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Topochemical Route from Supramolecular to Hybrid Materials: Tetraphenylmethane-based Tectons and Lanthanum Phosphonate Derivative Olivier Pérez, Clarisse Bloyet, Jean-Michel Rueff, Nicolas Barrier, Vincent Caignaert, Paul-Alain Jaffres, and Bernard Raveau Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.6b00823 • Publication Date (Web): 31 Oct 2016 Downloaded from http://pubs.acs.org on November 9, 2016

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Crystal Growth & Design is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

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Crystal Growth & Design

O

O

HO P HO

P

OH OH

O

O

HO P HO

P

RO RO P O OH OH

OR P

OR

O O P OH HO

O

OH

RO RO P O

OR P

OR

O

A

B

1a R = Et 1b R = H

ACS Paragon Plus Environment

TPM


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Structure of the ester [C6H4PO(OEt)2]4C.H2O. Red, grey and white balls are referring to oxygen, carbon and hydrogen atoms respectively. PO3C environments are represented using green tetrahedra. The different dashed lines are visualizing H bonds between water molecules and PO3C tetrahedra (purple), or free water molecules (orange), or the ethyl groups (dark blue) and also between the latter and the PO3C tetrahedra (dark green). 1249x833mm (96 x 96 DPI)


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Structure of the acid [C6H4PO(OH)2]4C.2H2O: Red, grey and white balls are referring to oxygen, carbon and hydrogen atoms respectively. PO3C environments are represented using green tetrahedra. Dark green dashed lines are visualizing H bonds between PO3C tetrahedra and phenyl groups. 1249x833mm (96 x 96 DPI)



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Structure of the lanthanum phosphonate La[C6H4PO7/4(OH)5/4]4C.4H2O: Red, blue, grey and white balls are referring to oxygen, lanthanum, carbon and hydrogen atoms respectively. PO3C environments are represented using green tetrahedra. The gold circle corresponds to the lanthanum environment reported in the supporting information (Fig. S5-1b). The different dashed lines are visualizing H bonds respectively between two phosphonate PO3C groups (light blue), between water molecules and PO3C tetrahedra (purple), or free water molecules (orange), or the phenyl groups (dark blue) and between the latter and the PO3C tetrahedra (dark green). 206x155mm (150 x 150 DPI)


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The ester [C6H4PO(OEt)2]4C.H2O: arrangements of the TPM and PO3C tetrahedra forming columns parallel to c. Hydrogen bonds are represented by dashes lines between water molecules and PO3C tetrahedra (purple), or free water molecules (orange), or the ethyl groups (dark blue). 253x208mm (96 x 96 DPI)



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Topochemical Route from Supramolecular to Hybrid Materials: Tetraphenylmethane-based Tectons and Lanthanum Phosphonate Derivative Olivier Perez*,† Clarisse Bloyet,† Jean-Michel Rueff, † Nicolas Barrier,† Vincent Caignaert,† Paul-Alain Jaffrès § and Bernard Raveau,†. † CRISMAT, UMR CNRS 6508, ENSICAEN, Université de Caen Basse-Normandie ; 6 boulevard du Maréchal Juin, 14050 Caen, France, § CEMCA CNRS UMR 652, Université de Brest, IBSAM, 6 Avenue Victor Le Gorgeu, 29238 BREST, France


1

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KEYWORDS : hybrid, hydrothermal synthesis, structure, phosphonate.

ABSTRACT: Three members of the tetraphenylmethane (TPM) phosphonate based family have been obtained: the acid [C6H4PO(OH)2]4C.2H2O, the ester [C6H4PO(OEt)2]4C.H2O and the lanthanum phosphonate La[C6H4PO7/4(OH)5/4]4C.4H2O. Their structures were revealed to be closely related to those of a series of tetrahedral tetraphosphonic acids templated or not by organic bases. The structural analysis of all these compounds, allows their topochemical behaviour to be understood on the basis of the existence of close packed columns, built up of CsCl-like pseudo-cubic bricks, involving one tetrahedral [C6H4]4C group surrounded by four PO3C tetrahedra. This model, complementary to the methodology developed by Zareba et al, paves the way to the research of TPM-based metal phosphonates in view of generating columnar hybrid materials.

INTRODUCTION Among the numerous hybrid frameworks, the metal organophosphonates represent an important class of materials, with an extremely rich chemistry (see for a review [1,2,3,4]) covering a wide range of applications, such as biotechnology, catalysis, gas storage, and photoluminescence.

1,5,6,7

Besides, the chemistry of supramolecular materials containing

phosphonic acids is also quite impressive.

