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Molecular tectonics: formation and structural studies on a 2-D directional coordination network based on a non-centric metacyclophane based tecton and zinc cation
J r me Ehrhart, Jean-Marc Planeix,* Nathalie Kyritsakas-Gruber and Mir Wais Hosseini* eo
Received 18th August 2009, Accepted 3rd December 2009 First published as an Advance Article on the web 15th January 2010 DOI: 10.1039/b917089h The combination of tectons based on the [1111]metacyclophane backbone blocked the 1,3-alternate conformation bearing two imidazoly or pyrazolyl groups located on the same side with metal halide complexes leads to the formation of either discrete metallmacrobicycles or innite 1-D coordination networks. The same backbone bearing two sets of two different coordinating poles composed of two pyridyl and two pyrazolyl units, owing to its non-centrosymmetric nature, forms a directional 2-D network packed in an anti-parallel fashion.

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Introduction
In the area of crystal engineering,1,2 the control of directionality is one of the most challenging tasks. Imposing a design of acentric orientation of the components which make up the crystal is of interest for exploiting, for example, directional physical properties such as photon or electron transfer processes in the solid state. Let us restrict ourselves to crystals composed of coordination networks3 made up of organic tectons4 and metal centres. For 3D networks, the formation of crystals results from the mutual interconnection of the organic and metallic parts in all three dimensions of space,5 whereas for 1- and 2-D networks, the generation of crystals may be described as resulting from the formation of the network by interconnection of the organic parts by metal centres and the packing of the networks in two and one directions of space respectively. We have previously reported the design and formation of directional 1-D networks in the crystalline phase.6-8 The design principle explored was based on combinations of acentric tectons possessing two differentiated coordination poles and metal cations.6 We have also succeeded in obtaining a polar crystal based on the use of a directional and chiral organic tecton.7 Furthermore, the same construction principle was used for surface patterning by directional 1-D networks.8 Here, we report on the design, formation and structural analysis of a directional 2-D coordination network formed upon combining an acentric tecton based on the [1111]metacyclophane backbone bearing two pyrazolyl and two pyridyl units and ZnCl2 .

coordination patterns, which dene the structural nodes of the assembly, are translated into one direction of space, for 2-D, they are translated into two directions of space. One of the possibilities for the design of directional 2-D architectures can be based on an acentric organic tecton offering four differentiated coordinating sites located on a backbone and oriented in a divergent fashion (Fig. 1(a)). Within this category, one may consider a tecton bearing two different sets of two monodentate coordination poles (Fig. 1(a)).

Fig. 1 Schematic representation of the formation of non-centric (b) and centric (c) 2-D coordination networks formed upon combination of a non-centric tecton (a) bearing two different sets of two coordinating sites with a metal centre offering two coordination sites and syn-parallel (d) and anti-parallel (e) arrangements of the consecutive directional planes.

Results and discussion

Coordination networks are periodic architectures dened by their dimensionality (1-, 2- or 3-D). Whereas for 1-D networks, the

Laboratoire de Chimie de Coordination Organique (UMR CNRS 7140), Universit de Strasbourg, Institut Le Bel, 4 rue Blaise Pascal, 67000 Strase bourg, France. E-mail: hosseini@chimie.u-strasbg.fr; Fax: 33 390241325; Tel: 33 390241323 CCDC reference numbers 744810744821. For crystallographic data in CIF or other electronic format see DOI: 10.1039/b917089h

The combination of such a tecton (Fig. 1(a)) with a metal centre offering two free coordination sites could lead to a 2-D network resulting from the bridging of consecutive organic moieties by metal centres (Fig. 1(b) and 1(c)). For such a sheet-type architecture, the directionality depends on the way the consecutive organic tectons are oriented with respect to each other. For the non-centrosymmetric arrangement, the 2-D network is directional (Fig. 1(b)), whereas for the centrosymmetric organisation of the tectons, owing to the presence of centres of symmetry, the overall architecture is non-directional (Fig. 1(c)). For the threedimensional organisation of the 2-D networks, the packing may occur either in a syn-parallel fashion leading thus to a directional Dalton Trans., 2010, 39, 21372146 | 2137

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crystal (Fig. 1(d)) or in an anti-parallel mode generating a nondirectional crystal (Fig. 1(e)). For the design of organic tectons schematically represented in Fig. 1(a), the [1111]metacyclophane backbone is particularly well suited. Indeed, this rigid unit adopts a thermally stable 1,3alternate conformation9 and can be readily tetra functionalised by a variety of groups such as hydoxy,9 cyano,10 mercapto,11 pyridyl,12 bipyridyl13 and quinolinyl.13 Examples of disubstituted derivatives have been also reported.14 Using the cyclophane backbone blocked in the 1,3-alternate conformation, a series of four new tectons (compounds 912, Scheme 1) bearing two different sets of coordinating sites have been designed and synthesised (see experimental).

