Collision-induced cage folding of partially condensed polyhedral oligomeric
silsesquioxanes (POSS) bearing naked and capped silanols.
Thierry Fouquet,1* Laurence Charles2 and David Ruch1.
1
Public Research Centre Henri Tudor
Department of Advanced Materials and Structures
ZAE Robert Steichen, L-4940 Hautcharage, Luxembourg.
2
Aix-Marseille Université – CNRS
Institut de Chimie Radicalaire ICR, UMR 7273
13397 Marseille, France
SUPPORTING INFORMATION
Content
Page
1. POSS(OH)2, POSS(OH)3
2
1.1. ESI-MS
2
1.2. ESI-MS/MS
3
2. POSS(OSiMe2iBu)2 and POSS(OSiMe2iBu)3 derivatives.
5
2.1. Synthesis
5
2.2 ESI-MS
6
2.3. ESI-MS/MS
7
3. ESI-MS/MS of incompletely capped POSS congeners from POSS(OH) 3
10
3.1. POSS(OH)2(OSiMe2iBu)
10
3.2. POSS(OH)(OSiMe2iBu)2
12
* To whom correspondence should be addressed.
Phone: +352 42 59 91 – 4598
E-mail: thierry.fouquet@tudor.lu
Page 1 of 14
1. POSS(OH)2, POSS(OH)3
1.1. ESI-MS
Figure S1. ESI-MS spectra of a) native POSS(OH)2 and b) native POSS(OH)3, detected as both a protonated
molecule (major signal for POSS(OH)3) and an ammonium adduct (major signal for POSS(OH) 2). Accurate
mass measurements of these four ions are reported in Table S1.
Table S1. Accurate mass measurements of ions detected in the ESI-MS spectrum of POSS(OH)2 (Fig. S1a) and
POSS(OH)3 (Fig. S1b). Accurate mass measurements were performed using two reference ions from a
poly(ethylene glycol) internal standard.
Spectrum
a
b
Elemental
composition
C32H75O13Si8+
C32H78NO13Si8+
C28H67O12Si7+
C28H70NO12Si7+
(m/z)theo
(m/z)exp
891.3356
908.3622
791.3012
808.3278
891.3400
908.3620
791.3030
808.3290
Error
(ppm)
+ 4.9
- 0.2
+ 2.3
+ 1.5
Assignment
[POSS(OH)2 + H]+
[POSS(OH)2+ NH4]+
[POSS(OH)3 + H]+
[POSS(OH)3 + NH4]+
Page 2 of 14 – T. Fouquet, L. Charles, D. Ruch. – Correspondence to : thierry.fouquet@tudor.lu
1.2. ESI-MS/MS
Table S2. Accurate mass measurements of product ions formed upon CID of ammoniated POSS(OH)2 at m/z
908.4 (Fig. 1a1-a3). I.S.: internal standard.
Elemental
composition
C32H78NO13Si8+
C32H75O13Si8+
C32H73O12Si8+
C29H67O12Si8+
C28H63O12Si8+
C25H57O12Si8+
C24H55O12Si8+
C21H49O12Si8+
C20H47O12Si8+
C17H41O12Si8+
C16H39O12Si8+
C14H35O12Si8+
C13H33O12Si8+
C12H31O12Si8+
C10H27O12Si8+
C9H25O12Si8+
C8H23O12Si8+
C6H19O12Si8+
C5H17O12Si8+
C4H15O12Si8+
C2H11O12Si8+
CH9O12Si8+
H7O12Si8+
(m/z)theo
(m/z)exp
908.3622
891.3356
873.3251
831.2781
815.2468
773.1999
759.1842
717.1373
703.1216
661.0747
647.0590
619.0277
605.0121
590.9964
562.9651
548.9495
534.9338
506.9025
492.8869
478.8712
450.8399
436.8243
422.8086
I.S.
