The Nature of Protic Ionic Liquids in the Gas Phase Revisited: Fourier Transform Ion Cyclotron
Resonance Mass Spectrometry Study of 1,1,3,3-Tetramethylguanidinium Chloride
Joana Vitorino,
a,b
João P. Leal,
a,b
Manuel E. Minas da Piedade,*
,a
José N. Canongia Lopes,
c,d
José M.
S. S. Esperança,
c
Luís Paulo N. Rebelo
c
a
Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade de Lisboa,
1649-016 Lisboa, Portugal; E-mail: memp@fc.ul.pt
b
Unidade de Ciências Químicas e Radiofarmacêuticas, Instituto Tecnológico e Nuclear, 2686-953 Sacavém,
Portugal.
c
Instituto de Tecnologia Química e Biológica, Universidade Nova de Lisboa, Av. República, Apartado 127,
2780-901 Oeiras, Portugal; www.itqb.unl.pt.
d
Centro de Química Estrutural, Complexo Interdisciplinar, Instituto Superior Técnico da Universidade
Técnica de Lisboa, 1049-001 Lisboa, Portugal.
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Supporting Information
SpinWorks 2.5: MSG10 - DMSO-d6 (1H)
PPM
8.0 7.6 7.2 6.8 6.4 6.0 5.6 5.2 4.8 4.4 4.0 3.6 3.2 2.8 2.4 2.0 1.6 1.2 0.8
0.4
3 .3 3 2 7 2 .5 2 4 6 2 .5 2 0 2 2 .5 1 5 7 2 .5 1 1 1 2 .5 0 6 7file: C:\Documents and Settings\IMIDAZOLIUM-PC\Desktop\RMN\TMG Cl\DMSO-d6 (1H)\fid expt: <zg30> transmitter freq.: 400.137471 MHz
time domain size: 65536 points
width: 8223.68 Hz = 20.552147 ppm = 0.125483 Hz/pt number of scans: 16
freq. of 0 ppm: 400.135000 MHz processed size: 32768 complex points LB: 0.000 GB: 0.0000
Figure S1.
1
H NMR spectrum of the solvent DMSO-d
6
recorded at ambient temperature. Chemical shifts
SpinWorks 2.5: MSG20 - 1,1,3,3-tetrametilguanidina em DMSO-d6 (1H)
PPM
8.0 7.6 7.2 6.8 6.4 6.0 5.6 5.2 4.8 4.4 4.0 3.6 3.2 2.8 2.4 2.0 1.6 1.2 0.8
0.4
1 2 .0 0 1 .0 2 2 5 .3 6 1 6 3 .3 5 2 3 2 .6 2 2 1 2 .5 1 9 8 2 .5 1 5 5 2 .5 1 1 3file: C:\Documents and Settings\IMIDAZOLIUM-PC\Desktop\RMN\TMG Cl\1,1,3,3-tetrametilguanidina (1H)\fid expt: <zg30> transmitter freq.: 400.137471 MHz
time domain size: 65536 points
width: 8223.68 Hz = 20.552147 ppm = 0.125483 Hz/pt number of scans: 16
freq. of 0 ppm: 400.135000 MHz processed size: 32768 complex points LB: 0.000 GB: 0.0000
Figure S2.
1
H NMR spectrum of tmg recorded at ambient temperature in DMSO-d
6
. Chemical shifts are
SpinWorks 2.5: MSG30 - N,N,N`,N`-tetrametil-N``-1H-guanidinio cloreto em DMSO-d6 (1H)
PPM
8.0 7.6 7.2 6.8 6.4 6.0 5.6 5.2 4.8 4.4 4.0 3.6 3.2 2.8 2.4 2.0 1.6 1.2 0.8
0.4
1 2 .0 0 2 .0 0 3 8 .0 2 5 5 3 .3 5 1 8 2 .9 1 0 5 2 .5 2 0 2 2 .5 1 5 9 2 .5 1 1 6file: C:\Documents and Settings\IMIDAZOLIUM-PC\Desktop\RMN\TMG Cl\N,N,N',N'-tetrametil-N''-1H-guanidinio cloreto (1H)\fid expt: <zg30> transmitter freq.: 400.137471 MHz
time domain size: 65536 points
width: 8223.68 Hz = 20.552147 ppm = 0.125483 Hz/pt number of scans: 16
freq. of 0 ppm: 400.135000 MHz processed size: 32768 complex points LB: 0.000 GB: 0.0000
Figure S3.