8,9,10,11,12,13,14,15,16,17,18,19

Although the crystal

engineering of these two classes of materials is based on the geometry and size of the phosphonic acid molecule involved in the synthesis, the structural relationships between them have been little studied. In this respect, the tetrakis[4-(dihydroxyphosphoryl)phenyl]methane (1b) acid (Scheme 1)16,19 should be considered as a model precursor for the topochemical synthesis of


2


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supramolecular materials and metal phosphonates with closely related structures. This statement is supported by the large size of the tetrahedral tetraphenyl methane (TPM) unit [C6H4]4C

20

(Scheme 1) which can govern the crystal chemistry of the TPM [C6H5]4C derivatives. Indeed, the functionalization of the four C apices with a phosphonate or a phosphonic acid group produces respectively the compounds 1a and 1b (Scheme 1). In these compounds the PO3C tetrahedra are themselves displayed at the corners of a larger tetrahedral tetraphenyl phosphonic methane unit (TPPM). To date, no example of metal organophosphonate with a [C6H5]4C TPM core is known, but a copper organophosphonate made from a closely related tetrahedral adamantane-based core functionalized with four 4-phosphono-phenyl groups was reported. 9 This copper-based material featured a fourfold interpenetrated diamondoïd network. Other works have also used this adamantane-based tetraphosphonic acid for the preparation of mesoporous materials

21

or

supramolecular self-assemblies. 22 Based on the above considerations, and after studying the construction of supramolecular assemblies

17

(Compound A, Scheme 1) or hybrid materials from rigid poly-phosphonic acid or

phosphono-carboxylic compounds

23

(Compound B, Scheme 1) in which the rigid platform was

constituted by a benzene ring, we have investigated the chemistry of the TPM supramolecular materials for their fascinating tetrahedral geometry and we have embarked in the synthesis of the lanthanum TPM derivative. Herein, we report on the original structures of three new compounds: tetrakis[4-(dietoxyphosphoryl)phenyl]methane [C6H4PO(OEt)2]4C.H2O (Scheme 1a), tetrakis[4(dihydroxyphosphoryl)phenyl]methane [C6H4PO(OH)2]4C.H2O (Scheme 1b) which is a new crystalline

form

of

the

acid,

and

one

lanthanum

TPM

tetraphosphonate

La[C6H4PO7/4(OH)5/4]4C.4H2O. Comparing the original structures of these three compounds with


3

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those of other tetrahedral TPM-based tectons,

18

we show the existence of close structural

relationships, paving the way for the tailoring of other metal tetraphenylmethane phosphonates. EXPERIMENTAL SECTION The synthesis of tetrakis[4-(dietoxyphosphoryl)phenyl]methane (Scheme 1a) and tetrakis[4(dihydroxyphosphoryl)phenyl]methane (Scheme 1b) was achieved following an adaptation of a reported procedure. 18 Details are available in supporting materials. La[C6H4PO7/4(OH)5/4]4C.4H2O was obtained by hydrothermal synthesis according to the following procedure. In a 25 mL PTFE liner were dissolved in 15 mL of distilled water 1 equivalent of the phosphonic acid [C6H4PO(OH)2]4C (0.05 g, 0.078 mmol) and 3 equivalents of Lanthanum(III) nitrate hexahydrate (0.101 g, 0.233 mmol). The PTFE liner was then transferred in a Berghof Pressure Digestion Vessel DAB-2 and heated from room temperature to 200 °C in 10 hours, left at 200 °C during 50 hours and cooled from 200 °C to room temperature in 40 hours. After filtration, a mixture of white powder and transparent crystals was obtained as final material. This mixture was washed with water and dried with ethanol. X-ray diffraction study. After a selection of single crystals based on the diffraction quality, X-ray single crystal diffraction experiments were performed for the [C6H4PO(OEt)2]4C.H2O ester and the La[C6H4PO7/4(OH)5/4]4C.4H2O phosphonate at room temperature, using Mo Kα radiation produced with a microfocus Incoatec Iµ sealed X-ray tube on a Kappa CCD (Bruker-Nonius) diffractometer equipped with an Apex2 CCD detector. Details of the data collection are summarized in Table S4a. Data were corrected from absorption using SADABS program

24


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developed for scaling, corrections for twin and area detector data. The structure was determined using SUPERFLIP

25

. Some C and O atoms are missing. However these first models allow the

phasing of the structure factors and then the calculation of Fourier difference syntheses; the analysis of the electronic residues allows the location of all the missing atomic sites. [C6H4PO(OEt)2]4C.H2O ester and La[C6H4PO7/4(OH)5/4]4C.4H2O were refined with SHELXL used with the graphical user interface Olex2

27

and Jana2006

28

26

respectively. Harmonic atomic

displacement parameters were considered for La, P, O and C species. Hydrogen atoms were geometrically added; distance and angle restrains were introduced for H belonging to water molecule and these H positions were refined. The electroneutrality of the proposed formula La[C6H4PO7/4(OH)5/4]4C.4H2O results from the balance between three positive charges coming from the lanthanum atom and three negative charges coming from three different monodeprotonated

phosphonic

acid

functional

groups.

