Post-Synthesis Modification of the Aurivillius Phase Bi2SrTa2O9 via In

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Post-Synthesis Modification of the Aurivillius Phase Bi2SrTa2O9 via In Situ Microwave-Assisted “Click Reaction” Yanhui Wang,† Emilie Delahaye,† Cédric Leuvrey,† Fabrice Leroux,‡ Pierre Rabu,† and Guillaume Rogez*,† †

Institut de Physique et Chimie des Matériaux de Strasbourg and Labex NIE, University of Strasbourg, CNRS UMR 7504, 23 rue du Loess, BP 43, 67034 Strasbourg cedex 2, France ‡ Institut de Chimie de Clermont-Ferrand, CNRS UMR 6296, UFR Sciences et Technologies, Equipe Matériaux Inorganiques, 24 avenue des Landais, BP 80026, 63171 Aubière cedex, France S Supporting Information *

ABSTRACT: A new strategy for the functionalization of layered perovskites is presented, based on the in situ post-synthesis modification of a prefunctionalized phase by copper(I)-catalyzed alkyne−azide cycloaddition (CuAAC). The microwave-assisted protonation and grafting of an alkyne alcohol provides the alkyne-functionalized precursor within a few hours, starting from Bi2SrTa2O9. The subsequent microwave-assisted in situ “click reaction” allows the postsynthesis modification of the precursor within ∼2 h, providing a layered perovskite functionalized by an alcohol-grafted 1,4-disubstituted-1H-1,2,3triazole. Two compounds are described here, bearing an aliphatic and an aromatic substituent, which illustrates the general application of the method. This work opens new perspectives for the functionalization of layered perovskites, going beyond mere insertion/grafting reactions, and thus broadens the design possibilities and the range of applications of these hybrid systems.

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INTRODUCTION Hybrid organic−inorganic materials constitute a class of materials of considerable interest, primarily because they might combine, within a single edifice, the multiple properties brought by their constituents.1−4 In this field, two-dimensional (2D) materials and, more specifically, layered insertion compounds are particularly worthy of interest, because of the variety of inorganic host structures that are available (hydroxides, chalcogenides, clays, ...) and the variety of possible applications they provide.5−7 Among layered materials, ionexchangeable oxides as layered perovskites exhibit especially interesting physical properties such as ferroelectricity,8−16 luminescence17,18 or photocatalytic19,20 properties. The functionalization of such phases is thus particularly interesting, in that it allows one to finely tune the interlayer spacing size and content, and, hopefully, the properties of the final hybrid compounds. Such hybridization of layered perovskite proceeds by acidification, followed by intercalation or grafting of the desired molecule.21 Yet, until now, this approach has been limited to very simple molecules and functions (aliphatic amines,22−30 alcohols,31−35 or phosphonic acids36 bearing mere alkyl chains), using long synthesis processes of several days. Very recently, the reaction time scales have been considerably reduced by using microwave irradiation,35,37,38 but the molecules that have been inserted/grafted using this approach remain very basic, even though some more elaborated amines have been successfully inserted (chiral amines or amines bearing an aromatic group for instance).38 This limitation of the © XXXX American Chemical Society

mere insertion/grafting strategy thus narrows the range of functionalization and, hence, applications of these hybridized layered perovskites. Post-synthesis modification (PSM) can then be proposed to overcome the difficulty to insert directly complex or lowreactivity molecular guests. Following this approach, the desired molecule would be synthesized in situ, within the interlamellar space. Indeed post-synthesis modification has been proposed at the beginning of the 1990s,39 and really developed for metal organic frameworks (MOFs) 10 years later.40 The use of PSM for MOFs has been thoroughly reviewed.41−43 PSM has also been employed for microporous materials44 or for mesoporous silicates.45,46 In the field of layered systems, PSM has been relatively seldom used in clay,47,48 layered silicates,49 layered double hydroxides,50,51 and, more recently, layered simple hydroxides.52 To the best of our knowledge, the post-modification strategy has been used so far only once in the field of layered perovskites, for the in situ hydrosilylation of a Dion−Jacobson phase.53 We report here the efficient microwave-assisted postsynthesis modification of a layered perovskite via copper(I)catalyzed alkyne−azide cycloaddition (“click reaction” or CuAAC reaction). Click reactions54 have proved to be particularly useful in molecular chemistry, in that they are Received: July 5, 2016