891.3368
873.3275
831.2827
815.2406
773.1897
759.1839
717.1360
703.1218
661.0727
647.0592
619.0265
605.0117
590.9968
562.9573
548.9546
534.9340
506.8911
492.8871
478.8700
450.8263
436.8244
422.8099
Error
(ppm)
+ 1.3
+ 2.7
+ 5.5
- 7.6
- 13.2
- 0.4
- 1.8
+ 0.3
- 3.0
+ 0.3
- 1.9
- 0.7
+ 0.7
- 13.9
+ 9.2
+ 0.4
- 22.5
+ 0.4
- 2.5
- 30.2
+ 0.2
+ 3.1
Assignment
[POSS(OH)2 + NH4]+
[POSS(OH)2 + H]+
m/z 891 – H2O
m/z 873 – propene
m/z 873 - butane
m/z 815 - propene
m/z 815 – butene
m/z 773 – butene / m/z 759 – propene
m/z 759 – butene
m/z 717 – butene / m/z 703 – propene
m/z 703 – butene
m/z 661 - propene
m/z 661 – butene / m/z 647 – propene
m/z 647 – butene
m/z 619 – butene / m/z 605 – propene
m/z 605 – butene / m/z 591 – propene
m/z 591 – butene
m/z 563 – butene / m/z 549 – propene
m/z 549 – butene / m/z 535 – propene
m/z 535 – butene
m/z 507 – butene / m/z 493 – propene
m/z 493 – butene / m/z 479 – propene
m/z 479 - butene
Page 3 of 14 – T. Fouquet, L. Charles, D. Ruch. – Correspondence to : thierry.fouquet@tudor.lu
Table S3. Accurate mass measurements of product ions formed upon CID of ammoniated POSS(OH)3 at m/z
808.4 (Fig. 1b1-b3). I.S.: internal standard.
Elemental
composition
C28H70NO12Si7+
C28H67O12Si7+
C28H65O11Si7+
C28H63O10Si7+
C25H57O10Si7+
C24H55O10Si7+
C21H49O10Si7+
C20H47O10Si7+
C18H43O10Si7+
C17H41O10Si7+
C16H39O10Si7+
C16H37O10Si7+
C14H35O10Si7+
C13H33O10Si7+
C13H31O10Si7+
C12H31O10Si7+
C12H29O10Si7+
C10H27O10Si7+
C9H25O10Si7+
C9H23O10Si7+
C8H23O10Si7+
C8H21O10Si7+
C7H21O10Si7+
C6H19O10Si7+
C5H17O10Si7+
C5H15O10Si7+
C4H15O10Si7+
C4H13O10Si7+
C3H13O10Si7+
C2H11O10Si7+
C2H9O10Si7+
CH9O10Si7+
CH7O10Si7+
H7O10Si7+
H5O10Si7+
C2H9O9Si6+
CH7O9Si6+
H5O9Si6+
(m/z)theo
(m/z)exp
808.3278
791.3012
773.2906
755.2801
713.2331
699.2175
657.1705
643.1549
615.1236
601.1079
587.0923
585.0766
559.0610
545.0453
543.0297
531.0297
529.0140
502.9934
488.9827
486.9671
474.9671
472.9514
460.9514
446.9358
432.9201
430.9045
418.9045
416.8888
404.8888
390.8732
388.8575
376.8575
374.8419
362.8419
360.8262
344.8857
330.8700
316.8544
I.S.
