1. Structures and Internal Dynamics of H 2 S  ICF 3 and H 2 O  ICF 3 Nicholas R. Walker, Susanna L. Stephens, Anthony C. Legon 1 67 th International Symposium on Molecular Spectroscopy, Ohio State University, 2012. Engineering and Physical Sciences Research Council

2. Introduction Perfluoroiodoalkanes are a fundamental building block in crystal engineering that exploits halogen bonding. 1 Key intermediates in synthesis of fluoropolymers such as fluorinated elastomers. Provides an opportunity to quantify differences between halogen bonds to the iodine atoms of ICl and ICF 3. CF 3 I and complexes containing this molecule are excellent targets for study by broadband rotational spectroscopy because of extensive nuclear quadrupole coupling and relatively intense transitions. Our group 2,3 has recently studied H 3 N  ICF 3, (CH 3 ) 3 N  ICF 3, OC  ICF 3, Kr  ICF 3 and characterised these in series of publications. 1. P. Metrangolo, Y. Carcenac, M. Lahtinen, T. Pilati, K. Rissanen, A. Vij and G. Resnati, Science, 323 1461 (2009) 2. S.L. Stephens, N.R. Walker and A.C. Legon, Phys. Chem. Chem. Phys. 13 20736 (2011) 3. S.L. Stephens, N.R. Walker and A.C. Legon, J. Chem. Phys. 135 224309 (2011)

3. Power divider SPST switch Mixer Low noise amplifier Pin diode limiter Adjustable attenuator 300 W Power amplifier AWG (0.5-12 GHz) Oscilloscope (0-12 GHz) 10 MHz reference frequency PDRO (19.00 GHz) 7.0-18.5 GHz 7.0-18.5 GHz 12.2 GHz Low-pass band filter CP-FTMW Spectrometer

4. H 2 S  ICF 3 Spectrum assigned using Hamiltonian of a symmetric top molecule. Exp. Sim. H 2 S  ICF 3 B 0 / MHz557.57473(81) D J / kHz0.12448(26) D JK / kHz2.7250(47)  aa (I) / MHz  2166.55(11) N 243  / kHz 10.2 75000 nozzle pulses. ~ 9 hours of averaging.

5. H 2 O  C 6 H 6 S. Suzuki, P.G. Green, R.E. Bumgarner, S. Dasgupta, W.A. Goddard III and G.A. Blake, Science, 257, 942-945 (1992) H 2 O  CF 4 W. Caminati, A. Maris, A. Dell-Erba and P.G. Favero, Angew. Chem. Int. Ed. 45, 6711 (2006) H 2 O  CF 3 Cl L. Evangelisti, G. Feng, P. Écija, E.J. Cocinero, F. Castaño and W. Caminati, Angew. Chem. Int. Ed. 50, 7807 (2011) H 2 O  CF 3 Cl Internal Dynamics in Complexes of H 2 O and H 2 S

6. H 2 S  ICF 3 HDS  ICF 3 D 2 S  ICF 3 B 0 / MHz 557.57473(81)548.524153(84)539.86533(9) D J / kHz 0.12448(26)0.12350(27)0.11893(27) D JK / kHz 2.7250(47)4.2139(59)6.21827(58)  aa (I) /MHz  2166.55(11)  2167.01(12)  2166.5(25) N 243197208  / kHz 10.27.99.4 H 2 S  ICF 3 rISrIS  r I  S = 3.5521(2) Å  = 93.2(1) 

7. Frequency / MHz 118301184011850118601187011880 11890 * * * * * * * H 2 O  ICF 3 Simulation (symmetric only) Exp. 90000 nozzle pulses. ~ 10 hours of averaging.

8. Frequency / MHz 11830118401185011860118701188011890 Simulation (symmetric only) Simulation (asymmetric only) Exp. H 2 O  ICF 3

9. H 2 16 O  ICF 3 H 2 18 O  ICF 3 m=0 m=  1 (K=1,2) m=0 m=  1 (K=0,1) B 0 / MHz 846.82030(19) 846.72766(41) 812.06102(30)811.99237(34) D J / kHz 0.1431(13) 0.1112(38) 0.1360(20)0.1029(22) D JK / kHz 1.921(16)8.517(68)1.840(24)23.59(24)  aa (I) / MHz  2199.275(84)  2198.92(17)  2198.82(16)  2199.37(23) N 10211410896  / kHz 8.414.413.715.0 HDO  ICF 3 D 2 O  ICF 3 m=0 B 0 / MHz 823.29900(14)801.16374(16) D J / 10 4 kHz 0.1385(9)0.1334(10) D JK / 10 4 kHz 2.071(11)1.937(13)  aa (I) / MHz  2199.208(49)  2199.416(50) N 143172  / kHz 7.410.3 Symmetric top fits Many lines fit. D J,  aa (I) are consistent. D JK is not.

10. Asymmetric top fits H 2 16 O  ICF 3 D 2 16 O  ICF 3 H 2 18 O  ICF 3 K=0,1 K=1 / MHz 846.74496(43)801.16414(20)812.00566(27) (B 0  C 0 ) / MHz 1.95945(58)3.29610(33)1.79942(34)  J / kHz 0.1318(44)0.1336(12)0.1352(18)  JK / kHz  11.36(26) 61.71(12)   aa (I) /MHz  2199.34(19)  2200.32(12)  2199.26(21)  bb (I)  cc (I) / MHz  20.05(48)  20.20(33)  20.43(44) N 6293 66  / kHz 11.78.3 10.5 rIOrIO  Sym. r I  O = 3.041(1) Å  = 33.8(11)  Asym. r I  O = 3.040(3) Å  = 32(3) 

11. CF 3 I  C 2 H 4 1380013900 Frequency / MHz 16300163501640016450 Frequency / MHz 0 10 1,10  11 1,11 10 1,9  11 1,10 13 1,13  12 1,12 13 1,12  12 1,11 J   J = 10  11 J   J = 12  13 80000 nozzle pulses. ~ 9 hours of averaging.

12. Acknowledgements University of Bristol Susanna Stephens Anthony C. Legon Financial Support Engineering and Physical Sciences Research Council Publication S.L. Stephens, N.R. Walker and A.C. Legon, Phys. Chem. Chem. Phys., 13 21093 (2011)