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Electronic Supplementary Material (ESI) for Physical Chemistry Chemical Physics.This journal is the Owner Societies 2015Garaga M.N. et al., Local Environments around Heteroatoms in Layered Borosilicates,Supporting InformationLocal Environments of Boron Heteroatoms in NonCrystalline Layered BorosilicatesMounesha N. Garaga,a Ming-Feng Hsieh,b Zalfa Nour,aMichael Deschamps,a Dominique Massiot,a Bradley F. Chmelka,b Sylvian Cadarsa,c,*abCNRS, CEMHTI UPR3079, Univ. Orléans, F-45071 Orléans, FranceDepartment of Chemical Engineering, University of California, Santa Barbara, California93106, U.S.Acpresent address: Institut des Matériaux Jean Rouxel (IMN), Université de Nantes, CNRS, 2 ruede la Houssinière, BP32229, 44322 Nantes cedex 3, France* To whom correspondence should be addressed: E-mail: sylvian.cadars@cnrs-imn.frDr. Sylvian CadarsInstitut des Matériaux Jean Rouxel (IMN), UMR6502, Université de Nantes, CNRS,2 rue de la Houssinière, BP32229, 44322 Nantes cedex 3, FranceE-mail : sylvian.cadars@cnrs-imn.frSupporting information1

Garaga M.N. et al., Local Environments around Heteroatoms in Layered Borosilicates,Supporting InformationFigure S1. Solid-state NMR 29Si refocused INADEQUATE spectra probing 29Si-O-29Si linkagesin 29Si-enriched (a) C16H33N Me3- and (b) C16H33N Me2Et- directed layered borosilicates (Si/B 140 and 52, respectively), collected on a BRUKER AVANCE I spectrometer equipped with amagnetic field of 7.0 T (1H and29Silarmor frequencies of 300 and 59.63 MHz, respectively).The sample was spun at a MAS frequency of 10 kHz with a 4 mm double resonance probehead.A half-echo delay of 6 ms and a cross-polarization (CP) contact time of 7ms were used for bothmaterials. The spectra were accumulated over 128 and 96 transients for each of 160 and 184increments in the indirect dimension, respectively. Heteronuclear 1H decoupling (SPINAL64) of60 kHz was applied during the entire pulse sequence.2

Garaga M.N. et al., Local Environments around Heteroatoms in Layered Borosilicates,Supporting InformationTable S1. Perturbation range induced by the B atoms.MaterialsSi/BC16H33Me3N -directedlayered borosilicate140C16H33Me2EtN -directedlayered borosilicate52Perturbationrange (Å)4567845678Number of Sineighbors affected a3.51013.516.5283.69.214.219.028.8% of 29Si signalaffected b2.57101220718273755a Thenumber of Si sites affected by the presence of a B atom nearby were calculated as follows.Considering a given silicate framework model of the material considered (taken from refs.1, 2for the C16H33Me3N and C16H33Me2EtN - directed materials, respectively), we substituted oneSi site by a B atom and counted the number of Si atoms located within the chosen perturbationrange. This task was repeated for B substituting each one of the (two or five, respectively)inequivalent T sites. The value given here is the average of the number of Si sites counted in allcases.bthe fraction of 29Si signal affected is calculated as the number of Si affected divided by the Si/Bratio.3

Garaga M.N. et al., Local Environments around Heteroatoms in Layered Borosilicates,Supporting InformationFigure S2. Transverse 11B dephasing time (T2’) measurements conducted (a, c, e) without and (b,d, f) with heteronuclear 1H decoupling on (a-d) C16H33Me3N - and (e, f) C16H33Me2EtN directed layered borosilicates to make distinction between Q3 and Q411Benvironments. WhileQ3 sites dephase much more rapidly without than with heteronuclear 1H decoupling due to thecloser proximity of 1H moieties, Q4 sites are not strongly affected since their couplings to theprotons are weaker.4

