Supplementary Information. New Journal of Chemistry. A molecular roundabout: triple cycle-arranged hydrogen bonds in light of

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1 Electronic Supplementary Material (ESI) for New Journal of Chemistry. This journal is The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2018 Supplementary Information. New Journal of Chemistry A molecular roundabout: triple cycle-arranged hydrogen bonds in light of experiment and theory Agnieszka Kwocz, a Jarosław Jan Panek, a Aneta Jezierska, a Łukasz Hetmańczyk, b,c Andrzej Pawlukojć, c,d Andrzej Kochel, a Paweł Lipkowski, e and Aleksander Filarowski* a,f a University of Wrocław, Faculty of Chemistry, F. Joliot-Curie str. 14, Wrocław, Poland. b Jagiellonian University, Faculty of Chemistry, Ingardena str. 3, Kraków, Poland. c Frank Laboratory of Neutron Physics, Joint Institute for Neutron Research, Dubna, Russia. d Institute of Nuclear Chemistry and Technology, Dorodna str. 16, Warsaw, Poland. e Theoretical Chemistry Group, Institute of Physical and Theoretical Chemistry, Wrocław University of Technology, Wyb. Wyspiańskiego str. 27, Wrocław, Poland. f Institute of Chemistry St. Petersburg State University Universitetskij pr. 26, St. Petersburg, Russia 1

.. N, O-H and H-N interatomic distances in the three hydrogen bridges of the investigated compounds 1

2 Bridge 1 Bridge 2 Bridge 3 Compound 4 Compound 3 Compound 2 R [Å] Compound 1 t [ps] Fig. S1 Time evolution of the O... N, O-H and H-N interatomic distances in the three hydrogen bridges of the investigated compounds 1 4obtained by gas-phase CPMD calculation. Red: hydroxyl oxygen bridged hydrogen distance, green: acetyl oxygen or imine nitrogen bridged hydrogen distance, blue: donor acceptor distance. 2

S2 Time evolution of interatomic distances in the three hydrogen bridges of the investigated compounds 1 and 2 for 10, 100

3 Bridge 1 Bridge 2 Bridge 3 Compound 2, 300K Compound 2, 100K Compound 2, 10K Compound 1, 300K R [Å] Compound 1, 100K Compound 1, 10K t [ps] Fig. S2 Time evolution of interatomic distances in the three hydrogen bridges of the investigated compounds 1 and 2 for 10, 100 and 300 K (for which the X-ray structure was determined). Red: hydroxyl oxygen proton distance, green: carbonyl oxygen or imine nitrogen proton distance, blue: donor acceptor distance. Results of the solid-state CPMD simulation. 3

4 Compound 1 Compound 2 Compound 3 Compound 4 Fig. S3 Power spectra of atomic velocities results of the CPMD runs for the studied compounds. Intensities (the y axis) are arbitrary and are not related to the IR absorption intensities. The spectra presented only for the bridged protons vibrational modes. 4

5 10K 100K 300K Compound 2 Compound 1 Power spectrum - arbitrary intensity wavenumber [cm -1 ] Fig. S4 Power spectra of the atomic velocity for the investigated compounds 1 and 2 - results of the solid-state CPMD simulation. For 1, total power spectrum (black) and joint contribution of the bridge protons (red) are given. For 2, total power spectrum (black) and individual contributions of the bridge protons are given. 5

6 Fig. S5 Infrared spectra of 1,1,1 -(2,4,6-trihydroxybenzene-1,3,5-triyl)triethanone (1, upper spectra) and its deuteroderivative (1D, lower spectra) in cm -1 (left side) and cm -1 (right side) regions measured as function of temperature - T = 300 K (black line) and 10 K (red line). 6

7 Fig. S6 Infrared spectra of (1E)-1-(3,5-diacetyl-2,4-dihydroxy-6-oxocyclohexa-2,4-dien-1-yl)-Nmethylethaniminium (2, upper spectra) and its deuteroderivative (2, lower spectra) in cm -1 (left side) and cm -1 (right side) regions measured as function of temperature - T = 300 K (black line) and 10 K (red line). 7

