# Supplementary Material (ESI) for Chemical Communications
# This journal is © The Royal Society of Chemistry 2005
Electronic Supplementary Information :
1. Determination of the volumic percentage of highly ordered domains by TEM
Sample 1 contains highly ordered 2D hexagonal domains that result in the p6mm diffraction peaks and more disordered
domains located at the centre of the spheres, still phase-separated at the nanometer scale, and that contribute to a broader
scattering peak under the diffraction peaks. Because the volumic fraction of the ordered domains can be overestimated
from the single analysis of one sphere hazardously cutted by ultramicrotome, we analysed 21 uncalcined cutted spheres.
For each resulting disk, we measured the diameters of the whole disk (D) and of the disordered domain (Ddis). The
quantity (D3 - Ddis3)/D3 is proportional to an apparent volumic fraction of highly ordered domains. Its variation as a
function of D is shown below. All the values are equal or above 0.6. Moreover, the diameters measured on TEM
micrographs are in the range of the diameters measured by SEM (DGM = 1.4 m). Therefore, we can estimate the volumic
percentage of ordered domains to at least 60 %.
1
D
0.8
(D3 - Ddis3)/D3
Ddis
0.6
0.4
Highly ordered domains
60 %
0.2
DGM = 1.4 m
from SEM
0
0
0.5
1
1.5
2
D (m)
1
2.5
3
3.5
# Supplementary Material (ESI) for Chemical Communications
# This journal is © The Royal Society of Chemistry 2005
Electronic Supplementary Information :
2. Quantification and spatial localisation of Si-Me groups by solid state NMR
The 1H one-dimensional spectrum of sample 1 recorded at high magnetic field (750 MHz) and fast MAS (30 kHz) is
shown with its assignment. Deconvolution of this spectrum by a proper software1 allows the quantification of each
organic function. Considering a fixed molar ratio [CTAB]/[Q units]=0.12 (in accordance with elemental analysis on
various mesoporous samples), the molar ratios [T units]/[Q units] and [Si-OR’ + Si-Me]/[Si] can be calculated. The values
found for [T units]/[Q units] are close to those found by 29Si NMR single pulse experiments.
The 1H-1H two dimensional spectrum of sample 1 shown below represents a BaBa Double Quantum ↔ Single Quantum
experiment.2 It allows identifying the pairs of spatially closed 1H nuclei coupled by dipolar interactions. The spectrum has
been recorded at high magnetic field (750 MHz) and fast MAS (30 kHz) using excitation and reconversion delays of 100
s. RF field strengths of c.a. 50 kHz were employed. From the off-diagonal peaks, we can observe a correlation between
signals of Si-CH3 and N-(CH3)+ that signs the spatial proximity between these groups, and thus the presence of Si-Me at
the siloxane-surfactant interface.
Other XHx
CH2N(CH3)3+
(CH2)15-CH3
CH2N(CH3)3+
Si-OCH2CH3
Si-OH
Si-CH3
Si-OCH(CH3)2
8
6
4
2
0
(1H) (ppm)
Off-diagonal peaks:
Double Quantum dimension
Other XHx ↔ Si-CH3
N-(CH3)+ ↔ Si-CH3
N-(CH3)+ ↔ Other XHx
CH(CH3)2 ↔ CH(CH3)2
MAS Single Quantum dimension
1
D. Massiot, F. Fayon, M. Capron, I. King, S. Le Calvé, B. Alonso, J.-O. Durand, B. Bujoli, Z. Gan and G. Hoatson,
Magn. Reson. Chem., 2002, 40, 70-76.
2
W. Sommer, J. Gottwald, D. E. Demco and H. W. Spiess, J. Magn. Reson. A, 1995, 113, 131-134.
2