Scheme 2 Structures of compounds 18.

Scheme 1 The black dots indicate the position of connection of the coordinating units to the cyclophane backbone in 1,3-alternate conformation.

For these four tectons 912, in order to impose the noncentrosymmetry, the north and south parts are differentiated by both the nature of the coordinating sites and the type of junction (direct connection through an ArAr junction for north and attachment through a methylene group for south). The two 5-membered ring heterocycles, imidazole15 and pyrazole,16 have been selected because of their propensity to form complexes with a variety of metal centres. Furthermore, being positional isomers, their use allows exploring the role played by the orientation of the coordinating N atoms once attached to the cyclophane backbone. The choice of imidazole17 and pyrazole18 was also based on our previous studies on metacyclophane derivatives bearing four such heterocycles. The choice of the methylene spacer connecting the two aromatic moieties located on the same side of the cyclophane skeleton to heterocycles through a CN bond was based on synthetic reasons and for introducing rotational exibility. For the other coordinating pole, two pyridines or thioether groups were used. Tectons 9 and 10 have in common the imidazolyl group and differ by the nature of the other coordinating sites (PhSMe for 9 and pyridyl for 10). The same holds for tectons 11 and 12 except that the two common imidazolyl groups are replaced by two pyrazolyl units (Scheme 1). The synthesis of compounds 912 requires the differentiation of the north and the south parts of the cyclophane blocked in 1,3alternate conformation. We thought that this could be achieved by using two different coupling reactions, one based on the classical nucleophilic displacement of halides centres and the other one the Suzuki ArAr coupling reaction. Thus, compound 4 bearing two ArBr groups and two ArCH2 Cl moieties appeared as the intermediate of choice (Scheme 2). The synthesis of 4 was achieved in 87% yield by a chloromethylation reaction of the dibromo derivative 3 using CH3 OCH2 Cl in
2138 | Dalton Trans., 2010, 39, 21372146

CHCl3 in the presence of SnCl4 .14 Precursor 3 was obtained in 30% yield upon treatment of the dichloro compound 2 by mesitylene in nitroethane and in the presence of SnCl4 .14 Finally, compound 2 was prepared in 84% yield by reacting bromomesitylene 1 with CH3 OCH2 Cl in CH2 Cl2 in the presence of SnCl4 .14 Intermediates 7 and 8 have been obtained in 81 and 79% yields respectively in DMF and in the presence of catalytic amounts of NaI upon nucleophilic displacement reactions between compound 4 and sodium imidazolate or pyrazolate. The desired compounds 912 have been synthesised using the Suzuki coupling reaction in DMF and in the presence of Cs2 CO3 using Pd(PPh3 )4 as the catalyst. It is worth noting that for this reaction, we have found the use of microwaves (120 W) at 130 C particularly useful for obtaining the desired compounds in acceptable yields and in rather short reaction times (ca. 30 min). Thus, the reaction of boronic ester 5 with compound 7 or 8 afforded tectons 9 and 11, possessing in common the PhSMe group and differentiated by the presence of either two imidazolyl (9) or two pyrazolyl (11) groups, in 22 and 38% yields respectively. On the other hand, the same type of coupling using the 4-pyridyl-boronic ester 6 afforded compounds 10 and 12 in 28 and 32% yields respectively. It is interesting to note that the two intermediates 7 and 8 bearing two imidazolyl or two pyrazolyl coordinating groups on the same side of the cyclophane mean plane may also be of interest for the formation of either discrete species of the metallamacrocyclic type or innite 1-D networks. Thus, they have been also combined with metal centres. Since compounds 712 are neutral species, in order to generate neutral coordination networks, they were combined with neutral metal halide MX2 type complexes offering two free coordination sites. Structural investigations For all compounds 712, although the [1111]metacyclophane backbone imposing the 1,3-alternate conformation because of steric reasons between CH3 groups is intrinsically rigid, the use of the methylene group between two of its phenyl group and either the two imidazolyl or pyrazolyl units introduces some rotational exibility. Indeed, compounds 712 can display three extreme conformers based on the orientation of the heterocycles with respect to centre of the cyclophane backbone. These rotamers This journal is The Royal Society of Chemistry 2010

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((ii), (io) and (oo)) are depicted in Fig. 2 for the dibromo intermediates 7 and 8.