791.0313
773.2898
755.2804
713.2341
699.2146
657.1731
643.1520
615.1225
601.1066
587.0933
585.0772
559.0603
545.0464
543.0319
531.0298
529.0150
502.9975
488.9837
486.9651
474.9640
472.9507
460.9515
446.9360
432.9202
430.9029
418.8995
416.8879
404.8887
390.8726
388.8585
376.8574
374.8377
362.8420
360.8231
344.8900
330.8730
316.8555
Error
(ppm)
+ 1.3
- 1.0
+ 0.4
+ 1.4
- 4.1
+ 4.0
- 4.5
- 1.8
- 2.2
+ 1.7
+1.0
- 1.3
+ 2.0
- 4.1
+ 0.2
+ 1.9
+ 8.2
+ 2.0
- 4.1
- 6.5
- 1.5
+ 0.2
+ 0.4
+ 0.2
- 3.7
- 11.9
- 2.2
- 0.2
- 1.5
+ 2.6
- 0.3
- 11.2
+ 0.3
- 8.6
+ 12.5
+ 9.1
+ 3.5
Assignment
[POSS(OH)3 + NH4]+
[POSS(OH)3 + H]+
m/z 791 – H2O
m/z 773 – H2O
m/z 755 – propene
m/z 755 - butene
m/z 713 – butene / m/z 699 – propene
m/z 699 – butene
m/z 657 – propene
m/z 657 – butene / m/z 643 - propene
m/z 643 - butene
m/z 643 - butane
m/z 615 – butene / m/z 601 - propene
m/z 601 – butene / m/z 587 - propene
m/z 601 - butane
m/z 587 - butene
m/z 587 - butane
m/z 559 – butene / m/z 545 – propene
m/z 545 – butene / m/z 531 – propene
m/z 545 – butane
m/z 531 - butene
m/z 531 - butane
m/z 503 – propene
m/z 503 – butene / m/z 489 – propene
m/z 489 – butene / m/z 475 – propene
m/z 489 - butane
m/z 475 - butene
m/z 475 - butane
m/z 461 – butene / m/z 447 – propene
m/z 447 – butene / m/z 433 – propene
m/z 447 – butane
m/z 433 – butene / m/z 419 – propene
m/z 433 - butane
m/z 419 - butene
m/z 419 - butane
m/z 390 – SiOH2
m/z 376 – SiOH2
m/z 360 – SiOH2
Page 4 of 14 – T. Fouquet, L. Charles, D. Ruch. – Correspondence to : thierry.fouquet@tudor.lu
Scheme S1. Dissociation routes accounting for the production
of the smallest product ions at m/z 422 and m/z 363 from
POSS(OH)2 and POSS(OH)3, respectively, through the
consecutive loss of butene and/or propene neutrals.
2. POSS(OSiMe2iBu)2 and POSS(OSiMe2iBu)3 derivatives.
2.1. Synthesis
Using a Shlenk flask preliminary dried and kept under inert atmosphere, 0.100 g of a) commercial
1,3,5,7,9,11-Octaisobutyltetracyclo[7.3.3.15,11]octasiloxane-endo-3,7-diol – further named POSS(OH)2
(0.112 mmol) or b) 1,3,5,7,9,11,14-Heptaisobutyltri-cyclo[7.3.3.15,11]heptasiloxane-endo-3,7,14-triol)
(POSS(OH)3, 0.126 mmol) were reacted with, respectively, 0.051 g (0.337 mmol) or 0.076 g (0.505
mmol) of i-butyldimethylchlorosilane, in the presence of 0.034 g (0.337 mmol) or 0.051 g (0.505
mmol) of triethylamine (TEA) in pentane at room temperature. The synthesis route is depicted in
Scheme S2. Aliquots were collected after 1h, 3h and 6h of reaction. To remove ammonium salt and
residual amine potentially deleterious for the ESI analysis, the mixture was dissolved in an excess of
n-pentane and washed with deionized water several times. Pentane was finally evaporated with a
rotary evaporator under vacuum. Samples were dissolved in methanolic solutions of ammonium
acetate (3 mM) and electrosprayed for MS and MS/MS analyses.
iBu
a)
iBu
O iBu
Si
O
iBu
iBu
O
Si
O O
Si
O
Si
O
Si
OH
iBu Si Cl
iBu
OH
O
Triethylamine
O iBu
Si
O
Si
O
Si O
Si
iBu
O
iBu
Si
Si
O
O
iBu
Si
iBu
O iBu
Si
O
OH
O
O
Si
Si O
Si
iBu
iBu Si Cl
OH
Si
O
O
iBu
iBu
Triethylamine
O
Si iBu
Si
O
iBu
iBu
Si
O
Si
O
Si
O
iBu
O iBu
Si
O
O Si iBu
O
O
Si
Si O
Si
iBu
Si iBu
iBu
O
Si iBu
O
iBu
OH
O
iBu
b)
iBu
O
Si
O
iBu
iBu
Si
Si O
Si
O
iBu
iBu
iBu
O
Si
O O
Si
O
iBu
O
iBu
Scheme S2. Synthesis route for the production of a) POSS(OSiMe2iBu)2 and b) POSS(OSiMe2iBu)3.