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DOI: 10.1021/acs.inorgchem.6b01600 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry

containers. Containers must be caref ully checked for any defect, and replaced if necessary to avoid possible explosion. Concentrated chlorohydric acid is corrosive and irritating. Azides are potentially explosive, especially in the absence of solvents. Synthetic Procedures. Bi2SrTa2O9 (BST) was synthesized according to published procedures.18,38,69,70 H2 Bi0.1Sr 0.85 Ta2 O7 (HST) and (C2 NH) 0.8 H1.2Bi0.1 Sr 0.85Ta 2 O7 (C2N⊂HST) were synthesized according to published procedures.38 1-Azidohexane71 and benzyl-azide72 were prepared according to published procedures. H0.9Bi0.1Sr0.85Ta2O5.9(OCH2CH3)1.1·0.3H2O (C2OH⊂HST). C2N⊂HST (0.1 g, 0.15 mmol), ethanol (8 mL, 137 mmol), and water (0.1 mL, 5.6 mmol) were sealed in a 30 mL vial and heated with microwave irradiation at 130 °C during 2 h (maximum incident power = 70 W). During these conditions, the mean incident power was ∼10 W and the autogenous pressure remained below 6 bar. The obtained white powder was collected after three centrifugations (9000 g (26 000 rpm with a radius of centrifugation of 11.5 mm), 5 min each) (the supernatant was replaced after each centrifugation by acetone in order to wash the product) and dried in an oven at 70 °C for 5 min. H 1.3 Bi 0.1 Sr 0.85 Ta 2 O 6.3 (OC 3 H 6 CCH) 0.7 ·0.5H 2 O (HCC⊂HST). C2OH⊂HST (0.1 g, 0.16 mmol), 4-pentyn-1-ol (2 mL, 21.5 mmol), and water (25 μL, 1.4 μmol) were sealed in a 10 mL vial under a protective argon atmosphere and heated with microwave irradiation at 110 °C during 2 h (maximum incident power = 70 W). Under these conditions, the mean incident power was ∼5 W and the autogenous pressure was too low to be measured. The obtained white powder was collected after three centrifugations (9000 g (26 000 rpm with a radius of centrifugation of 11.5 mm), 5 min each) (the supernatant was replaced after each centrifugation by acetone in order to wash the product) and dried in an oven at 70 °C for 5 min. H1.5Bi0.1Sr0.85Ta2O6.5(OC11N3H20)0.5·0.3H2O (hexyl-click⊂HST) and H1.4Bi0.1Sr0.85Ta2O6.4(OC12N3H14)0.6·0.6H2O (benzyl-click⊂HST). HC C⊂HST (200 mg, 0.32 mmol), CuBr(PPh3)3 (1 mol %, 3.0 mg, 3.2 μmol), and 1-azidohexane (0.5 g, 3.9 mmol) or benzyl-azide (0.52 g, 3.9 mmol) in dry THF (2 mL) were sealed in a 10 mL vial under a protective argon atmosphere and heated with microwave irradiation at 80 °C during 2 h (maximum incident power = 70 W). Under these conditions, the mean incident power was ∼2 W and the autogenous pressure was too low to be measured. The obtained white powder was collected after five centrifugations (9000 g (26 000 rpm with a radius of centrifugation of 11.5 mm), 5 min each) (the supernatant was replaced after each centrifugation by THF (twice) and acetone (twice) in order to wash the product) and dried in an oven at 70 °C for 5 min. Deintercalation Procedure. To 200 mL of NaOH aqueous solution (6 M), 600 mg of hexyl-click⊂HST or benzyl-click⊂HST was added. The reaction mixture was then stirred at 80 °C for 48 h. After reaction, the obtained solid and the aqueous suspension were separated via centrifugation (9000 g (26 000 rpm with a radius of centrifugation of 11.5 mm), 5 min). The obtained solid was washed with water (thrice) and acetone (twice) via centrifugation (9000 g (26 000 rpm with a radius of centrifugation of 11.5 mm), 5 min each) and air-dried. The aqueous basic suspension was extracted thrice with 100 mL of diethyl ether in the case of hexyl-click⊂HST or 100 mL of CH2Cl2 in the case of benzyl-click⊂HST. The combined organic fractions were dried over Na2SO4 and concentrated at reduced pressure.