8 Fig. S7 Experimental IR (black colour), Raman (red colour) and INS (blue colour) spectra of 1,1,1 - (2,4,6-trihydroxybenzene-1,3,5-triyl)triethanone (1) (A) and (1E)-1-(3,5-diacetyl-2,4-dihydroxy-6- oxocyclohexa-2,4-dien-1-yl)-n-methylethaniminium (2) (B). 8

9 arb. units CPMD (gas) CPMD (solid, 300 K) 5 B compound absorbance DFTP CPMD (solid, 10 K) Acompound [cm-1] [cm-1] Fig. S8 Experimental and calculated DFTP IR spectra, as well as CPMD and CPMD-solid hydrogens vibrational spectra (300 K and 10 K) of 1,1,1 -(2,4,6-trihydroxybenzene-1,3,5-triyl)triethanone (1, panel A) and (1E)-1-(3,5-diacetyl-2,4-dihydroxy-6-oxocyclohexa-2,4-dien-1-yl)-Nmethylethaniminium (2, panel B). 9

10 1 2 Fig. S9 The molecular structure and atom labelling scheme of 1,1,1 -(2,4,6-trihydroxybenzene-1,3,5- triyl)triethanone (1) and (1E)-1-(3,5-diacetyl-2,4-dihydroxy-6-oxocyclohexa-2,4-dien-1-yl)-Nmethylethaniminium (2). Crystal structures were visualized using the DIAMOND program

11 Table S1. Definitions of internal coordinates used in potential energy distribution (PED) analysis for the assignment of the vibrational spectra of compounds 1 and 2. (CH) stretching of the C-H bond (OH) stretching of the O-H bond (OD) stretching of the O-D bond (NH) stretching of the N-H bond (ND) stretching of the N-D bond (C=O) stretching of the C=O bond (CO) stretching of the C-O bond (C alk C alk ) stretching of the C alk -C alk bond (C ar C alk ) stretching of the C ar -C alk bond (C=N) stretching of the C=N bond (CC) - ring stretching (NC) - stretching of the N-C alk bond (CC) - in plane bending of the C=C=C chain in the aromatic ring (CC im N) - in plane bending of the C-C im =N chain (CCH 3 ) in plane bending of the C-CH 3 unit (NCH 3 ) in plane bending of the N-CH 3 unit (CCC im ) - in plane bending of the C=C-C im chain (CCC alk ) in plane bending of the C-C-C alk chain (CC=O) in plane bending of the C-C=O chain (CCO) in plane bending of the C-C-O chain (COH) - in plane bending of the C-O-H chain (COD) - in plane bending of the C-O-D chain (CNH) - in plane bending of the C=N-H chain (CND) - in plane bending of the C-O-D chain (C=O) out of plane bending of the C=O bond (the change in angle between the C=O and C-C bonds) (C=N) out of plane bending of the C=N bond (the change in angle between the C=N and C-C bonds) (COH) out of plane bending of the O-H bond (the change in angle between the O-H and C-O bonds) (COD) out of plane bending of the O-D bond (the change in angle between the O-D and C-O bonds) (CNH) out of plane bending of the N-H bond (the change in angle between the O-H and C-O bonds) (CND) out of plane bending of the N-D bond (the change in angle between the O-D and C-O bonds) (CO) out of plane bending of the C-O bond (the change in angle between the C-O and C=C bonds) (CC alk ) out of plane bending of the C-C alk (the change in angle between the C-C alk bond and plane defined by three carbon atoms in the ring) (CC) torsion angle in the ring (the change in the dihedral angle between two C=C=C planes in the ring) (CC alk ) torsion angle in the ring (the change in the dihedral angle between C=C=C and C=C-C alk planes) (C=N) torsion around the C=N bond (the change in the dihedral angle between C-C=N and C=C-C planes) (CH 3 ) torsion around the C alk -C alk bond (the change in the dihedral angle between C-C-H and C-C-C planes) (NC) torsion around the N-C alk bond (the change in the dihedral angle between C=N-C and C=C-C planes) 11