Garaga M.N. et al., Local Environments around Heteroatoms in Layered Borosilicates,Supporting InformationDescription of DFT calculations using surfactant-mimicking molecules. In addition to ethecharge-compensatingalkylammonium surfactants are simply omitted, another approach was also conducted, in whichsurfactant-mimicking molecules were incorporated explicitly. Specifically, short alkyl-chainCH3-(CH2)3-N Me3 or CH3-(CH2)3-N Me2Et molecules were included in the inter-layer space ofall reference layered silicate structure models to streamline computations while hopefullydescribing the organic-inorganic interactions at the interface. A series of geometry optimizationswere then conducted on model structures, in which one of the Si sites was manually replaced byone B atom. Several models containing different amounts of these surfactant-mimickingmolecules were used for both materials. In the case where the number of surfactant molecule isless than the negative charge presented in a specific structure, protons are added to form B(orSi)-O-H···O-Si species. Examples of B atoms in Q3 Si sites in the C4H9N Me3 andC4H9N Me2Et-directed borosilicates are shown in Figure S2 (a, b) and (c, d), respectively. Otherexamples of compositions for model structures of the material with -N Me3 headgroups arelisted in Table S3.5

Garaga M.N. et al., Local Environments around Heteroatoms in Layered Borosilicates,Supporting InformationFigure S3. Examples of model structures of surfactant-directed layered borosilicates asoptimized with planewave-based DFT, using surfactants with shortened C4 chains. (a, b)C4H9Me3N - directed borosilicate model with B incorporated in one site Si(Q3) out of the 8 Tsites per unit cell. (c, d) Model of C4H9Me2EtN - directed layered borosilicate with Si/Bsubstitution on one site 1 (Q3) among the 10 T-sites present in the unit cell of one of thecandidate structures of this material. Si site labels are given as number between 1 and 5. Theadditional charge introduced by the substitution is compensated in these particular models by the6

Garaga M.N. et al., Local Environments around Heteroatoms in Layered Borosilicates,Supporting Informationaddition of a proton on the boron in Q3 site. The black lines delimit the unit cell, with twoadjacent cells shown in each case.While model structures built with the approach described above were expected to describe thelocal Si structures near framework B species, calculated29Sichemical shifts are not consistentwith the NMR analyses of C16H33N Me3- and C16H33N Me2Et - directed layered borosilicatematerials. This is illustrated in Figure S3 for the C4H9N Me2Et - directed layered borosilicatemodels, for which broad distributions of calculated 29Si chemical shifts are obtained, which arenot well correlated with experimental results, and probably result from the frozen state of thesurfactant-mimicking molecules. Similar observations were made for the C4H9N Me3 - directedmodels (data not shown), confirming that the surfactant dynamics crucially impact the 29Si NMRsignatures (as already discussed from variable-temperature experiments on the referenceC16H33N Me2Et - directed layered silicate material3). Although the 11B chemical shifts calculatedvia this approach (see Tables S2 and S3) turn out to be less affected by this issue thanchemical shifts, a different modeling strategy was adopted for these systems.729Si

Garaga M.N. et al., Local Environments around Heteroatoms in Layered Borosilicates,Supporting InformationFigure S4. Comparisons of experimental29Sichemical shifts and isotropic chemical shiftscalculated by DFT for a series of C4H9Me2EtN - directed borosilicate models of composition(BSi9O11)5- · 4(C4H9N Me2Et). Shown in black above the plots are the29Si{1H}CP-MAScollected for the corresponding materials, and in red are projections extracted from 2D 11B{29Si}correlation experiments revealing Qn (1B)29Sienvironments. Open “ ”symbols in (a), (b)correspond to Si atoms that are not connected to a B atom, and whose experimental shifts shouldcorrespond (in first approximation) to the dominant29Sipeaks observed experimentally (andidentical to pure-silicate materials). Plots (a) and (b) correspond to two distinct situations, with Bincorporated either (a) in Q3 crystallographic site 1 or (b) in Q3 crystallographic site 2, with theresulting calculated Qn (1B) 29Si shifts shown as filled “ ” symbols. Studied models are basedon the three candidate structures of the C16H33Me2EtN - directed layered silicate material (seeref. 4).8