particularly efficient, with high yield and few side products and compatible with most functional groups.55 As for other reactions,56,57 the use of microwave irradiation for CuAAC reactions for molecular synthesis is developing.56−61 In the past few years, CuAAC reactions have been applied for the PSM of a large number of MOFs, either for selective surface modification,62 or for internal functionalization.63−68 In the present case, two different azide reactantsone bearing an aliphatic group, and the other bearing a more bulky and rigid aromatic grouphave been used to functionalize an alkyne-functionalized layered perovskite, which illustrates the generality and efficiency of this new approach for the functionalization of layered perovskites (Scheme 1). Scheme 1. Microwave-Assisted Post-Synthetic Modification of the Aurivillius Bi2SrTa2O9 Phase by In Situ Copper(I)Catalyzed Alkyne−Azide Cycloaddition (CuAAC) and General Scheme of CuAAC Reaction

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EXPERIMENTAL SECTION

Materials and Methods. Microwave syntheses were performed with a microwave synthesis reactor (Monowave 300, Anton Paar) under nonacidic conditions and with a microwave synthesis reactor (Model MultiwaveGO, Anton Paar) when aqueous acidic conditions are required. Elemental analyses for C, H, and N were carried out by the Service d’Analyze of the Université de Strasbourg. The powder XRD patterns were collected with a Bruker D8 diffractometer (Cu Kα1 = 0.1540598 nm) equipped with a LynxEye detector discriminating in energy. The SEM images were obtained with a JEOL Model 6700F microscope equipped with a field emission gun, operating at 3 kV in the SEI mode. Fourier transform infrared (FT-IR) spectra were collected in ATR mode on a SpectrumII spectrometer (PerkinElmer). TGA-TDA experiments were performed using a TA Instruments, Model SDT Q600 system (heating rates of 5 °C min−1 under a stream of air, using alumina crucibles). NMR spectra in solution were recorded using a Bruker AVANCE 300 (300 MHz) spectrometer. Solid-state NMR 13C (I = 1/2) experiments were performed with a 300 Bruker spectrometer at 75.47 MHz, using magic angle spinning (MAS) condition at 10 kHz and a 4-mm-diameter zirconia rotor. 13C spectra obtained using a proton-enhanced cross-polarization (CP) method were referenced to the carbonyl of the glycine calibrated at 176.03 ppm. Recycling and Hartman−Hahn contact times were 5 s and 1250 μs, respectively. Spinal 64 1H phase-decoupling was applied during 13C channel acquisition. Caution: Even though no problems were encountered during the course of this research, special care must be taken while working with sealed glass

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RESULTS AND DISCUSSION The protonated Aurivillius phase H2Bi0.1Sr0.85Ta2O7 (HST) was obtained within 3 h, using microwave-assisted acidification of the starting Bi2SrTa2O9 (BST) phase, according to a published procedure.38 Following our results on the microwave-assisted insertion of various amines,38 we first tried to functionalize HST by amines bearing a terminal alkyne or an azide group. Unfortunately, these reactions failed, because of the instability of the inserted molecules. Therefore, we took advantage of the possibility to graft alcohols into the interlamellar spacing of such layered perovskites. This possibility was evidenced on B