12 Table S2. Experimental (IR, Raman and IINS) and calculated (B3LYP/6-31+G(d,p)) vibrational frequencies (, cm -1 ) with the assignments (PED, %) for 1,1,1 -(2,4,6-trihydroxybenzene-1,3,5-triyl)triethanone (1) and its OD derivative. Only internal coordinates contributing more than 5% to the normal coordinates are reported. Compound 1 IR Raman IINS OH B3LYP/6-31+G(d,p), PED (%) OD B3LYP/6-31+G(d,p), PED (%) OH OD OH OD OH OD IR R PED (%) IR PED (%) (CH) (CH) (CH) (CH) (CH) (CH) (CH) (CH) (CH) (CH) (CH) (CH) (CH) (CH) (CH) 99` (CH) (CH) (CH) * * (OH) (OH) (OH) sh (COH) 44, (C=O) 8, (CC) (COH) 41, (C=O) 7, (CC) 7, (CCO) b (C=O) 44, (COH) (OD) (OD) (OD) (C=O) 26, (CC) 17, (CCC alk ) (C=O) 30, (CC alk ) 21, (CC) 11, (CCH 3 ) (C=O) 28, (CC) 11, (CCC alk ) (C=O) 29, (CC=O) 13, (CC) 7, (CC alk ) 6, (CCH 3 ) wb (C=O) (COH) 46, (CC) 9, (CO) (CC) 45, (CO) 11, (CCH 3 ) 8, (C=O) (CC) 40, (CO) 9, (CCH 3 ) 8, (C=O) 7, (C=O) (CC) 25, (CO) 19, (COH) 7, (CCC alk ) (CC) 24, (CO) 19, (COH) 7, (CCC alk ) (CH 3 ) 20, (CO) (CCH 3 ) (CH 3 ) (CCH 3 ) (CC) 93, (CC) 6 12

13 (CCH 3 ) (CH 3 ) (CH 3 ) 32, (CC) (CCH 3 ) 36, (CC) (CH 3 ) 47, (CC) (CCH 3 ) (CH 3 ) 53, (CC) (CCH 3 ) (CO) 18, (CC) 10, (CC) 9, (CC) 13, (C=O) (CC) 7, (C=O) (CCH 3 ) 73, (C alk C alk ) (CO) 17, (CC) 13, (CH 3 ) 8, (C=O) (CC) 62, (C alk C alk ) (CCH 3 ) 73, (C alk C alk ) (CC) 57, (C alk C alk ) 8, (CH 3 ) (CCH 3 ) (CH 3 ) 65, (C alk C alk ) (CC) 50, (C ar C alk ) (CC) (C ar C alk ) 24, (CC) 18, (C=O) 5, (COH) (C ar C alk ) 20, (CC) 11, (C=O) (C ar C alk ) 33, (CC) 16, (CO) sh (CC) sh (CO) 23, (CC) 16, (CC=O) 8, (C alk C alk ) 6, (C ar C alk ) 5 (CO) 26, (CC) 10, (CC=O) 7, (C alk C alk ) 7, (C ar C alk ) (C ar C alk ) 31, (COD) 9, (CC=O) 9, (C alk C alk ) (C ar C alk ) 29, (CC=O) 12, (C alk C alk ) (CO) 26, (COD) 10, (CC) 9, (CC=O) 7, (CCC alk ) (COD) 30, (CO) 25, (CCC alk ) 9, (CC) (COD) 48, (CH 3 ) (CC) 15, (CO) 11, (CCC alk ) 15, (CCO) 6, (C alk C alk ) (CC) 10, (CO) 16, (CCC alk ) 10, (CCO) 7, (CC=O) (CC) 21, (CH 3 ) 20, (CC) 15, (C alk C alk ) (CH 3 ) 25, (CC) 8, (CC) (COH) (COD) 43, (CH 3 ) 6, (CC) (COH) (COD) 46, (CC) 6, (CH 3 ) (COH) (CC) 62, (COD) sh (CCH 3 ) 69, (C=O) (CH 3 ) 62, (C=O) (CCH 3 ) 69, (C=O) (CH 3 ) 70, (C=O) (CCH 3 ) 64, (C=O) (CCH 3 ) 32, (C alk C alk ) 12, (CC=O) (CCH 3 ) 47, (C alk C alk ) 12, (C ar C alk ) (CH 3 ) 32, (C alk C alk ) 29, (CC) sh (CCH 3 ) 48, (C alk C alk ) 13, (C ar C alk ) (CC) 21, (CH 3 ) 20, (C alk C alk ) 16 13