Garaga M.N. et al., Local Environments around Heteroatoms in Layered Borosilicates,Supporting InformationTable S2. 11B chemical shift values calculated with DFT for the model structures of theC16H33N Me2Et - layered borosilicate material with C4H9N Me2Et EtN layeredborosilicateB/Si substitution siteRange of calculated isotropic 11Bchemical shifts (ppm) aSi1(Q3)-1.1 to -0.8Si2(Q3)-1.3 to 0.4Si3(Q4)-1.9 to -1.6Si4(Q4)-3.5 to -2.1Si5(Q4)-3.9 to -2.2Experimentalshift (ppm) b11B-0.4aThe range of values given here includes calculations conducted on models built from differentreference silicate structures (candidate structures #2, 3, or 4 in ref. 2), with compositions(BSi9O11)5- · 4(C4H9N Me2Et) in a 1 1 1 cell.bPosition of 11B peak at 17.6 T. This value should be close to the actual chemical shift valuebecause the quadrupolar interaction, and thus the corresponding contribution to the isotropic shiftof these 11B(IV) is small ( 1 MHz, as predicted from DFT calculations).9

Garaga M.N. et al., Local Environments around Heteroatoms in Layered Borosilicates,Supporting InformationTable S3. 11B chemical shift values calculated with DFT for the model structures of the C16H33N Me3 - layered borosilicatematerial with different amounts of C4H9N Me3 surfactant-mimicking molecules.Model composition and charge(BSi7O18)5- · 5(C4H9N Me3)B/Si substitutionsiteSi1(Q3) as BO-(BSi15O36)9- · 9(C4H9N Me3)Si1(Q3) as BO4 (BSi7O18H) · 4(C4H9N Me3)Si1(Q3) as BOH(BSi15O36H8)- · (C4H9N Me3)Si1(Q3) as BOH5 (BSi7O18) · 5(C4H9N Me3)Si2(Q4)9 (BSi15O36) · 9(C4H9N Me3)Si2(Q4)4 (BSi7O18H) · 4(C4H9N Me3)Si2(Q4) (BSi15O36H8) · (C4H9N Me3)Si2(Q4)Models with additional Si-O-Si connectivities(BSi23O53H)10- · 10(C4H9N Me3)Si1(Q3) (BSi23O53H10) · (C4H9N Me3)Si1(Q3) (BSi47O107H22) · (C4H9N Me3)Si1(Q3)14 (BSi31O71H) · 14(C4H9N Me3)Si2(Q4)15 (BSi31O71) · 15(C4H9N Me3)Si2(Q4)(BSi31O70)13- · 13(C4H9N Me3)Si2(Q4)(BSi31O70H12)- · (C4H9N Me3)Si2(Q4)aNew one1 Si-O-Si1 Si-O-Si1 Si-O-Si1 Si-O-Si1 Si-O-Si2 Si-O-Si2 Si-O-SiBOH/SiOHgroups1 BOH1 BOH / 7 SiOH1 SiOH1 BOH1 BOH / 9 SiOH1 BOH / 21 SiOH1 SiOH12 SiOH11BSupercellsize1x1x1Calculated iso(11B) (ppm)-0.7Experimental 11Bshift , -3.3 b-2.2, -3.6 al shift corresponds to the position of the experimental peak that gives the best match between all availableexperimental and calculation constraints.b depending on the position of the additional Si-O-Si connectivity.10

Garaga M.N. et al., Local Environments around Heteroatoms in Layered Borosilicates,Supporting InformationFigure S5. (a-f) Comparisons between experimental and calculated chemical shifts for candidatemodel structures of the reference C16H33N Me2Et-directed silicate material (without Bincorporation). All structures optimized of the original structures labeled 2, 3 and 4 reported inref. 2, with (a-c) no or (d-f) only 2 protons compensating the negative charges associated withnon-bridging O atoms per supercell (consisting of 10 Si atoms and 22 O atoms). In contrast, theoriginal structures published in ref. 2 had 4 H atoms per unit cell (data not shown here). Othernegative charges are compensated here by positive charges homogeneously distributed across the11