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Inorganic Chemistry Dion−Jacobson phases and Ruddlesden−Popper,31−34,73,74 and more recently demonstrated for Ta-based Ruddlesden−Popper perovskites.20 Some of the reported alcohol-grafting reactions take advantage of microwave irradiation.35,37 The precursor for the post-synthesis modification, HC C⊂HST, was obtained by functionalizing HST, using an alcohol bearing a terminal alkyne group. 4-Pentyn-1-ol was thus inserted using a multistep preintercalation strategy. Ethylamine was initially grafted onto HST. The resulting product C2N⊂HST was then transformed to the ethanol analogue C2OH⊂HST. Ethanol then was replaced by 4-pentyn-1-ol (HCC⊂HST). Attempts of direct insertion of 4-pentyn-1-ol in HST failed, as already described for the grafting of n-alcohols into Ruddlesden−Popper hosts.20,37 Attempts of insertion of 4pentyn-1-ol in HST prefunctionalized by ethylamine (C2N⊂HST) led to incomplete transformation and to badly crystallized products. The compound HCC⊂HST is thus obtained from the parent Aurivillius phase, BST, using one microwave-assisted acidification and two microwave-assisted preintercalation steps (BST → HST → C 2 N⊂HST → C2OH⊂HST → HCC⊂HST). Using standard vials, HC C⊂HST can be obtained in the 100 mg scale within ∼1 day starting from BST, with a total reaction time of ∼8 h. The powder X-ray diffraction (PXRD) pattern of HC C⊂HST is shown in Figure 1. The series of intense (00l)

for the grafting of aliphatic alcohols into Ta-based Ruddlesden−Popper perovskites,20,37 which may suggest partial interdigitation of the inserted molecules. The alcohol-exchange reaction is topotactic, as suggested by the preservation of unshifted characteristic out-of-plane reflections of HST (for instance, (100) at 22.68°, (110) at 32.59°, and (200) at 46.32° (Cu Kα1 radiation)). The purity of the compound and the grafting of 4-pentyn-1ol onto the Ta oxide layers are further confirmed by infrared spectroscopy (Figure 2). In addition to the Ta−O elongation

Figure 2. Infrared spectra of HST (black), C2OH⊂HST (green), HCC⊂HST (blue), and 4-pentyn-1-ol (magenta).

vibration at 580 cm−1, which is the dominant feature, the spectrum of HCC⊂HST clearly shows the C−H stretching vibration of the terminal alkyne at 3285 cm−1 and the CC stretching vibration at 2114 cm−1, as for 4-pentyn-1-ol. The C− O stretching vibration is blue-shifted by ∼90 cm−1 in HC C⊂HST (1132 cm−1), with respect to free 4-pentyn-1-ol (1046 cm−1). Moreover, the CH3 vibration at 2967 cm−1 observed for the starting C2OH⊂HST compound is no longer visible in the HCC⊂HST spectrum. Finally, there is no evidence of O−H stretching vibration at 3360 cm−1, as would be the case for a mere alcohol insertion. All these features indicate the complete replacement of grafted ethanol by 4-pentyn-1-ol. Solid-state 13C CP/MAS NMR spectrum of HCC⊂HST is presented later in Figure 6. The comparison with the spectrum of 4-pentyn-1-ol (Figure S1 in the Supporting Information) shows that the signals B, C, D, and E do not move upon grafting (32, 15, 85, and 70 ppm, respectively, in the hybrid HCC⊂HST, and 31, 15, 84, and 69 ppm, respectively, for the free molecule). In contrast, the signal of the α-carbon A is shifted downfield by ∼12 ppm in HCC⊂HST, with respect to the free molecule (73 and 61.4 ppm, respectively), which indicates the formation of a covalent C−O−Ta bond.20,32 The grafting rate was evaluated from thermogravimetric analysis (Table S1 and Figure S2 in the Supporting Information) and, along with elemental analysis, a consistent formula for HCC⊂HST is H1.3Bi0.1Sr0.85Ta2O6.3(OC3H6C CH)0.7·0.5H2O. This organic loading of 0.7 alcohol per Ta2 unit is within the range of reported alcohol loading in other layered perovskites, either by classical functionalization20,31,32,34,36,77 or by microwave-assisted functionalization.35,37