In

the

structure

of

La[C6H4PO7/4(OH)5/4]4C.4H2O, the five protons of the phosphonic acid groups are statistically distributed on the eight possible positions. In order to consider all these protonation sites, these eight positions were protonated in the La[C6H4PO7/4(OH)5/4]4C.4H2O structure depicted in Figure 1c. Atomic positions, ADP parameters and interatomic distances are listed in Tables S4b1-2 and S4c1-3. For the polycrystalline acid [C6H4PO(OH)2]4C.2H2O (see TGA results in Figure S-2-1 for the determination of the water contents) the powder X-ray diffraction (PXRD) data were first recorded with a laboratory Bruker D8 advance diffractometer using monochromated Cu-Kα1 radiation (λKα1 = 1.5406 Å) and a LynxEye detector. High resolution synchrotron data were collected on the CRISTAL beamline (Synchrotron SOLEIL, France) in Debye-Scherrer mode.


5

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The powder sample was introduced in a glass capillary tube of 0.5 mm diameter, and the PXRD pattern was registered at room temperature using a monochromatic wavelength of 0.7241 Å. The unit-cell parameters were found with the DICVOL06 program

29

using the laboratory

PXRD data. The PXRD pattern was indexed in a monoclinic unit cell with parameters given in the Table 1 and following figures of merit: M(20) = 33.4, F(20) = 102.8 (0.0034, 58). The first Lebail fits revealed the presence of anisotropic peak broadening and systematic reflection conditions consistent with the C2/c and Cc space groups. Preliminary attempts to solve the structure with the FOX

30

program in these two space groups from synchrotron data failed.

Nevertheless very small shouldering of the reflections (202) and (113) might correspond to the reflections (212) and (210), respectively suggesting the P21/n space group. However the great complexity of the profile of the synchrotron pattern did not allow this ambiguity to be lifted. Furthermore since this complex profile could not be fitted with Fox,

30

the structure was solved

from the PXRD laboratory data in the P21/n space group and then refined using JANA2006

28

from the synchrotron data. The anisotropic peak broadening seen on the synchrotron pattern was treated with the phenomenological model developed by Stephens. refinements were performed, assuming the model found with FOX

31

30

The first Rietveld in P21/n and some

geometrical restrictions: the geometry of the phenyl groups was fixed; each P-atom with their linked phenyl group and the central C2-atom had to stay in the same plan. The symmetry of this model was checked with the ADSYM tool available in the PLATON program.

32

A higher

symmetry was found and so the last Rietveld refinements were carried out in the C2/c space group. The geometrical restrictions indicated previously were maintained and Berar’s correction was systematically applied for standard uncertainty calculations. The final refinements gave the following factors: Robs = 5.61%; RwP = 4.75%; gof = 2.23. The PXRD synchrotron pattern


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corresponding to the final refinement is available as supporting material (Fig. S3-1). The presence of water molecules cannot be confirmed by this study. Atomic positions and interatomic distances are listed in Tables S3-1 to S3-3. Hirshfeld Surfaces and Crystal voids. The CrystalExplorer program

33

was used in order to generate the Hirshfeld surfaces and the

crystals voids on the three structures. Both were calculated respectively in very high resolution and in high resolution using a standard void cluster mode (i.e. unit cell + 5Å) and an isovalue of 0.002 e.au-3. The percentage of void corresponds to the ratio of the volume calculated by CrystalExplorer program by the volume of the cell. This program is also used in order to generate fingerprints plots

34

which show any contact types within the structures from the di-de

data points which represent the distances from an atom inside the molecule to the surface or from the surface to another molecule respectively.

RESULTS AND DISCUSSION Tetrakis[4-(diethoxyphosphono)-phenyl]methane [C6H4PO(OEt)2]4C.H2O, was synthesized from tetrakis(4-bromophenyl)methane and triethylphosphite by adapting the protocol previously described by Zareba et al. 16,18 This well crystallized compound was used for X-ray single crystal study and for the synthesis of the corresponding acid [C6H4PO(OH)2]4C.2H2O (see supporting materials). The structures of the three compounds (Fig. 1) are closely related to each other, in spite of their different symmetry and cell parameters (Table 1). In all of them, the tetrahedral TPM units share


7

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their four apices with a PO3C phosphonate tetrahedron forming then larger tetrahedral tetraphosphonic phenyl methane (TPPM) units (Fig. 2). The comparison of the three structures shows that the ester (Fig. 1a), the acid (Fig. 1b) and the La phosphonate (Fig. 1c) are all built up of similar TPPM units, with various orientations of their PO3C tetrahedra, and forming phenyl embraces (PE) similar to those described by Zareba et al.

