 1.047 H 5.048 -1.024 -0.024 H 4.775 0.642 -0.473 C 2.182 -2.427 -0.263 H 1.822 -3.173 -0.940 H 3.114 -2.744 0.156 H 1.469 -2.284 0.523 C 2.455 2.573 0.212 H 1.790 2.325 1.013 H 3.431 2.764 0.606 H 2.096 3.447 -0.291 C 2.521 1.399 -0.782 H 1.752 1.439 -1.524 H 3.479 1.465 -1.257 O 1.044 0.083 0.620 H 0.352 0.180 -0.039 S 17 1,1,1-Trifluoro-2-octanol A10 Monomer C -3.764 0.450 0.000 C -2.512 -0.409 0.000 C -1.272 0.458 0.000 H -2.521 -1.074 -0.902 H -1.277 1.125 -0.902 C -0.016 -0.387 0.000 H -1.277 1.124 0.903 H -0.012 -1.053 -0.903 H -0.011 -1.053 0.902 C 1.226 0.477 0.000 H 1.221 1.144 -0.903 C 2.482 -0.367 0.000 H 1.221 1.144 0.902 H 2.488 -1.034 -0.903 H 2.488 -1.034 0.902 C 3.727 0.496 0.000 H 3.719 1.162 -0.903 C 4.980 -0.341 0.000 H 3.718 1.163 0.902 H 5.018 -0.995 -0.904 H 5.017 -0.995 0.905 H 5.884 0.314 0.000 O -2.523 -1.258 1.151 H -2.880 -2.116 0.912 F -4.821 -0.390 0.000 F -3.802 1.236 1.097 F -3.802 1.236 -1.097 Dimer H 0.798794 1.497284 -1.177693 O 1.643826 1.980467 -1.267453 C 1.664179 3.023891 -0.318652 C 3.098249 3.559163 -0.257010 H 1.350122 2.674530 0.676380 H -0.394634 -0.528250 -0.452998 O -0.650351 0.324359 -0.843159 C -1.933564 0.683497 -0.329573 H -2.145660 1.671328 -0.744147 C -3.001553 -0.330720 -0.760923 H 3.732460 2.677192 -0.106593 C 3.390494 4.598099 0.834087 H 3.354423 3.959212 -1.245502 H 3.066115 4.207710 1.809964 H 2.802626 5.506658 0.659879 C 4.878592 4.965591 0.905242 H 5.470784 4.056754 1.088879 C 5.197200 6.006088 1.986226 H 5.204826 5.347188 -0.073602 H 4.874963 5.623040 2.966161 H 4.600654 6.912589 1.804827 C 6.682187 6.384547 2.055259 H 7.279058 5.479037 2.235636 H 7.003071 6.769325 1.076741 C -4.463953 0.109042 -0.589660 H -2.829144 -1.278148 -0.230902 H -2.803967 -0.524905 -1.822155 H -4.697077 0.240884 0.471964 C -5.448287 -0.893334 -1.207262 H -4.603758 1.092636 -1.061008 H -5.293153 -1.882711 -0.751855 H -5.224428 -1.012539 -2.277547 C -6.916130 -0.482025 -1.036868 H -7.138359 -0.364792 0.034110 C -7.906262 -1.478916 -1.652845 H -7.071228 0.508947 -1.488845 H -7.749128 -2.469728 -1.203181 H -7.685768 -1.593002 -2.723733 C 0.641879 4.094139 -0.718355 C -1.803090 0.849371 1.185864 C 6.991575 7.423008 3.138468 H 6.713387 7.052963 4.133105 H 8.058785 7.671739 3.162401 H 6.436516 8.353417 2.965925 C -9.369914 -1.063188 -1.474142 H -9.566053 -0.091042 -1.942965 H -10.051087 -1.793634 -1.925139 H -9.630560 -0.976028 -0.412167 F -0.571790 3.530880 -0.970457 F 0.448143 5.002298 0.267042 F 0.997458 4.769248 -1.827209 F -0.872940 1.769998 1.506847 F -2.959043 1.226161 1.766077 F -1.418487 -0.323317 1.754517