Figure 1. Powder X-ray diffraction (PXRD) patterns of HST (black), C2N⊂HST (red), C2OH⊂HST (green), and HCC⊂HST (blue).

reflections in the low 2θ range evidence the lamellar character of the compound. These (00l) reflections are shifted to lower angles, with respect to the starting and intermediate products HST (first basal spacing: d001 = 0.98 nm), C2N⊂HST (d001 = 1.57 nm), and C2OH⊂HST (d001 = 1.55 nm), which are no longer present in the final compound. This indicates the completeness of the reaction after the exchange process. An interlamellar spacing of 1.87 nm was deduced for HC C⊂HST, which is compatible with a bilayer arrangement of the alkyne molecules in the interlamellar space with a tilt angle of 60°, with respect to the normal to the layers (considering the size of the molecules (∼0.7 nm), the thickness of the inorganic layers (∼1 nm),18,75 and the distance between the terminal alkyne groups (0.3 nm)76). Assuming a bilayer arrangement, the tilt angle is approximately twice those previously reported C


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Inorganic Chemistry

hexyl-azide (hexyl-click⊂HST) or benzyl azide (benzylclick⊂HST). The (00l) reflections of the starting HC C⊂HST are no longer present and have been replaced by a set of intense (00l) reflections at lower angles. This indicates the preservation of the lamellar character with larger interlamellar spacing (2.72 nm for hexyl-click⊂HST and 2.60 nm for benzylclick⊂HST), as expected if the in situ reaction is indeed effective. Once again, the perovskite-like slabs remain unchanged, as proved by the unshifted out-of-plane reflections. The scanning electron microscopy (SEM) photomicrographs show that the shape, morphology, and size of the crystallites are preserved upon reaction (see Figure 4). The in situ click reaction is confirmed by infrared spectroscopy. The FTIR spectra in Figure 5 shows the

Despite the fact that the thermally activated 1,3-dipolar cycloaddition reaction between terminal or internal alkynes and organic azides (without catalyst) has been thoroughly investigated,78 no reaction occurred between the immobilized alkyne in HCC⊂HST and hexyl-azide or benzyl-azide without the use of a catalyst. Several catalysts, commonly used in organic chemistry, such as Cu metal,79 Cu metal/ Cu(SO 4 ), 80 CuI, 81,82 CuI/(Pr 2 )EtN, 83−85 and CuBr/ CH3SCH3,86,87 have been tried unsuccessfully in various solvent and temperature conditions. For the common Cu(SO4)/sodium ascorbate, the click reaction using the conditions described below worked only partially, with the presence of the starting material and HST in the final product. This is likely due to the use of water, which is necessary with this catalyst, which leads to hydrolysis of the alcohol−Ta bonds.34 Therefore, our choice went to CuBr(PPh3)3 which could be used in dry THF.88,89 The quantity of catalyst has further been optimized to 1 mol % (with respect to HCC⊂HST). For lower ratios, the reaction is clearly incomplete, whereas, for higher ratios, the reaction works well, but then the Cu ions cannot be removed completely, and solid-state NMR is impossible to record in that case, likely because of partial oxidation of the remaining Cu(I) ions. The microwave-assisted click reaction was thus carried out between HCC⊂HST and an excess of hexyl-azide or benzyl azide, in dry THF, in the presence of CuBr(PPh3)3 as a catalyst (1 mol %), at 80 °C for 2 h under argon (maximum incident power = 70 W). Under these conditions, the mean incident power was ∼2 W. Figure 3 shows the powder X-ray diffraction (XRD) patterns of the compounds obtained by reacting HCC⊂HST and