16

This viewpoint is confirmed by the

calculation of the geometrical parameters corresponding to the shortest Ccore…Ccore distances between central atoms of TPM units, and to the mean colinearity angle (Cipso- Ccore…Ccore) as defined by previous authors.

16,35

The Ccore…Ccore distances comprised between 7.13 and 7.66 Å

and the colinearity angles smaller than 130 ° are indeed characteristic of 4PE interactions between tetrahedral units (Table 2). Thus, those phenyl embraces are similar to those previously described for the tetrakis phosphonyl phenyl methane pyridine and bipyridine.

16

Consequently

these four-fold phenyl embraces form linear TPPM columns (Fig. 3), that will be discussed further in a different way for the comparison of the closely related structures. The analysis of the hydrogen bonds in the perpendicular plane to these columns (Fig. 1) shows that the PO3C tetrahedra play an important role in the cohesion of the structure in this plane. Each PO3C tetrahedron of one TPPM unit forms strong hydrogen bond either with H2O molecules or with the phenyl group of the next TPPM unit according to the scheme “P-O…H-O” or “P-O…H-C” respectively. In the ester (Fig. 1a), the strongest hydrogen bonds are formed between the PO3C tetrahedra and the inserted H2O molecules, forming the sequence “P-O…H-O-H…O-H-H…OP” between two neighbouring TPPM units along ܽԦ (or ܾሬԦ). The corresponding O...H distances (Table 3), comprised between 1.799 Å and 2.138 Å show that both H2O molecules and PO3C tetrahedra play a primordial role in the cohesion of this 2D hydrogen bond network. For the acid (Fig. 1b), TPPM units are directly connected to each other by hydrogen bonds between one


8


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PO3C tetrahedron of one TPPM unit and one C6H5 cycle of the next unit according to the sequence “P-O…H-C” along ܿԦ. It results in H-bonded tapes running along ܿԦ characterized by rather short O…H bonds of 2.709 Å (Table 3). The cohesion along ܽԦ between these tapes cannot be discussed here, since the H2O molecules of this compound could not be localized. Nevertheless, we can affirm that the cohesion along this direction should be insured by hydrogen bonds between the PO3C tetrahedra and the H2O molecules. In the case of the La phosphonate (Fig. 1c), it is clear that the ionocovalent La-O bonds between the PO3C group and lanthanum play a major role in the stability of the 2D lattice, each La3+ cation being linked to four TPPM units with La-O distances ranging from 2.38 Å to 2.46 Å (Table S4c-3). Moreover additional Hbonds between the PO3C tetrahedra of each TPPM unit and the phenyl group of the next unit are running along ܽԦ, with the sequence “P-O…H-C”, corresponding to rather short O…H distances of 2.713 Å (Table 3). The latter form tapes parallel to ܽԦ, reinforcing the cohesion of the structure along this direction. In order to get insight into the nature of the bonds within the TPPM columns, we have analysed the geometry and the interactions between the molecules and ligands in those columns (Fig. 3). The stacking of the tetrahedral TPM units is practically identical in the three structures. Two successive TPPM tetrahedra (coloured in green and pink) are practically interpenetrated, with distances between their successive central C atom ranging from 7.66 Å for the ester [C6H4PO(OEt)2]4C.H2O (Figure 3a), to 7.35 Å for the acid [C6H4PO(OH)2]4C.2H2O (Fig. 3b) and to 7.13 Å for the lanthanum phosphonate (Fig. 3c). This shows that in the three columns, the TPPM groups tend to stack in the form of a close packed array. In fact, the important feature concerns the existence of strong hydrogen bonds (blue dotted lines) between phenyl groups of one TPPM tetrahedron (e.g. green) and the PO3C tetrahedra of the next one (e.g. pink) and vice-


9

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versa. It is this characteristic which governs the topochemistry of these compounds, ensuring the cohesion of each TPPM column. Note that these intra-column hydrogen bonds vary from one compound to the other, following the very flexible orientation of the phenyl planes with O…H distances comprised between 2.479 Å and 2.664 Å (Table 3). In fact, they depend on the orientation of the PO3C tetrahedral groups, which is itself dependent on the inter-columns hydrogen bonds. The consideration of the Hirshfeld Surface (HS)

36

of the phenyl embraces which form these

columns shows that the shape index mapped into HS of these three compounds (Fig. 3d-e-f) is characteristic of 4PE interaction as previously observed for tetrakis phosphonyl phenyl pyridine and bipyridine polymers. 16 Indeed, the complementary double red and blue elongated spots that are observed on the HS of these three compounds can be assigned to the C-H…π interactions. Thus, each molecule is engaged into 4 PE’s, forming eight donor (blue spot) and acceptor (red spots) C-H…π interactions with its neighbours. The two-dimensional fingerprint plots of these embraces (Fig. 4) show that the hydrogen bonds O---H are dominant (20.2 % to 39.4 %) with respect to the C---H contacts (10.2 % to 13.5 %) (Table 4). Thus, the C-H…π interactions, which represent for a main part the C---H contacts, play also a significant role in the stability of these columns. Details on the different intermolecular interactions present in those 4PE’s compounds are referred in Table 4 and the different area of these contributions on their respectives fingerprint plots can be obtained in Fig. S5-2. The crystal voids mapping shows that the structure of the ester and acid are both close packed with 22.40 % and 13.86 % of free space left for water molecules (not included in the