14 (C alk C alk ) 25, (C ar C alk ) 21, (CC) 8, (CCO) 7, (CCC alk ) 6 (C alk C alk ) 27, (C ar C alk ) 26, (CC) 8, (CCO) 7, (CCC alk ) (CH 3 ) 23, (C alk C alk ) 27, (CC) (C ar C alk ) 25, (C alk C alk ) 23, (CH 3 ) 8, (CO) 7, (CC alk ) (C ar C alk ) 26, (C alk C alk ) 25, (CH 3 ) 8, (CC alk ) 7, (C=O) (CC alk ) 46, (CH 3 ) 28, (CCC alk ) (CH 3 ) 34, (CO) 21, (CC alk ) 19, (CCC alk ) (CCO) 48, (CCC alk ) (CO) 51, (CH 3 ) 12, (CH 3 ) 9, (CC alk ) 9, (CCC alk ) (COD) 18, (CC=O) (COD) 41, (CC=O) 24, (CH 3 ) (COD) 32, (C=O) 14, (CCC alk ) 12, (CC) 11, (CCO) (CC) 50, (CO) 31, (CC alk ) (C=O) 14, (CO) 28, (CC alk ) 26, (CC=O) (CO) 47, (CC) 29, (CC alk ) (CH 3 ) 50, (CCC alk ) 20, (CCC alk ) 10, (CCO) 12, (CC=O) (CCC 708sh 702sh (CO) 46, (CC) 29, (CC alk ) 16 alk ) 45, (CH 3 ) 30, (CCO) 10, (CC=O) (CC=O) (CCC alk ) 45, (CH 3 ) 30, (CCO) 10, (CC=O) (CC=O) 64, (CC) (CC=O) 65, (CH 3 ) (CC=O) 68, (CC) (CCH 3 ) 41, (CC) 21, (CC) sh (CC) 39, (CC) 28, (CO) (C=O) 46, (CO) 15, (CCH 3 ) 11, (CC alk ) (C=O) 47, (CO) 18, (CCH 3 ) 16, (CC alk ) (C=O) 47, (CO) 17, (CC) 17, (CCH 3 ) (CCO) 38, (CC=O) (C=O) 47, (CCC alk ) 18, (CH 3 ) 15, (CC=O) (C=O) 32, (CH 3 ) 26, (COD) 14, (CCC alk ) (CO) 28, (COD) 14, (CC=O) 13, (CH 3 ) (CC=O) 28, (C=O) 19, (CO) 6, (CH 3 ) (CCO) 48, (CC=O) (CC=O) 22, (COD) 11, (CO) 18, (C=O) (CH (CCC alk ) 27, (CCO) 26, (CC=O) 22 3 ) 20, (CO) 14, (CC=O) 14, (C=O) 9, (OD) (CH (CC=O) 25, (CC) 19, (CCO) 15 3 ) 17, (COD) 17, (CO) 11, (C=O) 8, (CC=O) 8, (OD) (CC=O) 32, (CC) 18, (CCO) (OD) 13, (C ar C alk ) 11, (CC alk ) 9, (CO) 8 14