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Fig. 2 Schematic representation of the three possible extreme rotamers (ii), (io) and (oo); i (in) and o (out) for the disubstituted compounds 7 and 8 corresponding to the orientation of the coordinating sites with respect to the centre of the cyclophane backbone.

Schematic representations of the extreme rotamers for the differentiated compounds 912 are given in Fig. 3. It is worth noting that for the other sets of coordinating sites, since the junction between the cyclophane backbone and PhSMe and pyridyl units are achieved using position 4, no rotational conformer may be expected.

Fig. 4 Schematic representation of the formation of a discrete metallamacrobicycle (b) by the (ii) rotamer (a) of compound 7 and different innite 1-D networks ((d)(g)) by the (oo) rotamer (c) of tecton 8 differing by different orientation of the cyclophane backbone.

and Hg; X = Cl or Br) afforded a series of crystalline materials (see experimental) that were structurally investigated in the solid state by X-ray diffraction on single-crystals (see Table 4 in experimental). For all cases, the same type of metallamacrobicycle (Fig. 4(b)) is formed (Fig. 5). For 7-CoX2 (X = Cl or Br) (Fig. 5(a) and (b)), 7-ZnBr2 (Fig. 5(c)), 7-CuBr2 (Fig. 5(d)) and 7-HgBr2 (Fig. 5(e)) complexes, the crystal system is triclinic with P1 as the space group. All complexes studied crystallise with solvent molecules (H2 O in the case of 7-CoCl2 and CHCl3 for the other complexes, see experimental). Although the ve cases are isostructural, as

Fig. 3 Schematic representation of the three possible extreme rotamers (ii), (io) and (oo); i (in) and o (out) for the tetrasubstituted compounds 912 corresponding to the orientation of the imidazolyl or pyrazolyl groups with respect to the centre of the cyclophane backbone.

Dealing with the disubstituted compounds 7 and 8, based on our previous investigations on the tetrakis imidazolyl derivative,17 for the (ii) rotamer (Fig. 4(a)) of the bisimidazole based compound 7, we expect the formation of a discrete metallamacrobicycle19 (Fig. 4(b)) in the presence of metal halides MX2 . Again based on our previous observations for the tetrakis pyrazolyl based tecton,18 for the (oo) rotamer (Fig. 4(c)) we predict the formation of 1-D coordination networks (Fig. 4(d)(g)) in the presence of metal halides serving as bridging inorganic tectons. The four schematically represented 1-D networks in Fig. 4(d)(g) possess the same connectivity mode but differ only by the orientation of the cyclophane backbone. The combination in solution (mixture of CHCl3 MeOH) of ligand 7 with different metal halides MX2 (M = Co, Zn, Cu This journal is The Royal Society of Chemistry 2010

Fig. 5 The solid-state structure of the discrete metallamacrobicycles formed upon associating compound 7 with CoCl2 (a); CoBr2 (b); ZnBr2 (c); CuBr2 (d); HgBr2 (e). For clarity, H atoms and solvent molecules are omitted. For bond distances and angles see text.

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Table 1 Average bond distances (A) and angles ( ) for 7-CoX2 (X = Cl or Br), 7-ZnBr2 , 7-CuBr2 and 7-HgBr2 M X dNM dXM NMN XMX NMX Co Cl 2.00 2.25 113.2 123.8 105.0 Co Br 2.01 2.39 115.2 123.9 104.6 Zn Br 2.01 2.38 112.5 123.2 105.3 Cu Br 1.96 2.39 138.5 134.7 97.8 Hg Br 2.30 2.54 106.6 135.7 102.9

