ISMS 2018 CHAMPAIGNURBANA ILLINOIS SULFUR HYDROGEN BONDING A

ISMS 2018 – CHAMPAIGN-URBANA, ILLINOIS SULFUR HYDROGEN BONDING: A COMPARISON OF THE DIMERS AND MONOHYDRATES OF THENYL AND FURFURYL MERCAPTANS 1, R. T. Saragi 1, AND 2, J. E. Rubio 2, L. M. Juanes. ALCOHOLS R. Pinacho Enriquez 2, M. Jaraiz 2, A. Lesarri 1 1 Departamento de Química Física y Química Inorgánica, Facultad de Ciencias. 2 Departamento de Electrónica, ETSIT. UNIVERSIDAD DE VALLADOLID (Spain)

Outline ISMS 2018 – CHAMPAIGNURBANA 1. MOLECULAR MODEL: - Intermolecular clusters - Sulfur hydrogen bonding: Furfuryl and Thenyl alcohol/mercaptan 2. EXPERIMENT: - The lab: Chirped-pulsed FT-Microwave Spectroscopy 3. RESULTS: - Furfuryl and Thenyl monohydrated - Dimers: Sulfur HB vs. Oxygen HB (Furfuryl alcohol)2 and (Thenyl alcohol)2

Sulfur Hydrogen Bonding ISMS 2018 – CHAMPAIGNURBANA • Hydrogen bonds (HBs) to sulfur centers are weak interactions of dispersive character, with reduced structural influence compared to conventional first-row HBs like O-H···O, O-H···N or N-H···O • Rotational analysis of hydrogen-bonded clusters allows comparing the different behavior of oxygen and sulfur compounds • Isolated clusters in gas-phase: Molecular models

ISMS 2018 – CHAMPAIGNURBANA Models: Furfuryl and Thenyl • Five membered ring with oxygen/sulfur atom (furfuryl/thenyl) + alcohol/thiol group • Similar ring skeleton with O/S heteroatoms • Low-barrier orientation of the alcohol/thiol group S or O O Furfuryl alcohol/mercaptan S S or O Thenyl alcohol/mercaptan

ISMS 2018 – CHAMPAIGNURBANA Monohydrated dimers • Geometries indicate hydrogen bonding strengh in each cluster • Different alcohol/thiol group orientation • O-H···O vs O-H···S vs S-H···O, etc • The orientation and preferences of the attached water strongly depends on the sulfur position

ISMS 2018 – CHAMPAIGNURBANA (Homo)Dimers • Alcohol homodimers • O-H···O Hydrogen Bond • Other plausible interactions: • Weak Hydrogen Bonds C-H···p (disp/electrost) • Dispersive interactions p···p

ISMS 2018 – CHAMPAIGNURBANA Experiment

ISMS 2018 – CHAMPAIGNURBANA The lab: Chirped-pulsed FTMW Chirped-Pulsed FT-MW spectrometer Facultad de Ciencias, Univ. Valladolid (Spain)

The lab: Chirped-pulsed FTMW ISMS 2018 – CHAMPAIGNURBANA 2 -8 GHz Pre- SS-Amp 20 W Horn Antenna Jet AWG Tek 70002 A Pulse Generator Low-noise 2 -8 GHz, 25 GS/s Amp Switch Oscilloscope DPO 70804 C Valve Driver Gas line Brooks Pate “design” Chirped-Pulsed FT-MW spectrometer Facultad de Ciencias, Univ. Valladolid (Spain)

Microwave spectrum 2 -8 GHz ISMS 2018 – CHAMPAIGNURBANA Furfuryl alcohol (85°C) 8000 MHz 2000 MHz Zoom x 10 (FA)2 Isomer I FA ··· H 2 O monohydrated 4396 MHz (FA)2 Isomer II 4697 MHz

ISMS 2018 – CHAMPAIGNURBANA Microwave spectrum 2 -8 GHz Thenyl alcohol (75°C) 8000 MHz 2000 MHz Zoom x 6 (TA)2 Isomer II (TA)2 Isomer I 2445 MHz TA ··· H 2 O monohydrated 3015 MHz