15 (C ar C alk ) 26, (CC=O) 18, (CC) 6, (OH) (CH 3 ) 22, (CO) 6, (CC=O) 26, (CC alk ) (CH 3 ) 22, (COD) 20, (CC=O) 8, (CO) 6, (C ar C alk ) 6, (CC alk ) (CC) 23, (CC=O) 20, (CCO) 6, (CCC alk ) 6, (C ar C alk ) (CC) 23, (CC=O) 28, (C ar C alk ) 6, (CC=O) 34, (COD) 16 (CCC alk ) (C alk C=O) (CCO) 31, (CC=O) 23, (CH 3 ) 28, (CC alk ) (CC alk ) 54, (CC) 28, (COH) (CCO) 42, (CH 3 ) 28, (CC=O) 13, (CO) (CH (CC alk ) 55, (CC) 28, (COH) 7 3 ) 32, (CC alk ) 19, (CC alk ) 12, (CC=O) 6, (CCO) (CC) 33, (CH 3 ) 28, (CC alk ) (CC alk ) 39, (CC alk ) 38, (CH 3 ) 6, (CC) (CH 3 ) 76, (CCH 3 ) (CC alk ) 56, (CC alk ) 14, (CH 3 ) (CH 3 ) 70, (CCH 3 ) (CC alk ) (CC) 35, (CH 3 ) 27, (CC alk ) (CC=O) 46, (CC alk ) 27, (CO) (CCC alk ) (CCC alk ) (CH 3 ) 35, (CC alk ) 19, (CC=O) 8, (CCO) 14, (CC alk ) (COH) 38, (CC alk ) 33, (CC) (CCO) 26, (CO) 12, (CH 3 ) 11, (CH 3 ) (COH) 38, (CC alk ) 36, (CC) (CC alk ) 24, (CH 3 ) 37, (CO) 14, (CH 3 ) (COH) 40, (CC alk ) 32, (CC alk ) (CC alk ) 14, (CO) 14, (CH 3 ) 33, (CCO) 24, (CCO) (CC alk ) 49, (CC) 29, (CH 3 ) (CH 3 ) 30, (CCO) 23, (CH 3 ) 26, (CC alk ) (CC) 49, (CC alk ) (CH 3 ) 48, (CH 3 ) 17, (CCO) (CC alk ) 37, (CC) 46, (CH 3 ) (CH 3 ) 37, (CH 3 ) 47, (C ar C alk ) 6 * Sub-picks of stretching vibration mode (OH) observed in IR spectra: 2650, 2395, 2190, 1795 cm -1 and (OD): 2700, 2531, , and cm -1. The (OH) bands are sensitive on deuteroreplacement in hydrogen bond. 15

16 Table S3. Experimental and calculated (B3LYP/6-31+G(d,p)) vibrational frequencies (cm -1 ) with the assignments (PED, %) for (1E)-1-(3,5- diacetyl-2,4-dihydroxy-6-oxocyclohexa-2,4-dien-1-yl)-n-methylethaniminium (2) and its OD/ND derivative. Only internal coordinates contributing more than 5% to the normal coordinates are reported. Compound 2 IR Raman IINS DFT H D H D H D IR R OD B3LYP/6-31+G(d,p), PED (%) IR OD B3LYP/6-31+G(d,p), PED (%) (CH) (CH) (CH) (CH) (CH) (CH) (CH) (CH) (CH) (CH) (CH) (CH) (CH) (CH) (CH) (CH) (CH) (CH) (CH) (CH) (CH) (CH) (CH) (CH) (NH) * (OH) (OH) (ND) (93) 1000* (OD) 89, (C=O) (OD) 89, (C=O) (COH) 50, (CCO) (C=N) 31, (CO) 16, (CC alk ) 9, (CC alk C alk ) 8, (CC alk ) sh (COH) 21, (CNH) 19, (C=N) 11, (C=O) 22, (CC alk ) 22, (CС) 16, (C=O) 10 (CC) (CNH) 22, (COH) 28, (C=O) 9, (C=N) 8 (C=O) 24, (CC alk ) 10, (CO) sh 1615sh (CO) 17, (CCC alk ) 10, (C=N) 9, (CO) 16, (CC) 16, (C=N) 12, (C=O) 13, (CC) 6 (C=O) sh (CO) 20, (C=O) 19, (CCC alk ) 7, (CC) (C=O)17, (CO)8, (COH)8, (CC)6, (CC) 25, (CO) 13, (CO) 11, (C=O) (CCC alk )6, (CCC im )5 8, (OD) (NCH 3 ) (CH 3 ) 71, (NCH 3 ) (NCH 3 ) 83, (CH 3 ) (CH 3 ) 88, (NCH 3 ) (CH 3 ) 29, (CC) 10, (CO) (CC) 15, (CH 3 ) (CC) 19, (CO) 10, (CH 3 ) (CH 3 ) 23, (CC) 8, (NCH 3 ) 6, (CO) , (CC) 5 (CH 3 ) (CH 3 ) 81, (NCH 3 ) (CH 3 ) 94 16