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calculations), whereas small tunnels are available in the La-phosphonate (31.58 %), that are partially occupied by La3+ cations and H2O molecules (both not included in the calculations) (Fig. S5-3). The topochemistry of these compounds can be understood by using the representation of figure 2, i.e. replacing the TPM [C6H4]4C core by a large C4 tetrahedron. Thus, the structures can be described by the assemblage of TPM and PO3C tetrahedra (PT). In the three structures, these TPM tetrahedra are preferentially stacked along one direction, forming remarkably identical single columns running along c in the tetragonal ester (Fig. 5a), along b in the monoclinic acid (Fig. 5b) and in the monoclinic lanthanum phosphonate (Fig. 5c). In these columns each PO3C tetrahedron shares one apex with one TPM tetrahedron, but the orientation of the PO3C tetrahedra is different in the three structures. Importantly, the orientation of the columns of TPM tetrahedra is different in the three structures. In the tetragonal ester [C6H4PO(OEt)2]4C.H2O, the TPM [C6H4]4C tetrahedra of the successive columns along the a and b directions are turned by 90°

rotation

around

c

alternately

(Fig.

5a),

whereas

in

the

monoclinic

acid

[C6H4PO(OH)2]4C.H2O the columns keep the same orientation along c but are turned 90° along a (Fig. 5b). In the monoclinic lanthanum phosphate the relative orientation of the columns is similar to that observed in the phosphonic acid: along the c direction the TPM tetrahedra of the successive columns are turned alternately by a 90° rotation around b, whereas they are all oriented parallel in the a direction (Fig. 5c). The above analysis shows the isolated character of the TPPM columns and raises the question of the nature of the bonding between those columns in order to ensure the structure stability. In order to answer this question we have to examine the influence of the ligands or additional molecules or cations for the creation of hydrogen bonds in the structure.


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In the ester [C6H4PO(OEt)2]4C.H2O, two ethoxy groups are connected to each phosphonate group, forming isolated neutral [C6H4PO(OEt)2]4C molecules. These ethoxy groups increase the distances between the columns and as a consequence, are too far apart from the PO3C groups to form strong hydrogen bonds. However, due to their large size, free space is available between the TPPM columns, where H2O molecules can be interleaved. The latter play a significant role in the stability of the structure, since they form helical chains running along c (Fig. S5-1a), so that hydrogen bonds appear between them, but also with oxygen atoms of the phosphonate groups which are known to be a good hydrogen bond acceptor 37 (see Table 3) In the hydrated acid [C6H4PO(OH)2]4C.2H2O, due to the replacement of ethoxy groups by hydroxy, adjacent columns are much closer to each other, and as a consequence, the cohesion of the structure is directly insured by hydrogen bonds between two adjacent columns, i.e. C-H--O=P bonds as previously observed,

38

between two adjacent columns (see Table 3, Fig. 1b).

Water molecule expected from the chemical analysis but not evidenced in the structural study should also play a role in this cohesion. The lanthanum phosphonate La[C6H4PO7/4(OH)5/4]4C.4H2O displays the same TPPM columns as the two other phases, but exhibits POO7/4(OH)5/4C tetrahedra, leading to tetrahedral anionic groups [C6H4POO7/4(OH)5/4]4C]3- . This confers the possibility to install ionic bonds between the columns and foreign cations. Consequently, this structure (Fig. 3c) differs from the two others by the fact that the [C6H4POO7/4(OH)5/4]4C]3- anionic groups are interconnected through La3+ cations, so that the cohesion of the structure is mainly ensured by ionic bonds, leading to a much higher stability. In fact, La3+ exhibits an eight-fold coordination, forming distorted bicapped LaO4(H2O)4 octahedra (Fig. 3c). Thus, in this structure the LaO4 basal planes of the bicapped octahedra share their four oxygen apices with the tetrahedral anionic groups, whereas the four