ISMS 2018 – CHAMPAIGNURBANA Results

Furfuryl – H 2 O A / MHz B / MHz C / MHz DJ / k. Hz DJK / k. Hz DK / k. Hz d 1 / Hz d 2 / Hz |μa|/ D |μb|/ D |μc|/ D s / k. Hz N ISMS 2018 – CHAMPAIGNURBANA Isomer I 3053. 15505(71) 1444. 99459(36) 1036. 46165(14) 0. 3855(39) -0. 277(25) 5. 59(12) -0. 1234(25) -0. 01995(62) 4. 7 44 Theory** 3019. 26 1478. 45 1055. 00 0. 4230 -0. 475 6. 51 -0. 1195 -0. 02769 2. 22 1. 94 0. 27 Isomer II Isomer I Experimental Theory** Experimental Isomer II Isomer I monosubstituted monohydrated isotopologue with H 218 O was used to calculate the effective structure (r 0) A / MHz 2183. 8117(29) 2189. 88 B / MHz 1142. 99515(73) 1140. 09 C / MHz 830. 52727(40) 835. 82 0. 2285(46) DJ / k. Hz 0. 1586 0. 554(49) DJK / k. Hz 0. 618 5. 05(25) DK / k. Hz 2. 35 -0. 0599(31) d 1 / Hz -0. 0376 -0. 0184(18) d 2 / Hz -0. 0120 |μa|/ D 3. 08 |μb|/ D 2. 57 |μc|/ D 0. 50 s / k. Hz 8. 3 N 30 (**) B 3 LYP-GD 3 BJ/def 2_TZVP Experimental 2164. 0642(22) 1160. 1117(62) 828. 46438(29) 0. 1795(44) 0. 409(44) 2. 03(18) -0. 0263(27) [0] 9. 2 29 Theory** 2168. 91 1173. 86 823. 46 0. 21 0. 93 3. 1 -0. 07 -0. 015 2. 8 0. 4 0. 5 M. Juanes, A. Lesarri et al. , Chem. Eur. J. 2018, 24, 6564 – 6571

0+ 0 - A / MHz 2194. 4109(12) 2194. 4803(13) B / MHz 1265. 93393(63) 1265. 93612(25) C / MHz 1103. 18197(37) 1103. 23363(13) 202 101 Tunnelling splitting Relative intensity rate 1: 3, exchange of equivalent pair of hydrogens atoms, agree with the statistical weight 1: 3 associated to the internal rotation of water DJ / k. Hz DJK / k. Hz DK / k. Hz d 1 / Hz d 2 / Hz |μa|/ D |μb|/ D |μc|/ D �s / k. Hz N 0. 7549(63) 1. 954(53) [ 0. ] 0. 0527(48) -0. 0415(51) 9. 6 11. 1 72 Experimental 0+ 0 - A / MHz 1861. 917(15) 1862. 708(35) B / MHz 983. 1121(11) 983. 02830(98) C / MHz 845. 80994(56) 845. 97410(80) DJ / k. Hz 0. 2403(63) DJK / k. Hz 3. 122(17) DK / k. Hz [ 0. ] d 1 / Hz 0. 0228(44) d 2 / Hz [ 0. ] |μa|/ D |μb|/ D |μc|/ D 8. 1 3. 5 s / k. Hz 41 N Theory 2224. 81 1277. 88 1108. 11 0. 5956 1. 946 -1. 07 0. 0874 -0. 0648 2. 57 1. 63 0. 21 Theory 1885. 74 990. 07 844. 35 0. 1716 1. 343 0. 04 0. 0052 0. 001 1. 36 3. 03 1. 07 B 3 LYP-GD 3 BJ/def 2_TZVP ISMS 2018 – CHAMPAIGNURBANA Experimental B 3 LYP-GD 3 BJ/def 2_TZVP 202 101 Tunnelling splitting Thenyl – H 2 O

Thenyl vs. Furfuryl hydrates Experimental ISMS 2018 – CHAMPAIGNURBANA A / MHz B / MHz C / MHz 3053. 16 1444. 99 1036. 46 Experimental A / MHz B / MHz C / MHz (Furfuryl Alcohol)··· H 2 O A / MHz B / MHz C / MHz 02194. 48 1265. 94 1103. 23 (Thenyl Alcohol)··· H 2 O A / MHz B / MHz C / MHz (Furfuryl Mercaptan)··· H 2 O Experimental 0+ 2194. 41 1265. 93 1103. 18 Experimental 2183. 81 1143. 00 830. 53 Experimental A / MHz B / MHz C / MHz 0+ 1861. 92 983. 11 845. 81 01862. 71 983. 03 845. 97 (Thenyl Mercaptan)··· H 2 O 2164. 06 1160. 11) 828. 46

ISMS 2018 – CHAMPAIGNURBANA (Furfuryl Alcohol)2 O-H···Oring Isomer I O-H···O Isomer II