17 (CH 3 ) (CH 3 ) (CH 3 ) (CH 3 ) (CH 3 ) 28, (CC) 15, (CO) (CH 3 ) 22, (CC alk ) (CH 3 ) (CH 3 ) (CH 3 ) 57, (N-C) (CH 3 ) (CH 3 ) 39, (C=N) (CH 3 ) 28, (CC alk ) 5, (C=O) sh (CH 3 ) (CH 3 ) (CH 3 ) 77, (C alk C alk ) sh (CH 3 ) 73, (C alk C alk ) (CH 3 ) (CH 3 ) 65, (C alk C alk ) (CC) 23, (CO) 21, (C=O) 15, (OD) (C ar C alk ) 21, (CO) 12, (CH 3 ) 6, (CC) 17, (CO) 13, (CC alk ) 12, alk alk alk (CC=O) 6, (CC) 5 (NCC ) 10, (OD) 9, (C C ) (C ar C alk ) 20, (CC) (CC alk ) 30, (CC) 16, (CC) (CC) 29, (CC=O) 6, (C=O) 6, (CC) 25, (CC alk ) 14, (С=O) 10, (CCC alk ) 5, (C ar C alk ) 5 (CC) (CC) 30, (C ar C alk ) 16, (CC=O) (CC) 21, (С=O) 15, (CC alk ) 8, (CC alk ) 7, (C alk C alk ) (CO) 22, (C ar C alk ) 12, (CC) (CC) 27, (CO) 13, (C alk C alk ) 6, (N-C) 14, (ND) 13, (CO) 9, (CC alk ) (CC=O) 6 8, (CC alk ) 7, (CC alk C alk ) 7, (CO) 20, (OD) 10, (CC alk ) 9, (CC) 8, (С=O) (NCH 3 ) 40, (NC) 8, (CNH) 7, (CO) (OD) 20, (CC) 15, (CO) 6, (CO) 6, 5, (CC im N) 5 (CC alk ) (CCC im )13, (CC)20, (CCO) 7, (NCH 3 ) sh sh (COH) 93, (NCH 3 ) (COH) (OD) (CCC alk ) 7, (C alk C alk ) 6 (NCH 3 ) 15, (CCC alk ) 10, (CO) 9, (CC) (NCH 3 ) 82, (COH) (NCH 3 ) 89, (CH 3 ) (CH 3 ) 19, (OD) 17, (N-C) 11, (CC) (CH 3 ) 20, (OD) 14, (CC) 8, (CC) 9, (C alk C alk ) (OD) 38, (OD) (CH 3 ) 12, (CC) 11, (C alk C alk ) 11, (CC) 14, (CC im N) (NC) 37, (CH 3 ) 11, (C alk C alk ) 7, (CC) (CH 3 ) 71, (C=N) 9, (C=N) (CH 3 ) 78, (C=N) (CH 3 ) 73, (C=O) (CH 3 ) 63, (C=O) (CH 3 ) 73, (C=O) (CH 3 ) 63, (C=O) (CH 3 ) 48, (C alk C alk ) (CNH) 46, (C=N) 27, (CH 3 ) 11,