expected, the metrics (bond distances and angles) are different for each complex (Table 1). The metallamacrobicycles are formed by simultaneous binding of MX2 centres by both imidazolyl groups located on the same face of the molecule ((ii) rotamer, Fig. 4(a)) through two MN bonds (dMN in the range of 1.96 2.30 A). In all cases, the metal centre, adopting a distorted tetrahedral coordination geometry (for bond angles see Table 1), is tetracoordinated and its coordination sphere is composed of two N and two X atoms (dMN in the range of 2.242.54 A). The bond distances and angles observed here are similar to those obtained for the metallamacrotricyclic analogues previously formed by reacting the tetraimidazolyl derivative with MX2 type complexes.17 The ability of pyrazolyl-based tecton 8 to generate innite coordination networks was also investigated by combining 8 with metal halides (MX2 , M = Co2+ and Zn2+ ; X= Cl- and Br- ). Whereas for 8-CoX2 (X = Cl or Br) and 8-ZnCl2 similar neutral 1-D networks are obtained (Fig. 6), in the case of 8-ZnBr2 , although again a 1-D network is observed, the consecutive tectons 8, adopting a different conformation, are differently arranged (Fig. 7). In all four cases, the crystals contained solvent molecules. Except in the case of CoCl2 for which CHCl3 molecules could be localised, for all other three cases, the solvent molecules were disordered and the SQUEEZE command20 was used (see crystallographic Table 5 in experimental). For the rst type, the 1-D networks are similar but not isostructural (see crystallographic Table 5 in experimental). They are generated by bridging of consecutive tectons 8, adopting the (oo) conformation (Fig. 4(c)), by CoCl2 (Fig. 6(a)), CoBr2 (Fig. 6(b)) or ZnCl2 (Fig. 6(c)). In all three cases, the bridging takes place between Co and Zn centres and consecutive tectons through MN bonds (dMN in the range of 2.012.06 A, Table 2). Both metal centres adopt a distorted tetrahedral coordination geometry (for bond angles see Table 2). Their coordination spheres are composed of two N and two X atoms (dMN in the range of 2.222.37 A). Within each 1-D network, the consecutive tectons 8 are tilted by ca. 90 (see Fig. 4(g)).
Table 2 Average bond distances (A) and angles ( ) for (8-MX2 )n (M = Co or Zn, X = Cl or Br) M X dNM dXM NMN XMX NMX Co Cl 2.02 2.23 104.6 120.8 107.6 Co Br 2.02 2.37 105.6 111.0 110.1 Zn Cl 2.06 2.23 98.2 121.3 108.7 Zn Br 2.01 2.35 98.6 120.5 108.9

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Fig. 6 Portion of the 1-D coordination network (view perpendicular to the network axis) generated upon combining the tecton 8 with CoCl2 (a); CoBr2 (b); ZnCl2 (c) and the packing of consecutive 1-D networks (d) (view along the network axis) for (8-CoCl2 )n . For the other two cases, the same packing is observed. H atoms and solvent molecules are omitted for clarity. For bond distances and angles see text.

The packing of consecutive 1-D networks perpendicular to the network axis is given in Fig. 6(d). Again, the bond distances and angles observed here are similar to those obtained for innite networks previously obtained by combining MX2 type complexes with the tetrapyrazolyl analogue.18 Rather surprisingly, for the combination of 8 with ZnBr2 , the organic tecton adopts the (io) conformation (Fig. 2). Consequently, the type of 1-D network obtained is different in geometry (Fig. 7). The crystal (orthorhombic, Pbca), in addition to 8 and ZnBr2 , contains disordered solvent molecules). The neutral network, of the type schematically presented in Fig. 4(e), is again generated by bridging of consecutive tectons 8 by ZnBr2 through the formation of two ZnN bonds (dZnN = 2.01 A). Zn2+ cation again adopts a distorted tetrahedral geometry and is surrounded by two N and two Br atoms (dZnBr = 2.35 A). Within the 1-D network, the consecutive tectons 8 are parallel and This journal is The Royal Society of Chemistry 2010

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Fig. 8 Portions of the structure of 1-D networks obtained upon combining 11 with CoX2 . (X = Cl (a) and X = Br (c)) and a view along the network axis for 11-CoCl2 (b). H atoms and solvent molecules are omitted for clarity.