2.2 ESI-MS
Page 5 of 14 – T. Fouquet, L. Charles, D. Ruch. – Correspondence to : thierry.fouquet@tudor.lu
Figure S2. ESI mass spectra of POSS(OH)2 + isobutyldimethyl-chlorosilane reacting mixture after a1) 3h and
a2) 6h of reaction at room temperature, and of POSS(OH)3 + isobutyldimethylchlorosilane reaction mixture after
b1) 1h and b2) 6h of reaction at room temperature. Structures of the reaction products are depicted as insets with
their associated m/z value as ammonium adducts. Mass measurements are listed in Table S4.
Table S4. Accurate mass measurements of ions detected in the ESI mass spectra of POSS(OH)2 and derivatives
(Fig. S2a), and of POSS(OH)3 and derivatives (Fig. S2b). Accurate mass measurements were performed using
two reference ions from a poly(ethylene glycol) internal standard.
Spectrum
a1
a2
b1
b2
Elemental
composition
C38H89O13Si9+
C38H92NO13Si9+
C38H92NO13Si9+
C44H106NO13Si10+
C34H81O12Si8+
C34H84NO12Si8+
C40H98NO12Si9+
C40H98NO12Si9+
C46H112NO12Si10+
(m/z)theo
(m/z)exp
1005.4221
1022.4487
1022.4487
1136.5352
905.3877
922.4142
1036.5007
1036.5007
1150.5872
1005.4205
1022.4465
1022.4475
1136.5345
905.3893
922.4150
1036.5060
1036.5020
1150.5876
Error
(ppm)
- 1.6
- 2.2
- 1.2
- 0.6
+ 1.8
+ 0.9
+ 5.1
+ 1.3
+ 0.3
Assignment
[POSS(OH)( OSiMe2iBu) + H]+
[POSS(OH)( OSiMe2iBu) + NH4]+
[POSS(OH)( OSiMe2iBu) + NH4]+
[POSS(OSiMe2iBu)2 + NH4]+
[POSS((OH)2(OSiMe2iBu) + H]+
[POSS((OH)2(OSiMe2iBu) + NH4]+
[POSS(OH)(OSiMe2iBu)2+ NH4]+
[POSS(OH)(OSiMe2iBu)2 + NH4]+
[POSS(OSiMe2iBu)3 + NH4]+
Page 6 of 14 – T. Fouquet, L. Charles, D. Ruch. – Correspondence to : thierry.fouquet@tudor.lu
2.3. ESI-MS/MS
Detailed description of mechanisms depicted in Scheme 1 (reproduced below for sake of clarity)
Proposed mechanisms for the production of small linear ions via expulsion of fully condensed neutral POSS
from a) m/z 1103 ([POSS(OSiMe2iBu)2+NH4]+ – NH3 – CH4) to produce the m/z 231 product ion and b) m/z
1117 ([POSS(OSiMe2iBu)3+NH4]+ – NH3 – CH4) to produce the m/z 347 product ion.
Scheme 1a – After a concerted release of ammonia and methane from [POSS(OSiMe2iBu)2+NH4]+
(m/z 1136), the main m/z 1103 product ion has its positive charge located on a silicon atom of a
pendant group. A first methylide transfer from the second intact OSi(iBuMe 2) group to the
neighboring silicon vertex in a concerted reaction with a silicon-oxygen bond relocation would lead to
a OSi(iBuMe)OSi(iBuMe)+ pendant moiety with the positive charge still being located on the last
silicon atom. Upon a second methylide transfer onto the charged Si of the pendant group, a new Si-O
bond would form, allowing a fully condensed cage to be expulsed as a neutral and the m/z 231 product
ion to be generated. Apart from the additional iBu group, this large neutral can be seen as the neutral
equivalent of the fully condensed m/z 815 product ion formed during MS/MS of ammoniated
POSS(OH)2 whose consecutive fragmentation was found to account for all lower mass product ions
(Fig. 1a2).