12


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H2O corners are free (Fig. 3c). It results in a three-dimensional framework, where both ionic and strongly covalent bonds alternate. Thus, besides the ionic La-O bonds there exist numerous hydrogen bonds via O, OH species between the POO7/4(OH)5/4C tetrahedra (see Table 3 and Fig. 1c). Let us signal that besides the coordination water, the structure also hosts free H2O molecules. The consideration of La and its four surrounding PO3C tetrahedra (gold circle on Figure 1c) shows that the free H2O molecules and the structural H2O reinforce the stability of the structure along ܾሬԦ (Fig. S5-1b). The H---O distances are indeed ranging from 2.111 to 2.530 Å (Table 3). The analysis of the crystal structure of the supramolecular compounds, determined by Zareba et al

16,18

and Schütrumpf et al

19

shows that three of them are closely related to the present

phases. Very similar TPPM columns can be indeed identified for the anhydrous acid [C6H4PO(OH)2]4C and for the supramolecular polymers [C6H4PO1+x(OH)2-x]4C.C5H6N, and [C6H4PO(OH)2]4C.(C10H8N2)2 templated by pyridine and bipyridine respectively. 16 Thus, the TPPM columns represent the driving force for the generation of these six different structures. The high stability of these columns can be easily understood by considering the unidimensional pseudo-cubic lattice formed by the PO3C tetrahedra (Fig. 6). Each pseudo-cube (pC) is built up of two sets of (PO3C)4 tetrahedra (green and pink colours) and the central carbon (black) of the TPM sits at the centre of the pC’s forming four “bonds” with only one set of (PO3C)4 tetrahedra, i.e. either green or pink alternately along the column. Representing the PO3C groups and the central carbon (surrounded by its diphenyl ligands) by spheres, we observe that the structure of these columns consists of pC bricks that are directly derived from the cubic centred CsCl structure, by a tetragonal distortion. To summarize, the structure of these six compounds can be described as the assemblage of close packed columns, with a square section


13

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(Fig. 7). In each column, the pairs of (PO3C)4 tetrahedra which form the pC bricks are always oriented at 90°, but the relative orientation of the columns with respect to each other depends on the nature of the inter-columns hydrogen bonds. In the ester [C6H4PO(OEt)2]4C.H2O, one observes a 90° rotation of all the columns alternately (Fig. 7a), whereas in anhydrous [C6H4PO(OH)2]4C acid and in the bipyridine templated polymer [C6H4PO(OH)2]4C.(C10H8N2)2 all the columns exhibit the same orientation (Figure 7c, f). All the other compounds consist of rows with a parallel orientation, but two successive rows are turned 90° (Fig. 7b, d, e). It is quite remarkable that rather large molecules such as pyridine or even bipyridine, can be introduced between the columns, forming additional hydrogen bonds between them, without any destruction of the pC bricks. The structural analysis of all the tetrahedral tectons synthesized by Zareba et al 16

shows that much larger amounts of template are required to split these bricks, as exemplified

for several adducts discovered by these authors. Remarkably, the great ability of the tetraphenyl methane units (TPM) to form such close packed columns can be transposed to tetrasulphonic (TS) units which exhibit a very similar tetrahedral geometry. Indeed, the analysis of the structure of tetrasulphonic acid [C6H4SO3H]4C.12H2O

39

shows that it consists of very similar CsCl-type

columns (Fig. 7g), opening the topochemical route for the generation of various tetrasulfonic acid derivatives. CONCLUSIONS Besides the anhydrous phosphonic acid [C6H4PO(OH)2]4C, recently synthesized and studied by Zareba et al

16,18

and Schütrumpf et al

19

a second form of acid containing water

[C6H4PO(OH)2]4C.2H2O with a closely related structure has been synthesized. The structure of the corresponding ester [C6H4PO(OEt)2]4C.H2O, involved in the first step of preparation of the acids has been shown to be closely related to those of these compounds. Starting from the acid,


14


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Page 40 of 50

the possibility to generate a hybrid phosphonate La[C6H4PO7/4(OH)5/4]4C.4H2O, containing lanthanum, with a closely related structure, has been demonstrated. Considering the tetrahedral nature of the tetraphenylmethane (TPM) group and its association with PO3C tetrahedra, a model for the synthesis of closely related frameworks, is set up in complement to the attractive methodology developed by Zareba et al. 16,18 This topochemical model is based on the fact that the tetrahedral TPM molecules and phosphonate groups form a unidimensional pseudo-cubic body centred stacking, derived from the CsCl structure. The resulting square section columns are the basis of the structure of these compounds, and their interconnection through hydrogen and possibly ionic bonds is quite flexible. This opens the route to the introduction of numerous species going from lanthanides to transition metal cations, in view of the creation of hybrid materials with various architectures and properties. Importantly we show that this topochemical route can be extended to other supramolecular materials, as shown for other tetrasulfonic acid derivatives.