18 sh (C=N) 8 (CH 3 )51, (C alk C alk )15, (C ar C alk )6, (CC=O) 5, (C=O) 5 (CH 3 ) 21, (NC) 12, (C alk C alk ) 14, (C=N) 6, (C ar C alk ) (COH) (C alk C alk ) 25, (C ar C alk ) 24, (CC) 8, (CCC im ) (C alk C alk )23, (CCO)14, (CCC alk )11, (C ar C alk )9, (CC) (CCO) 48, (CCC alk ) 26, (CCC im ) (CH 3 ) 45, (C alk C alk ) 13, (OD) (CH 3 ) 44, (C alk C alk ) 16, (CC alk ) (ND) 14, (CH 3 ) 14, (C alk C alk ) 20, (CC alk ) 9, (C=N) (N-C) 33, (ND) 28, (ND) 8, (CH 3 ) (C alk C alk ) 43, (CC alk ) 9, (CC) 8, (CO) (C alk C alk ) 26, (CC alk ) 16, (CO) 11, (CC) 6, (CC alk ) (C-O) 28, (C alk C) (CO) 45, (CC alk ) (CC) 37, (C-O) 31, (C (CC) 45, (CO) 31, (CC alk ) 13 alk C) 17, (ND) (COD) 79, (C-O) (COD) 77, (C-O) 8, (CC) (CC) 28, (CO) 49, (CC alk ) (CO) 47, (CC alk ) 18, (CC) (C-O) 44, (CC) 25, (C alk C) (C-O) 50, (CC) 24, (C alk C) 5, (ND) (CC=O) 32, (CC im N) 16, (CC) 8, (С=O) 35, (NC alk ) 9, (CC) 7, (ND) (CNH) (CC=O) 59, (CC) (С=O) 54, (CC) (CC) 30, (CC=O) 11, (CC) 26, (CC) 25, (С=O) 24, (CC) 19, (CO) (CO) 7 7, (CC im N) 34, (CNH) 13, (CC=O) 11, (CC) 8 590sh (C=O) 47, (CC alk ) 10, (CO) 10, (CH 3 ) (C=O) 49, (CH 3 ) 16, (ND) 15, (C alk C) 15, (C-O) (NC alk ) 27, (C alk C alk ) 7, (CC) 7, (С=O) (C=O) 32, (C=N) 18, (CO) 17, (CH 3 ) 7, (CC alk ) (C=O) 43, (C-O) 17, (CH 3 ) 14, (C=N) (C=N) 34, (C=O) 24, (CH 3 ) 8, (CC) (C=N) 46, (CH 3 ) 12, (C=O) 8, (C-O) 7, (CO) (CCO) 35, (CC=O) 16, (CCC alk ) (CO) 29, (С=O) 25, (CC alk ) (CCO) 42, (CC) (CO) 40, (C alk C alk ) 12, (CC) 12, (OD) (CCC alk ) 32, (CC=O) 21, (CCC im ) 8, (С=O) 31, (CC alk ) 22, (CO) 12, (CCO) 14 (CC) (CC) 16, (CC=O) 23, (C ar C alk ) 8,

19 (OH) 7, (CCC im ) (OH) 6 9, (OD) 9, (CC alk ) 6 (CC) 18, (CC=O) 38, (CCO) 17, (С=O) 24, (CC) 12, (ND) 9, (CC alk ) (CC im N) 47, (CCO) 19, (CNH) 6, (С=O) 31, (CO) 23, (OD) 10, (CC) 5 (CC alk ) 9, (CC) sh (OO) and (ON) (CCC im ) 6, (CC) 6, (C ar C alk ) 6 (OD) 6 (CC) 26, (CC=O) 16, (CNH) 6, (CC alk C alk ) 38, (CO) 22, (CC) 11, (CC) 24, (C ar C alk ) 12, (CC) 7, (CC) 24, (CC alk ) 13, (CC) 7, (С=O) (CC=O) 17, (CCO) (CC alk ) 40, (CC) 21, (CN) 11, (COH) 8, (CNH) (CC) 25, (С=O) 17, (ND) 8, (CC alk ) 7, (CC alk ) 6, (CC) (CC=O) 26, (C ar C alk ) 12, (CCC im ) 7, (C alk C) 42, (CC) 21, (C=N) 12, (CC) 6 (COD) 8, (ND) (С=O) 25, (CC alk ) 7, (CC) 6, (ND) 6, (CC ) 6 alk (CC alk ) 58, (CC) 22, (COH) (C alk C) 58, (CC) 22, (COD) (CC im N) 35, (CCC alk ) 26, (CCC im ) (CC alk ) 27, (NC alk ) 22, (C alk C alk ) 13, 13, (CNH) 9, (CC=O) 7 (ND) 9, (С=O) (CH 3 ) 43, (CC) 24, (CC alk ) (C alk C alk ) 45, (CC) 23, (C alk C) (CC) 22, (CH 3 ) 34, (CC alk ) (C alk C alk ) 37, (CC) 21, (C alk C) (CCC ) 72, (CCO) 5 alk (CC ) 78 alk (CH 3 ) 72, (CH 3 ) (C alk C alk ) 75, (CH 3 ) (CC) 21, (CH 3 ) 26, (CC alk ) 26, (C alk C alk ) 24, (C alk C) 26, (CC) 22, (C=N) 6 (C=N) (CNH) 30, (CH 3 ) 23, (NC) 17, (CC) (ND) 29, (N-C) 20, (C=N) 18, (C alk C alk ) 6, (CC) (NC) 32, (CNH) 26, (COH) 10, (N-C) 29, (ND) 28, (CC) 12, (C=N) (C=N) 9, (CC) 12 10, (COD) (CCC im ) 34, (CCC alk ) 14, (CC im N) (CC alk ) 46, (NC alk ) 11, (ND) 9, 11, (CCO) 6 (CNH) 6 (CO) (COH) 36, (CH 3 ) 25, (CC alk ) 13, (C=O) 37, (COD) 36, (CC) 12 (CC) (COH) 39, (CC alk ) 31, (CC) (COD) 39, (C=O) 31, (CC) (CC alk ) 37, (C=N) 22, (CH 3 ) 11, (C=N) 47, (C=O) 11, (C alk C alk ) 11, (CC) 7 (CC) (CC) 28, (CC alk ) 42, (CH 3 ) (C=O) 43, (CC) 28, (C alk C alk ) (CC) 55, (CC alk ) (CC) 55, (C=O) (CC alk ) 33, (CC) 44, (CH 3 ) (CC) 43, (C=N) 33, (C alk C alk ) 12 * Sub-picks of stretching vibration mode (OH): 1924, 1744 and (OD): 2078, These bands are sensitive on deuteronsubstitution in hydrogen bonding. **Assignments made on base of experimental deuteronsubstitution spectrum. 19