Scheme 1b – For the case of POSS(OSiMe2iBu)3, a similar methylide transfer/Si-O bond relocation
process repeated three times from the m/z 1117 product ion would explain the production of the m/z
347 ion, with the release of a fully condensed neutral, “structurally equivalent” to the fully condensed
main dissociating species at m/z 755 generated during CID of ammoniated POSS(OH)3 (Fig. 1b2).
Page 7 of 14 – T. Fouquet, L. Charles, D. Ruch. – Correspondence to : thierry.fouquet@tudor.lu
Table S5. Accurate mass measurements of product ions formed upon CID of ammoniated POSS(OSiMe2iBu)2 at
m/z 1136 (Figs. 2a1 and a2). I.S.: internal standard.
Elemental
composition
C44H106NO13Si10+
C44H103O13Si10+
C43H99O13Si10+
C40H93O13Si10+
C39H91O13Si10+
C38H87O12Si9+
(m/z)theo
(m/z)exp
Error
(ppm)
1136.5352
1119.5086
1103.4773
1061.4304
1047.4147
987.4116
I.S.
1119.5339
1103.4802
1061.4231
1047.4130
987.4113
+ 22.6
+ 2.6
- 6.9
- 1.6
- 0.3
[POSS(OSiMe2iBu)2 + NH4]+
m/z 1136 – NH3
m/z 1119 – CH4
m/z 1103 – propene
m/z 1103 – butene
m/z 1061 – C2H6SiO
C36H81O13Si9+
973.3595
973.3601
+ 0.6
m/z 1103 –
iBu Si
C33H75O13Si9+
931.3126
931.3139
+ 1.4
m/z 1103 –
iBu Si iBu
C30H69O13Si9+
889.2656
889.2653
- 0.3
m/z 1103 –
C28H63O10Si7+
755.2801
755.2776
- 3.3
m/z 1103 –
C25H57O10Si7+
713.2331
713.2287
- 6.2
m/z 1103 –
iBu Si iBu
iBu
iBu
Si
O
O
Si
Si iBu
iBu O
iBu
Si
O
O
Si
Si iBu
iBu O iBu
C11H27OSi2+
231.1595
231.1613
+ 7.8
iBu
+
iBu Si O Si
C10H25OSi2+
217.1438
217.1442
+ 1.8
C12H27Si+
199.1877
199.1860
- 8.5
C7H19OSi2+
175.0969
175.0972
+ 1.7
C6H17OSi2+
161.0812
161.0817
+ 3.1
C9H21Si+
157.1407
157.1412
+ 3.2
C8H19Si+
143.1251
143.1265
+ 9.8
C3H11OSi2+
119.0343
119.0343
+ 0.0
C6H15Si+
115.0938
115.0949
+ 9.6
iBu Si
C5H13Si+
101.0781
101.0787
+ 5.9
C4H11Si+
87.0625
87.0630
+ 5.7
iBu Si
H
H
+
iBu Si
H
C3H9Si+
73.0468
73.0483
+ 20.5
Si
C2H7Si+
59.0312
59. 0320
+ 13.6
H
+
Si
Assignment
iBu
+
iBu Si O Si
H
iBu
+
iBu Si
iBu
+
iBu Si O Si
H
H
+
iBu Si O Si
H
+
iBu Si
iBu
H
+
iBu Si
iBu
H
+
Si O Si
H
+
+
+
Page 8 of 14 – T. Fouquet, L. Charles, D. Ruch. – Correspondence to : thierry.fouquet@tudor.lu
Table S6. Accurate mass measurements of product ions formed upon CID of ammoniated POSS(OSiMe2iBu)3 at m/z 1150.6 (Figs. 3b1 and b2). I.S.: internal standard.
Elemental
composition
C46H112NO12Si10+
C45H105O12Si10+
(m/z)theo
(m/z)exp
1150.5872
1117.5293
I.S.