15

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SCHEMES

Scheme 1. Chemical structure of some polyfunctionnal rigid phosphonic acid precursors


16


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Page 42 of 50

FIGURES

Figure 1a: Structure of the ester [C6H4PO(OEt)2]4C.H2O. Red, grey and white balls are referring to oxygen, carbon and hydrogen atoms respectively. PO3C environments are represented using green tetrahedra. The different dashed lines are visualizing H bonds between water molecules and PO3C tetrahedra (purple), or free water molecules (orange), or the ethyl groups (dark blue) and also between the latter and the PO3C tetrahedra (dark green).

Figure 1b: structure of the acid [C6H4PO(OH)2]4C.2H2O: Red, grey and white balls are referring to oxygen, carbon and hydrogen atoms respectively. PO3C environments are represented using green tetrahedra. Dark green dashed lines are visualizing H bonds between PO3C tetrahedra and phenyl groups.

Figure 1c: Structure of the lanthanum phosphonate La[C6H4PO7/4(OH)5/4]4C.4H2O: Red, blue, grey and white balls are referring to oxygen, lanthanum, carbon and hydrogen atoms respectively. PO3C environments are represented using green tetrahedra. The gold circle corresponds to the lanthanum environment reported in the supporting information (Fig. S5-1b). The different dashed lines are visualizing H bonds respectively between two phosphonate PO3C groups (light blue), between water molecules and PO3C tetrahedra (purple), or free water molecules (orange), or the phenyl groups (dark blue) and between the latter and the PO3C tetrahedra (dark green).


17

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Figure 2: Representation of the TPM [C6H4]4C core and of the PO3C group by a large C4 tetrahedron (continuous line) and four small tetrahedra. The larger tetrahedra TPPM unit is represented by red dashed lines.

Figure 3. Geometry and representation of the Hirshfeld surface with shape index properties mapped

onto

the

surface

of

the

ester

[C6H4PO(OEt)2]4C.H2O

(a,

d),

the

acid

[C6H4PO(OH)2]4C.2H2O (b, e) and the lanthanum phosphonate La[C6H4PO7/4(OH)5/4]4C.4H2O (c, f). Hydrogen bonds between the phenyl radicals of one TPM tetrahedron and the PO3C groups of the adjacent interpenetrated TPM’s are represented on a, b, c of the figure whereas the C-H---π interactions are put in highlight on d, e, f of the figure.

Figure 4. Two-dimensional Fingerprint plots representing atoms contacts with their overall percentage in (a) ester [C6H4PO(OEt)2]4C.H2O, (b) acid [C6H4PO(OH)2]4C.2H2O and (c) lanthanum phosphonate La[C6H4PO7/4(OH)5/4]4C.4H2O. di-de data points represent respectively distances from the surface to the closest atom inside the molecule or to another molecule. Pictures are generated with the CrystalExplorer program.

Figure 5a: The ester [C6H4PO(OEt)2]4C.H2O: arrangements of the TPM and PO3C tetrahedra forming columns parallel to c. Hydrogen bonds are represented by dashes lines between water molecules and PO3C tetrahedra (purple), or free water molecules (orange), or the ethyl groups (dark blue).


18


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Page 44 of 50

Figure 5b: The acid [C6H4PO(OH)2]4C.2H2O: arrangements of the TPM and PO3C tetrahedra forming columns parallel to b.

Figure 5c: The lanthanum phosphonate La[C6H4PO7/4(OH)5/4]4C.4H2O: arrangements of the TPM and PO3C tetrahedra forming columns parallel to b. The latter are interconnected by rows of LaO4(H2O)4 bicapped octahedra (cyan colour).

Figure 6: Building scheme of the pseudo cube in the ester [C6H4PO(OEt)2]4C.H2O.

Figure 7: Schematic representation using the pseudo cube of: a) ester [C6H4PO(OEt)2]4C.H2O; b) hydrated acid [C6H4PO(OH)2]4C.2H2O; c) anhydrous acid [C6H4PO(OH)2]4C after atomic positions in reference 19; d)

Lanthanum phosphonate La[C6H4PO7/4(OH)5/4]4C.4H2O; e)

supramolecular polymer templated by pyridine after atomic positions in reference 16; f) supramolecular polymer templated by bipyridine after atomic positions in reference 16; g) tetrasulfonic acid [C6H4SO3H]4C.12H2O after atomic positions in reference 39.


19

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Table 1. Cell parameters and space groups.

[C6H4PO(OH)2]4C.2H2O [C6H4PO(OEt)2]4C.H2O La[C6H4PO7/4(OH)5/4]4C.4H2O

a (Å) 18.3048(15) 25.1305(6) 21.5042(12)

Cell parameters b (Å) c (Å) 7.3677(4) 21.2685(18) 25.1305(6) 7.6607(4) 7.1347(4) 22.2125(12)

Space group

β (°) 111.276(4)

C2/c I41/a P2/a

89.924(3)

Table 2. Geometrical parameters.