ISMS 2018 – CHAMPAIGNURBANA (Thenyl Alcohol)2 O-H···O Isomer II

(Furfuryl/thenyl alcohol)2 Experimental Theory** d 2 / Hz 1054. 71641(47) 436. 11244(22) 419. 35674(23) 0. 2218(14) -0. 7835(41) 1. 586(10) 0. 03884(46) [ 0. ] |μa|/ D |μb|/ D |μc|/ D 1056. 72 442. 06 427. 87 0. 1872 -0. 6586 1. 4292 -0. 0318 0. 0004 0. 80 2. 58 1. 31 0. 0 A / MHz B / MHz C / MHz DJ / k. Hz ISMS 2018 – CHAMPAIGNURBANA DJK / k. Hz DK / k. Hz d 1 / Hz DEZPE / k. J ΔG / k. J mol-1 s / k. Hz N (TA)2 - Isomer I 824. 07911(75) 382. 68442(25) 348. 11932(24) 0. 1066(11) -0. 1297(46) 0. 272(34) -0. 00658(77) [0]. A / MHz B / MHz C / MHz DJ / k. Hz DJK / k. Hz DK / k. Hz d 1 / Hz d 2 / Hz |μa|/ D |μb|/ D |μc|/ D DEZPE / k. J mol-1 ΔG / k. J mol-1 12. 6 202 s / k. Hz N Experimental Theory** 1096. 59893(71) 1090. 50 414. 49672(44) 416. 33 B / MHz 400. 89791(55) 393. 80 C / MHz DJ / k. Hz 0. 1640(33) 0. 0611 DJK / k. Hz -0. 6516(78) 0. 1895 DK / k. Hz 1. 749(26) 0. 1312 d 1 / Hz 0. 0162(13) -0. 0037 d 2 / Hz -0. 00155(25) -0. 0009 |μa|/ D 0. 55 |μb|/ D 1. 17 |μc|/ D 1. 63 3. 2 DEZPE / k. J mol-1 -1 2. 22 ΔG / k. J mol 13. 1 s / k. Hz 87 N A / MHz (FA)2 - Isomer I Experimental 813. 40950(30) 394. 62968(15) 354. 53842(17) 0. 16796(65) -0. 4039(17) 0. 5515(27) -0. 01353(29) [ 0. ] A / MHz B / MHz C / MHz DJ / k. Hz DJK / k. Hz DK / k. Hz d 1 / Hz d 2 / Hz |μa|/ D |μb|/ D |μc|/ D mol-1 (FA)2 - Isomer II (TA)2 - Isomer II ΔG / k. J mol -1 s / k. Hz N 833. 26 381. 90 347. 94 0. 1149 -0. 2145 0. 3128 -0. 0098 -0. 0001 2. 20 2. 61 0. 42 0. 0 10. 3 138 Experimental DEZPE / k. J Theory** 12. 3 276 Theory** 815. 47 393. 71 356. 51 0. 0445 0. 0336 0. 0302 -0. 0029 0. 0007 0. 76 2. 87 0. 07 2. 12 2. 52 B 3 LYP-GD 3 BJ/def 2_TZVP

ISMS 2018 – CHAMPAIGNURBANA

ISMS 2018 – CHAMPAIGNURBANA

ISMS 2018 – CHAMPAIGNURBANA Conclusions • Isolated clusters in gas-phase provide structural and energetic information on hydrogen bonding • Comparison between oxygen and sulfur compounds illustrate interactions involving sulfur • Chirped-pulse MW spectroscopy is a powerful tool for intermolecular interactions • Benchmark for ab initio and DFT calculations • Role of empirical dispersion-corrected DFT

Team ISMS 2018 – CHAMPAIGNURBANA Lab team Alberto Lesarri Project-head Ph. D Supervisor Chirped-Pulsed FT-MW spectrometer Facultad de Ciencias, Univ. Valladolid (Spain)

ISMS 2018 – CHAMPAIGNURBANA Thank you very much! Acknowledgements • FPI Grant: BES-2016 -077736 • MINECO/FEDER Project CT 2015 -68148 -C 2 -2 -P

2 -8 GHz Pre- SS-Amp 20 W Horn Antenna Jet Low-noise Amp 2 -8 GHz, 25 GS/s AWG Tek 70002 A Oscilloscope DPO 70804 C Switch Pulse Generator Valve Driver Gas line The detection is made of a power limiter (omitted in the drawing), a PIN-diode switch and the low-noise amplifier. Both the AWG and the scope (Tektronix) are 25 MSamples/s, but the bandwidth of the scope is 8 GHz. The chirp is usually 4 microseg. The limiting factor is the solid state power amplifier for excitation, which is 20 W