1117.5280
Error
(ppm)
- 1.2
Assignment
Elemental
composition
(m/z)theo
(m/z)exp
Error
(ppm)
[POSS(OSiMe2iBu)3 + NH4]+
m/z 1150 – NH3 – CH4
C11H27OSi2+
231.1595
231.1650
+ 23.8
C38H87O12Si9+
987.4116
987.4115
- 0.1
m/z 1117 –
iBu Si
C10H25OSi2+
217.1438
217.1497
+ 27.2
C35H81O12Si9+
945.3646
945.3661
+ 1.6
m/z 1117 –
iBu Si iBu
C34H79O12Si9+
199.1877
199.1944
+ 33.6
931.3491
+ 0.1
m/z 987 – butene
C12H27Si+
931.3490
C32H75O12Si9+
903.3177
903.3189
+ 1.3
m/z 1117 –
C4H15O2Si3+
179.0374
179.0400
+ 14.5
C31H73O12Si9+
889.3020
889.3052
+ 3.6
C7H19OSi2+
175.0969
175.0980
+ 6.3
C33H75O11Si8+
C30H69O11Si8+
C29H67O11Si8+
871.3458
829.2989
815.2832
871.3418
829.3017
815.2785
- 4.6
+ 3.4
- 5.8
C6H17OSi2+
161.0812
161.0860
+ 29.8
C9H21Si+
157.1407
157.1451
+ 28.0
C8H19Si+
143.1251
143.1289
+ 26.6
C3H11OSi2+
119.0343
119.0370
+ 22.7
C6H15Si+
115.0938
115.0967
+ 25.2
C2H9OSi2+
105.0186
105.0205
+ 18.1
C5H13Si+
101.0781
101.0812
+ 30.7
iBu Si
H
H
+
Si
C3H9Si+
73.0468
73.0501
+ 45.2
Si
+
C2H7Si+
59.0312
59.0350
+ 64.4
H
+
Si
iBu Si iBu
iBu
m/z 945 – butene /
m/z 931 – propene
m/z 945 – C2H6OSi
m/z 871 – propene
m/z 871 – butene
iBu
C30H69O9Si7+
769.3321
769.3342
+ 2.7
m/z 1117 –
O
Si
727.2852
727.2863
+ 1.5
m/z 1117 –
C25H57O8Si6+
653.2664
653.2657
-1.1
m/z 727 – C2H6OSi
C16H39O2Si3
347.2252
347.2302
+ 14.4
C15H37O2Si3+
333.2096
333.2151
+ 16.5
C12H31O2Si3+
291.1626
291.1675
+ 16.8
C8H23O2Si3+
235.1000
235.1053
+ 22.5
O
Si iBu
iBu O
iBu
Si
O
O
Si
Si iBu
iBu O iBu
C27H63O9Si7+
iBu iBu
+
iBu Si O Si O Si
iBu
iBu Si O Si O
H
iBu
iBu Si O Si O
Si
iBu
+
Si
iBu Si O Si O Si
H
H
Page 9 of 14 – T. Fouquet, L. Charles, D. Ruch. – Correspondence to : thierry.fouquet@tudor.lu
Assignment
iBu
+
iBu Si O Si
iBu
+
iBu Si O Si
H
iBu
+
iBu Si
iBu
iBu Si O Si O Si
H
H
+
iBu Si O Si
H
H
+
iBu Si O Si
H
+
iBu Si
iBu
H
+
iBu Si
iBu
H
+
Si O Si
H
iBu Si
+
H
+
Si O Si
H
H
+
+
+
3. ESI-MS/MS of incompletely capped POSS congeners from POSS(OH)3
3.1. POSS(OH)2(OSiMe2iBu)
iBu
Si
a.
iBu
O
iBu
Si
Si
O
OH
Si
O
iBu
O iBu
Si
O
OH
O
O
Si
Si O
Si
iBu
+
NH4
O
iBu
O
iBu
m/z 922.4
0.44 eV
b.
m/z 922.4
1.03 eV
c.
m/z 922.4
1.33 eV
Page 10 of 14 – T. Fouquet, L. Charles, D. Ruch. – Correspondence to : thierry.fouquet@tudor.lu
d.
m/z 922.4
1.62 eV
e.
m/z 922.4
1.92 eV
f.
m/z 922.4
2.36 eV
Figure S3. ESI-MS/MS spectra of the ammoniated POSS(OH)2(OSiMe2iBu) at m/z 922, using a center-of-mass
collision energy of a) 0.44 eV, b) 1.03 eV, c) 1.33 eV, d) 1.62 eV, e) 1.92 eV and f) 2.36 eV.