Table 3 Average bond distances (A) and angles ( ) for (11-CoX2 )n (X = Cl or Br) M X dNM dXM NMN XMX NMX Co Cl 2.01 2.22 100.1 115.8 109.8 Co Br 2.02 2.35 100.2 113.8 110.4

Fig. 7 A portion of the 1-D coordination network (view perpendicular to the axis of the network (a)) and packing of two consecutive networks (b) generated upon combining the tecton 8 with ZnBr2 . H atoms and solvent molecules are omitted for clarity. For bond distances and angles see text.

tilted by 180 . Consequently, the network is of the zigzag type. The packing of consecutive 1-D networks is given in Fig. 7(b)). Much to our surprise, despite many attempts consisting in using different metal halides (variation of both metal and halide), different tecton/metal ratio, solvent systems and crystallisation techniques, no crystalline materials could be obtained using tectons 9 and 10 having in common two imidazolyl groups. The rst attempt to generate directional architecture using the acentric tecton 11 bearing two PhSMe and two pyrazolyl units and MX2 complexes failed. Indeed, X-ray diffraction studies on single crystals containing 11 and either CoCl2 (Fig. 8(a) and (b)) or CoBr2 (Fig. 8(c)) revealed the formation of isostructural 1-D networks. Both crystals (monoclinic, P21 /c) contained disordered solvent molecules which could not be localised and thus the SQUEEZE command was used for solving their structures (see crystallographic Table 6 in experimental).20 Unexpectedly, none of the two PhSMe groups behave as a coordinating site. This is probably due to the weak binding ability of the thioether group. The 1-D networks are thus formed by the bridging of consecutive CoX2 centres by tecton 11 through the formation of CoN bonds (dCoN of 2.01 A and 2.02 A for CoCl2 and CoBr2 respectively). The Co(II) is surrounded by two N atoms belonging to two consecutive tectons 11 (coordinating N atom of pyrazolyl unit) and two halide anions (dCoX of 2.22 A and 2.35 A for This journal is The Royal Society of Chemistry 2010

CoCl2 and CoBr2 respectively). The metal centre adopts a distorted tetrahedral geometry (see Table 3 for angles). Thus, compound 11 behaves as a tecton bearing two coordinating sites located on the same face of the cyclophane backbone (analogue of tecton 8) and the isostructural 1-D networks formed in the presence of CoX2 are of the type schematically represented in Fig. 4(d)). Finally, the combination of the acentric tecton 12, bearing two pyrazolyl groups on one face of the backbone and two pyridyl units on the other face, with ZnCl2 afforded the desired directional 2-D network (Fig. 9(a)). The crystal (monoclinic, C2/c) in addition to tecton 12 and ZnCl2 contains MeOH and H2 O solvent molecules. Bridging of consecutive tecton 12 by ZnCl2 complexes generates the 2-D network. The bridging mode takes place in a non-centrosymmetric fashion. Indeed, the coordination node is composed of a Zn2+ cation, two Cl- anions, one pyridyl and one pyrazolyl unit (Fig. 10). The translation of the above mentioned node into two directions of space generates the sheettype architecture. The organic tecton 12, adopts the (oo) conformation (Fig. 3), however the coordinating N atoms of both pyrazolyl groups are outwardly oriented. The Zn2+ cation is tetracoordinated and adopts a distorted tetrahedral coordination geometry (Npyraz ZnNpy , ClZnCl, ClZnNpyraz and ClZnNpy angles of 102.3, 122.6, 106.8 and 108.0 respectively). The coordination sphere around Zn2+ is composed of two Cl- anions (dZnCl of 2.195 and Dalton Trans., 2010, 39, 21372146 | 2141

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Fig. 9 A portion (perpendicular view to network axis) of the structure of the 2-D networks formed by combining tecton 12 with ZnCl2 (a) and a portion of the structure showing the centric packing of two consecutive planes (b). For clarity, the two consecutive networks are differentiated by the colour of C atoms. H atoms and solvent molecules are omitted for clarity.

In conclusion, the functionalised [1111]metacyclophane derivatives 7 and 8 bearing two imidazolyl or two pyrazolyl groups behave as a ligand and a tecton respectively. In the presence of a variety of MX2 complexes, whereas compound 7 leads to discrete metallamacrobicycles, compound 8 generates neutral analogous innite 1-D coordination networks. The acentric compound 11, bearing two different sets of coordinating poles (two PhSMe and two pyrazolyl), owing to the weak binding ability of the thioether group behaves as an analogue of the disubstituted tecton 8 and forms 1-D coordination networks in the presence of MX2 centres. Finally, the combination of ZnCl2 with the acentric tectons 12, composed of two pyrazolyl and two pyridyl groups, led to the formation of neutral directional 2-D networks resulting from the unsymmetrical nature of the coordination node composed of Zn2+ cation, two Cl- anions and one pyrazolyl and one pyridyl moieties. However, the packing of consecutive sheets takes place in an antiparallel fashion leading thus to a non-directional 3-D organisation. We are currently attempting to generate new coordination networks by combining tectons 912 with other metal centres and metal complexes.