[C6H4PO(OEt)2]4C.H2O [C6H4PO(OH)2]4C.2H2O [C6H4PO(OH)2]4C La[C6H4PO7/4(OH)5/4]4C.4H2O [C6H4PO1+x(OH)2-x]4C.C5H6N [16] C6H4PO(OH)2]4C.(C10H8N2)2 [16] [C6H4SO3H]4C.12H2O [39]

Distances between columns (Å) along : ഥ0] [100] [010] [001] [110] [1૚ 12.65 12.65 10.86 9.85 10.07 10.07 11.11 10.90 12.79 11.54 12.48 12.48 11.07 12.24

d(Ccore-Ccore) (Å)

α(Ccore-Ccore…Cispso) (°)

7.66 7.35 7.56 7.135 6.89 7.21 7.36

128.49 129.1 128.0 127.13 126.5 127.01 127.27

Table 3. Hydrogen bonds ensuring the cohesion of the structure for the ester [C6H4PO(OEt)2]4C.H2O, the acid [C6H4PO(OH)2]4C and the lanthanum phosphonate La[C6H4PO7/4(OH)5/4]4C.4H2O. intramolecular C-H---O-P 1.993-2.743 Å C-H---C 2.003-2.742 Å

C-H---C C-H---O-P

intramolecular 2.030-2.738 Å 2.614-2.675 Å

intramolecular La(H2O)---O-P 2.540 Å La(H2O)---(H2O)La 2.601-2.674 Å C-H---C 2.010-2.671 Å C-H---O-P 2.527-2.740 Å C-H---(P)-O-(La) 2.689 Å La(H2O)---(P)-O-(La) 2.639-2.732 Å

[C6H4PO(OEt)2]4C.H2O inter-columns H-O-H---O-P 2.138 Å C-H---OH2 2.674 Å H-O-H---OH2 1.799 Å [C6H4PO(OH)2]4C inter-columns C-H---O-P 2.709 Å La[C6H4PO7/4(OH)5/4]4C.4H2O inter-columns P-O---H-O-P 2.065-2.298 Å P-O---H-O-H 2.144-2.709 Å H2O---H-O-P 2.521-2.724 Å H2O---H-O-H 2.173-2.640 Å La-H-O-H---OH2 2.111-2.530 Å C-H---OH2 2.659-2.695 Å C-H---OP 2.713 – 2.740 Å

intra-columns C-H---C 3.122-3.246 Å C-H---O-P 2.664 Å

intra-columns C-H---C 3.188-3.290 Å C-H---O-P 2.479 Å intra-columns C-H---C 2.850-2.903 Å C-H---O-P 2.609 Å


20


Table 4. Contribution of the different intermolecular interactions in percentage present in a defined surface area of the ester [C6H4PO(OEt)2]4C.H2O, the acid [C6H4PO(OH)2]4C and the lanthanum phosphonate La[C6H4PO7/4(OH)5/4]4C.4H2O compounds. [C6H4PO(OEt)2]4C.H2O 10.2 C---H 68.5 H---H 20.2 O---H 1.1 C---C 0 O---O 0 C---O 100 Sum 99.5 Surface area included (%) * Lanthanum atom and water molecules are not taken in account. Contact types (%)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 46 of 50

[C6H4PO(OH)2]4C 13.5 14.2 39.4 0.6 26.3 6 100 99.1

La[C6H4PO7/4(OH)5/4]4C.4H2O 12.9 32.9 31.1 0 14.9 0.8 92.6 80.2*


21

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ASSOCIATED CONTENT Supporting Information. This material is available free of charge via the Internet at http://pubs.acs.org. Synthesis methods, X-ray powder and single crystal diffraction refinement details (CIF)

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. ACKNOWLEDGMENT The authors express their grateful acknowledgment for technical support to :Sylvie Collin from the CRISMAT laboratory, Erik Elkaim from the synchrotron SOLEIL, France and Sylvie Hernot form the CEMCA laboratory and the Service de RMN, UFR Sciences et Techniques, Université de Bretagne Occidentale, Brest. ABBREVIATIONS tetraphenylmethane (TPM) tetraphosphonic phenyl methane (TPPM) Hirshfeld Surface (HS)


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Page 48 of 50

For Table of Contents Use Only,

Topochemical Route from Supramolecular to Hybrid Materials: Tetraphenylmethane-based Tectons and Lanthanum Phosphonate Derivative Olivier Perez*, Clarisse Bloyet, Jean-Michel Rueff, Nicolas Barrier, Vincent Caignaert, PaulAlain Jaffrès and Bernard Raveau.

Synopsis: A large series of tetraphenylmethane (TPM) based phosphonates can be described from the stacking of tetrahedral TPM cores, forming CsCl-type close packed columns. This open a topochemical route for founding new hybrid materials with closely related structures, which can even be expanded to tetrasulfonic acid derivatives. REFERENCES

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