1
H NMR spectrum of [Htmg]Cl (sample 1) recorded at ambient temperature in DMSO-d
6
.
SpinWorks 2.5: MSG11 - DMSO-d6 (13C)
PPM
180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0
4 0 .1 2 3 0 3 9 .9 1 4 0 3 9 .7 0 5 2 3 9 .4 9 6 1 3 9 .2 8 7 0 3 9 .0 7 8 4 3 8 .8 6 8 5file: C:\Documents and Settings\IMIDAZOLIUM-PC\Desktop\RMN\TMG Cl\DMSO-d6 (13C)\fid expt: <jmod> transmitter freq.: 100.624087 MHz
time domain size: 65536 points
width: 24038.46 Hz = 238.893710 ppm = 0.366798 Hz/pt number of scans: 1000
freq. of 0 ppm: 100.614077 MHz processed size: 32768 complex points LB: 0.000 GB: 0.0000
Figure S4.
13
C NMR spectrum of the solvent DMSO-d
6
recorded at ambient temperature. Chemical shifts
SpinWorks 2.5: MSG21 - 1,1,3,3-tetrametilguanidina em DMSO-d6 (13C)
PPM
180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0
1 6 6 .1 9 7 4 4 0 .1 2 5 5 3 9 .9 1 7 0 3 9 .7 0 8 1 3 9 .4 9 9 0 3 9 .3 9 2 9 3 9 .2 9 0 3 3 9 .0 8 4 8 3 9 .0 4 9 3 3 8 .8 7 2 8file: C:\Documents and Settings\IMIDAZOLIUM-PC\Desktop\RMN\TMG Cl\1,1,3,3-tetrametilguanidina (13C)\fid expt: <jmod> transmitter freq.: 100.624087 MHz
time domain size: 65536 points
width: 24038.46 Hz = 238.893710 ppm = 0.366798 Hz/pt number of scans: 1000
freq. of 0 ppm: 100.614077 MHz processed size: 32768 complex points LB: 0.000 GB: 0.0000
Figure S5.
13
C NMR spectrum of tmg recorded at ambient temperature in DMSO-d
6
. Chemical shifts are
SpinWorks 2.5: MSG31 - N,N,N`,N`-tetrametil-N``-1H-guanidinio cloreto em DMSO-d6 (13C)
PPM
180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0
1 6 0 .8 9 8 9 4 0 .1 2 4 6 3 9 .9 1 5 9 3 9 .7 0 7 1 3 9 .4 9 8 3 3 9 .4 2 6 8 3 9 .4 1 6 9 3 9 .2 8 9 5 3 9 .0 8 0 7 3 8 .8 7 1 4file: C:\Documents and Settings\IMIDAZOLIUM-PC\Desktop\RMN\TMG Cl\N,N,N',N'-tetrametil-N''-1H-guanidinio cloreto (13C)\fid expt: <jmod> transmitter freq.: 100.624087 MHz
time domain size: 65536 points
width: 24038.46 Hz = 238.893710 ppm = 0.366798 Hz/pt number of scans: 1000
freq. of 0 ppm: 100.614077 MHz processed size: 32768 complex points LB: 0.000 GB: 0.0000
Figure S6.
13
C NMR spectrum of [Htmg]Cl (sample 1) recorded at ambient temperature in DMSO-d
6
.
(a)
Figure S10.
Isothermal thermogravimetry results for a [Htmg]Cl sample 1 maintained at ambient pressure
and 373 K.