20 Table S4. Selected normal modes of compound 1 calculated by DFPT method (frequencies in cm -1 ). (OH) = 2082 (OH) = 2074 (OH) = 2063 (OH) = 1639 (OH) =1664 (OH) =1665 (OH) = 1568 (OH) = 1566 (OH) = 1536 (OH) = 1477 (OH) = 1467 (OH) = 1170 (OH) = 1156 (OH) = 1153 = 492 = 491 = 425 = 403 β = 146 β = 135 β =

(NH) = 2798 (OH) = 2133 (OH) = 1958 (OH) =1656 (OH) =1632 (OH) =1630 (OH) =1617 (NH)

21 Table S5. Selected normal modes of compound 2 calculated by DFTP method (frequencies in cm -1 ). (NH) = 2798 (OH) = 2133 (OH) = 1958 (OH) =1656 (OH) =1632 (OH) =1630 (OH) =1617 (NH) = 1562 (NH) = 1263 (OH) = 1181 (OH) = 1132 (NH) = 1021 (NH) = , 616, 615, , =500, 499, 498, 497 =485 = =454,

22 = =399 =395 = β = 142 β = 140 β = 139 β =

23 Table S6. Crystal data and structure refinement for 1,1,1 -(2,4,6-trihydroxybenzene-1,3,5- triyl)triethanone (1) and (1E)-1-(3,5-diacetyl-2,4-dihydroxy-6-oxocyclohexa-2,4-dien-1-yl)- N-methylethaniminium (2). Identification code 1 2 Empirical formula C 12 H 12 O 6 C 13 H 15 N O 5 Formula weight Temperature 100(2) K 100(2) K Wavelength Å Å Crystal system, space group Monoclinic, P2 1 /c Orthorhombic, Pbca Unit cell dimensions a = 9.298(3) Å b = (4) Å = (4) o c = 7.232(3) Å a = (7) Å b = (3) Å c = (9) Å Volume (6) A (18) Å 3 Z, Calculated density 4, mg/m 3 8, mg/m 3 Absorption coefficient mm mm -1 F(000) Crystal size 0.15 x 0.13 x 0.11 mm 0.25 x 0.10 x 0.08 mm Theta range for data collection 3.19 to o 3.14 to o Limiting indices -11<=h<=11, -20<=k<=19, -8<=l<=8-22<=h<=19, -9<=k<=9, - 21<=l<=25 Reflections collected / unique 11575/2111 [R(int) = ] 11591/2870 [R(int) = ] Absorption correction Analytical Analytical Max. and min. transmission and and Completeness to theta = % 99.6% Refinement method Full-matrix least-squares on F 2 Full-matrix least-squares on F 2 Data / restraints / parameters 2111/0/ /0/176 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R1 = , wr2 = R indices (all data) R1 = , wr2 = R1 = , wr2 = Largest diff. peak and hole and e.a and e. Å -3 23

Diborane Heterolysis: Breaking and Making B-B bonds at Magnesium

Electronic Supplementary Material (ESI) for Dalton Transactions. This journal is The Royal Society of Chemistry 2018 Supplementary Information for Diborane Heterolysis: Breaking and Making B-B bonds at