Figure 5. Infrared spectra of HCC⊂HST (blue), hexyl-click⊂HST (red), and benzyl-click⊂HST (green).

disappearance of the terminal alkyne C−H stretching band at 3285 cm−1 and of the CC stretching vibration at 2114 cm−1. Several other bands appear, indicating the effectiveness of the click reaction: 1551 cm−1, attributed to NN stretching band, signals at 1632 and 1457 cm−1, attributed to the triazole group,90 and weak signal at 3132 cm−1, attributed to the C C−H group of the pentaheterocyclic structure. In addition, the absorption bands due to CH2 groups at 2926 and 2826 cm−1 are clearly enhanced in hexyl-click⊂HST, with respect to the starting HCC⊂HST. Moreover, a pronounced shoulder, attributed to the CH3 group present in hexyl-click⊂HST, appears at 2955 cm−1. For benzyl-click⊂HST, characteristic signals of the phenyl group are visible (weak C−H stretching bands at 3064 and 3029 cm−1, and C−C stretching at 1497

Figure 3. PXRD patterns of HCC⊂HST (blue), hexyl-click⊂HST (red), and benzyl-click⊂HST (green).

Figure 4. SEM images of HCC⊂HST (left), hexyl-click⊂HST (middle), and benzyl-click⊂HST (right) (scale bar = 1 μm). D


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Inorganic Chemistry cm−1). Finally, the presence of the intense C−O stretching bands at 1137 and 1128 cm−1 for hexyl-click⊂HST and benzylclick⊂HST, respectively, and the absence of O−H stretching vibration at 3360 cm−1 suggest that the grafting of the molecules to the Ta-perovskite layers has remained essentially intact during the click reaction. Yet, a small shoulder at ∼1050 cm−1 in the spectra of hexyl-click⊂HST and benzyl-click⊂HST suggests the presence of a small amount of alcohol that has been ungrafted during the in situ reaction. Solid-state 13C CP/MAS NMR spectra of the two products are shown in Figure 6, along with the starting HCC⊂HST.

leaching of the grafted alkyne-alcohol precursor is thus relatively moderate. The organic content decreases from 0.7 alcohol per Ta2 unit in HCC⊂HST to 0.5 and 0.6 for hexylclick⊂HST and benzyl-click⊂HST, respectively. This partial leaching may be due to traces of water present during the in situ click reaction. Finally, the molecules formed in situ were further deintercalated by alkaline treatment (6 M NaOH, 80 °C, 48 h). As reported for Dion−Jacobson phases,34 this treatment leads to hydrolysis of the R−O−Ta bond. The solid, which separates from the aqueous suspension via centrifugation, is badly crystallized (see Figure S3 in the Supporting Information), with the persistence of the characteristic out-ofplane reflections of the perovskite phase, and large reflections at lower angles, attributed to the 00l reflection. IR spectroscopy shows the disappearance of the signals of the organic phase (see Figure S4 in the Supporting Information). EDX analysis reveals the presence of a large amount of Na, with a ratio Na/Ta close to 1/3, suggesting that this phase may be the protonated HST phase, where protons have been partially replaced by Na+ cations. The basic aqueous suspension was subsequently extracted with organic solvent and dried. The 13C NMR spectra in solution (CDCl3) of the organic phase, which is obtained after evaporation of the solvent, is very similar to the one of the corresponding hybrid in the solid state (see Figures S5 and S6 in the Supporting Information). The only difference concerns the position of the signal of the carbon bearing the anchoring oxygen (labeled as “A”), which is shifted upfield (by ∼11 ppm), as expected for free alcohol α-carbon.