Garaga M.N. et al., Local Environments around Heteroatoms in Layered Borosilicates,Supporting Informationentire supercell. Best agreement between calculated and experimental29Sichemical shifts areobtained for the structures with 2 H per cell, which are superimposed and viewed from the topand from the side of the layer in (g) and (h). Structure 4 turns out to be identical to structure 2when optimized under such conditions, and is consequently not shown.12

Garaga M.N. et al., Local Environments around Heteroatoms in Layered Borosilicates,Supporting InformationFigure S6. Illustration describing the procedure used to construct models of the C16H33Me3N directed borosilicate material with two new Si-O-Si connectivities involving tetrahedralneighbors of a B atom incorporated in substitution of a Q4 Si site. This situation can explain theunexpected absence of incompletely condensed Q3(1B) Si sites among the four connectedtetrahedral neighbors of boron site B2. The DFT-optimized model at the bottom was obtained byreplacing manually two pairs of nearby non-bridging O atoms in a 2x2x1 supercell of theoriginal model by a single O atom located at the center of mass of the corresponding Si atoms.13

Garaga M.N. et al., Local Environments around Heteroatoms in Layered Borosilicates,Supporting InformationTable S4. Description of pseudopotentials used for planewave-based DFT calculations.AtomHBCNOSiCore-states1s1s1s1s1s, 2s, 00.91.3Pseudopotentialprojectors2x2s2x2s, 2x2p2x2s, 2x2p2x2s, 2x2p2x2s, 2x2p2x3s, 2x3pPAW projectors2x2s2x2s, 2x2p2x2s, 2x2p2x2s, 2x2p2x2s, 2x2p2x3s, 2x3p, 2x3dPseudopotentials used for calculations on reference crystalline systems (see below)LiNa1spd1.21.31.21.30.81.01x1s, 2x2s1x2s, 2x2p, 1x3sMg1s, 2sd1.62.01.42x3s,1x2p, 2x3pAlPCa1s, 2s,2p1s, 2s, 2p1sddf2.01.81.62.01.82.01.41.31.42x3s, 2x3p2x3s, 2x3p1x3s, 2x3p, 1x4s1x1s, 2x2s1x2s, 2x2p, 1x3s2x3s, 1x2p, 2x3p,2x3d2x3s, 2x3p, 2x3d2x3s, 2x3p,2x3d1x3s, 2x3p, 1x4sWhere rloc is the pseudisation radius for the local component of the pseudopotential, rnonloc is thepseudisation radius for the non-local components of the pseudopotential, and raug is thepseudisation radius for the charge augmentation functions. The corresponding Materials Studiocastep on-the-fly strings used to generate these potentials are:H 1 0.8 3.675 7.35 11.025 10UU(qc 6.4)[]Li 1 1.2 11 13.2 15 10U:20UU(qc 5.5)[]B 2 1.4 9.187 11.025 13.965 20UU:21UU(qc 5.5)[]C2 1.4 9.187 11.025 12.862 20UU:21UU(qc 6)[]N2 1.5 11.025 12.862 14.7 20UU:21UU(qc 6)[]O 2 1.3 16.537 18.375 20.212 20UU:21UU(qc 7.5)[]Na 2 1.3 1.3 1 11.8 13.6 15.3 20U -2.07:30U -0.105:21U -1.06U 0.25[]Mg 2 1.6 2 1.4 6 7 8 30NH:21U:31UU:32LGG(qc 4.5)[]Al 2 2 3.675 5.512 7.717 30UU:31UU:32LGG[]Si 2 1.8 3.675 5.512 7.35 30UU:31UU:32LGG[]P 2 1.8 3.675 5.512 6.982 30UU:31UU:32LGG[]Ca 3 1.6 2.0 1.4 7 9 10 30U:40U:31:32U 0@ 0.12U 1.0@ 0.12The pseudopotential of Ca used the correction described by Profeta et al.514