Page 11 of 14 – T. Fouquet, L. Charles, D. Ruch. – Correspondence to : thierry.fouquet@tudor.lu
Table S7. Accurate mass measurements of product ions formed
POSS(OH)2(OSiMe2iBu) at m/z 922.4 (Fig. S3). I.S.: internal standard.
Elemental
composition
C34H84NO12Si8+
C34H81O12Si8+
C32H73O12Si8+
C33H75O11Si8+
C29H67O12Si8+
C30H69O11Si8+
C29H67O11Si8+
C26H61O11Si8+
C25H59O11Si8+
C28H63O10Si7+
C22H53O11Si8+
C21H51O11Si8+
C24H55O10Si7+
C18H45O11Si8+
C17H43O11Si8+
C20H47O10Si7+
C14H37O11Si8+
C13H35O11Si8+
C16H39O10Si7+
C10H29O11Si8+
C9H27O11Si8+
C6H21O11Si8+
C5H19O11Si8+
C2H13O11Si8+
CH11O11Si8+
C2H11O10Si7+
CH9O10Si7+
H7O10Si7+
(m/z)theo
(m/z)exp
922.4142
905.3877
873.3251
871.3458
831.2781
829.2989
815.2832
773.2363
759.2206
755.2801
717.1737
703.1580
699.2175
661.1111
647.0954
643.1549
605.0485
591.0328
587.0923
548.9859
534.9702
492.9233
478.9076
436.8607
422.8450
390.8732
376.8575
362.8419
I.S.
905.3910
873.3269
871.3486
831.2809
829.3021
815.2835
773.2392
759.2184
755.2816
717.1679
703.1573
699.2220
661.1060
647.0933
643.1620
605.0432
591.0291
587.0929
548.9800
534.9703
492.9075
478.9042
436.8463
422.8479
390.8719
376.8551
362.8349
Error
(ppm)
+ 3.6
+ 2.1
+ 3.2
+ 3.4
+ 3.9
+ 0.4
+ 3.8
- 2.9
+ 2.0
- 8.1
- 1.0
+ 6.4
- 7.7
- 3.2
+ 11.0
- 8.8
- 6.3
+ 1.0
- 10.7
+ 0.2
- 32.1
- 7.1
-33.0
+ 6.9
- 3.3
- 6.4
- 19.3
upon
CID
of
ammoniated
Assignment
[POSS(OH)2(OSiMe2iBu) + NH4]+
m/z 922 – NH3
m/z 905 – 2*CH4
m/z 905 – CH4 – H2O
m/z 873 – propene
m/z 871 – propene
m/z 871 – butene
m/z 815 – propene
m/z 815 – butene
m/z 829 – SiOC2H6
m/z 773 – butene / m/z 759 – propene
m/z 759 – butene
m/z 755 – butene
m/z 717 – butene / m/z 703 – propene
m/z 703 – butene
m/z 699 – butene
m/z 661 – butene / m/z 647 – propene
m/z 647 – butene
m/z 643 – butene
m/z 605 – butene / m/z 591 – propene
m/z 591 – butene
m/z 549 – butene / m/z 535 – propene
m/z 535 – butene
m/z 493 – butene / m/z 479 – propene
m/z 479 – butene
m/z 450 – SiOCH4
m/z 436 – SiOCH4
m/z 422 – SiOCH4
3.2. POSS(OH)(OSiMe2iBu)2
a.