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CONCLUSIONS In conclusion, the microwave-assisted grafting of an alcohol bearing a reactive terminal alkyne group into a protonated Aurivillius phase H2Bi0.1Sr0.85Ta2O7 has been described. The efficient post-synthesis modification of this phase by means of in situ microwave-assisted copper(I)-catalyzed alkyne−azide cycloaddition (CuAAC) has further been carried out. The microwave-assisted CuAAC in situ reaction, which has been used here, is fast and particularly efficient. It is worth underlining that the reaction occurs on the entire interlamellar spacing, without noticeable reactivity limitations due to potential difficulties for the azide reactant (even if bulky) and the Cu(I) complex catalyst to diffuse. This strategy completes the ones used up to now to functionalize layered perovskite oxides (amine insertion, alcohol, or phosphonic acid grafting). This post-synthesis modification approach allows one to consider the functionalization of layered perovskites by a much broader range of molecules and, hence, expand the properties and functionalities of the obtained hybrids.

Figure 6. 13C CP/MAS solid-state NMR spectra of HCC⊂HST (blue), benzyl-click⊂HST (green), and hexyl-click⊂HST (red).

The signal of the carbon bearing the anchoring oxygen (denoted as “A” in Figure 6) remains unshifted at 73 ppm in all compounds, confirming the grafting of the molecules. Yet, a small signal at 62 ppm (marked with an asterisk) may indicate that a tiny amount of molecules has been ungrafted during the reaction, corroborating the observation from IR spectroscopy. Despite several attempts, this ungrafting seems unavoidable. Finally, in addition to the presence of the signals of the aliphatic or aromatic moieties of the azido reactants, one observes a downfield shift of signals D and E of the terminal alkyne group from 85 ppm and 70 ppm to ca. 150 and 120 ppm. This shift is a clear indication of the formation of a triazole moiety.91 The position of signal E, at ∼120 ppm, indicates the formation of a unique regio-isomer of the 1H-1,2,3-triazole, i.e. the 1,4disubstituted isomer, and not the 1,5-disubstituted isomer for which signal E would be expected at ∼133 ppm, as expected for a copper(I)-catalyzed 1,3-dipolar cycloaddition.91 The C/N ratios, determined from elemental analyses, are in accordance with the expected values for an in situ triazole formation by click reaction (experimental values, 3.8 and 4.2; expected values, 3.7 and 4.0 for hexyl-click⊂HST and benzylclick⊂HST, respectively). The organic content can be determined from thermogravimetric analysis (TGA) (see Table S1 and Figure S2 in the Supporting Information) and, along with elemental analysis, the formulas deduced for hexylclick⊂HST and benzyl-click⊂HST are as follows: H1.5Bi0.1Sr0.85Ta2O6.5(OC11N3H20)0.5·0.3H2O and H1.4Bi0.1Sr0.85Ta2O6.4(OC12N3H14)0.6·0.6H2O, respectively. The

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.6b01600. Elemental analyses, TGA curves, SEM images, 13C NMR in solution of 4-pentyn-1-ol and of the deintercalated molecules, and XRD patterns and IR spectra of the inorganic phase after alkaline treatment (PDF) E


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Inorganic Chemistry

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Author Contributions

The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS The authors thank the CNRS, the Université de Strasbourg, the Université de Clermont-Ferrand and the Agence Nationale de la Recherche (Contract No. ANR-14-CE07-0004-01) for financial support, the Chemistry Department of the CNRS and the Région Alsace for the Ph.D. grant of Yanhui Wang, and the icFRC (http://www.icfrc.fr) for support. The present work is part of the research activity supported by the European COST action MP1202: HINT (Rational Design of Hybrid Organic−Inorganic Interfaces: The Next Step Towards Advanced Functional Materials, http://www.cost-hint.cnrs.fr). The authors thank D. Burger and C. Kiefer for technical assistance.

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Post-Synthesis Modification of the Aurivillius Phase Bi2SrTa2O9 via In

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