Garaga M.N. et al., Local Environments around Heteroatoms in Layered Borosilicates,Supporting InformationTable S5. Calculated shielding ( iso) and experimental chemical shifts ( iso) of reference systems ofknown crystal structure.Compound, formulaSite #α-quartz SiO2Cristoballite SiO2Reedmegnerite NaBSi3O81132111111112121Experimentalshift 85.6-87.5-90.6-90.2-1.9Datolite CaBSiO4(OH)1Danburite CaB2Si2O8Nucleus7Calculatedshielding 5.45BN cubic11.6794.80BN hexagonal130.4766.40diomignite Li2B2O7dilithium tetraborate117.921.7BPO41-3.3798.23Sassolite B(OH)3118.8774.70albite NaAlSi3O8datolite CaBSiO4(OH)danburite CaB2Si2O8Pyrophyllite Si4Al2O10(OH)2Talc ions of shieldings for crystalline model systems of known structure and experimentalshifts are used to accurately calculate the isotropiccalculated29Siand11B29Siand11Bchemical shifts ( iso) fromshieldings ( iso). This procedure compensates for possible systematicerrors of the DFT calculations. All calculations were conducted on structures previouslyoptimized with fixed unit cell parameters. The series of compounds listed in Table S3 led to thefollowing relationships: iso(ppm) -0.920* iso 288.45 for95.3 for 11B.1529Si; and iso(ppm) -1.0* iso

Garaga M.N. et al., Local Environments around Heteroatoms in Layered Borosilicates,Supporting InformationFigure S7. Correlation plots between experimental isotropic chemical shifts and isotropicshielding calculated by DFT for the series of reference crystals of known structures listed inTable S3. The figures (a) and (b) correspond to 11B and 29Si NMR data, respectively.16

Garaga M.N. et al., Local Environments around Heteroatoms in Layered Borosilicates,Supporting InformationReferences of the Supporting Information section.1.I. Wolf, H. Gies and C. A. Fyfe, The Journal of Physical Chemistry B, 1999, 103, 5933-5938.2.D. H. Brouwer, S. Cadars, J. Eckert, Z. Liu, O. Terasaki and B. F. Chmelka, J. Am.Chem. Soc., 2013.3.S. Cadars, N. Mifsud, A. Lesage, J. D. Epping, N. Hedin, B. F. Chmelka and L. Emsley,J. Phys. Chem. C, 2008, 112, 9145–9154.4.D. H. Brouwer, S. Cadars, J. Eckert, Z. Liu, O. Terasaki and B. F. Chmelka, J. Am.Chem. Soc., 2013, 135, 5641-5655.5.M. Profeta, M. Benoit, F. Mauri and C. J. Pickard, J. Am. Chem. Soc., 2004, 126, 12628-12635.6.J. F. Stebbins, in Handbook of Physical Constants, ed. T. J. Ahrens, AmericanGeophysical Union, Washington D.C., 1995, vol. 2.7.K. J. D. Mackenzie and M. E. Smith, multinuclear solid-state NMR of inorganicmaterials, Pergamon Press, Oxford, 2002.8.H. Koller, G. Engelhardt, A. P. M. Kentgens and J. Sauer, J. Phys. Chem., 1994, 98,1544-1551.9.L. Martel, S. Cadars, E. Véron, D. Massiot and M. Deschamps, Solid State Nucl. Mag.,2012, 45–46, 1-10.17

reference silicate structures (candidate structures #2, 3, or 4 in ref. 2), with compositions (BSi9O11)5-· 4(C4H9N Me2Et) in a 1 1 1 cell. b Position of 11B peak at 17.6 T. This value should be close to the actual chemical shift value because the quadrupolar interaction, and t

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