iBu
Si
iBu
O
iBu
Si
O
Si
O
iBu
O
O
O
Si iBu
Si
Si O
Si
iBu
OH
Si
O
O iBu
Si
O
m/z 1036.5
+
NH4
iBu
O
iBu
0.54 eV
Page 12 of 14 – T. Fouquet, L. Charles, D. Ruch. – Correspondence to : thierry.fouquet@tudor.lu
b.
m/z 1036.5
0.79 eV
c.
m/z 1036.5
1.05 eV
d.
m/z 1036.5
1.58 eV
Figure S4. ESI-MS/MS spectra of the ammoniated POSS(OH)(OSiMe2iBu)2 at m/z 1036, using a center-of-mass
collision energy of a) 0.53 eV, b) 0.79 eV, c) 1.05 eV and d) 1.58 eV.
Page 13 of 14 – T. Fouquet, L. Charles, D. Ruch. – Correspondence to : thierry.fouquet@tudor.lu
Table S8. Accurate mass measurements of product ions formed
POSS(OH)(OSiMe2iBu)2 at m/z 1036.5 (Fig. S4). I.S.: internal standard.
Elemental
composition
C40H98NO12Si9+
C40H95O12Si9+
C38H87O12Si9+
C35H81O12Si9+
C34H79O12Si9+
C31H73O12Si9+
C30H71O12Si9+
C33H75O11Si8+
C30H69O11Si8+
C26H63O12Si9+
C29H67O11Si8+
C25H59O11Si8+
C22H53O11Si8+
C21H51O11Si8+
C18H45O11Si8+
C17H43O11Si8+
C14H37O11Si8+
C13H35O11Si8+
C9H27O11Si8+
(m/z)theo
(m/z)exp
1036.5007
1019.4742
987.4116
945.3646
931.3490
889.3020
875.2864
871.3458
829.2989
819.2238
815.2832
759.2206
717.1737
703.1580
661.1111
647.0954
605.0485
591.0328
534.9702
I.S.
1019.4729
987.4129
945.3622
931.3485
889.3031
875.2856
871.3458
829.3025
819.2356
815.2614
759.2241
717.1527
703.1587
661.0982
647.1020
605.0350
591.0365
534.9723
Error
(ppm)
- 1.3
+ 1.3
- 2.5
- 0.5
+ 1.2
- 0.9
+ 0.0
+ 4.3
+ 14.4
- 26.7
+ 4.6
- 29.3
+ 1.0
- 19.5
+ 10.2
- 22.3
+ 6.3
+ 3.9
C12H27Si+
199.1877
199.1876
- 0.5
C7H19OSi2+
175.0969
175.0968
- 0.6
iBu Si O Si
H
C9H21Si+
157.1407
157.1420
+ 8.3
C8H19Si+
143.1251
143.1249
- 1.4
iBu Si
iBu
H
+
iBu Si
iBu
C6H15Si+
115.0938
115.0941
+ 2.6
iBu Si
C5H13Si+
101.0781
101.0784
+ 3.0
C4H11Si+
87.0625
87.0631
+ 6.9
iBu Si
H
H
+
iBu Si
H
C3H9Si+
73.0468
73.0474
+ 8.2
Si
C2H7Si+
59.0312
59.0322
+ 16.9
H
+
Si
upon
CID
of
ammoniated
Assignment
[POSS(OH)(OSiMe2iBu)2 + NH4]+
m/z 1036 – NH3
m/z 1019 – 2*CH4
m/z 987 – propene
m/z 987 – butene
m/z 945 – butene
m/z 931 – butene
m/z 945 – SiOC2H6
m/z 871 – propene
m/z 875 – butene
m/z 871 – butene
m/z 815 – butene
m/z 759 – propene
m/z 759 – butene
m/z 717 – butene / m/z 703 – propene
m/z 703 – butene
m/z 661 – butene / m/z 647 – propene
m/z 647 – butene
m/z 591 – butene
iBu
+
iBu Si
iBu
+
+
+
+
+
Page 14 of 14 – T. Fouquet, L. Charles, D. Ruch. – Correspondence to : thierry.fouquet@tudor.lu