Experimental
General: all reagents were purchased from commercial sources and used without further purication. 1 H NMR spectra were recorded at room temperature on a Bruker (300 MHz) NMR spectrometer. Microanalyses were performed by the Service de Microanalyses de la F d ration de Recherche de Chimie, Universit de Strasbourg, e e e Strasbourg. Synthesis
Fig. 10 Schematic representation of the directional 2-D coordination network formed upon combining the acentric tecton 12 with ZnCl2 .

2.200 A) and two N atoms, one belonging to the pyridine unit (dZnNpy = 2.032 A) and the other to pyrazole moiety (dZnNpyraz = ) of consecutive tectons 12 (Fig. 9(a)). Owing to the un2.049 A symmetrical nature of the assembling node, the 2-D architecture, oriented along the b axis, is directional (Fig. 10). Unfortunately and as often observed, the packing of consecutive directional 2-D networks takes place in the centrosymmetric fashion thus leading to a non-polar 3-D organisation (Fig. 9(b)). The parallel packing of sheets, of the ABA type, generates p p interactions between the aromatic moieties of the cyclophane backbones belonging to consecutive sheets with 3.58 A distance between them. The overall 3-D structure exhibits two sorts of channels along the c axis (Fig. 9(b)) with different dimensions, one small (4 A 11 A) and one large (7 A 15 A). The H2 O and MeOH solvents molecules are located within the large channels. The percentage of the potential accessible volume calculated using the PLATON software is 23%. Unfortunately, except for crystals composed of discrete metallamacrobicyclic units obtained with ligand 7, all other solid materials were found to lose their structural integrity upon release of solvent molecules. In particular, for crystals composed of tecton 12 and ZnCl2 offering channels, X-ray diffraction study on powder revealed the complete loss of crystalline order upon release of H2 O and MeOH molecules.
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Compound 4. To a solution of compound 3 (1.5 g, 2.19 mmol) and chloromethyl-methylether (0.5 ml, 6.55 mmol) dissolved in 35 ml of CHCl3 , at -10 C anhydrous SnCl4 (0.75 ml) was added drop wise. After complete addition, the solution was stirred for 60 min at -10 C and overnight at RT. To the reaction mixture, 20 ml of an aqueous HCl solution (10%) was added drop wise. The organic phase is separated and washed with water (25 ml) and then with an aqueous solution of NaOH (25 ml, 1M). The organic phase was dried over MgSO4 . After ltration and removal of the solvent, the residue was dissolved in a minimum of CH2 Cl2 and 100 ml of Et2 O are added. The precipitate was ltered affording pure compound 4 in 87% yield (1.49 g) as a white powder. M. P. > 300 C. 1 H-NMR (CDCl3 , 300 MHz, 25 C) d (ppm): 1.06 (s, 6H, p-CH3 ); 1.14 (s, 6H, p-CH3 ); 2.45 (s, 12H, o-CH3 ); 2.59 (s, 12H, o-CH3 ); 4.05 (s, 8H, Ar-CH2 -Ar); 4.72 (s, 4H, CH2 Cl); 13 C-NMR (CDCl3 , 75 MHz, 25 C) d (ppm): 18.2; 18.5; 21.7; 22.2; 34.3; 46.2; 130.8; 131.1; 133.6; 133.9; 134.6; 135.3; 133.3; 139.2. Compound 7. To a solution of sodium imidazolate (234 mg, 2.6 mmol) dissolved in 30 ml of dry DMF, compound 4 (500 mg, 0.64 mmol) and a spatula of NaI were added. The solution was stirred for 24 h at 95 C. After cooling to RT, the solvent was removed and the residue dissolved in 50 ml of CH2 Cl2 and washed with 50 ml of an aqueous saturated solution of NaHCO3 and then with 50 ml of water. The organic layer was separated and dried over MgSO4 . After ltration and removal of the solvent, the residue was dissolved in 10 ml of CH2 Cl2 . Addition of 2 ml of MeOH This journal is The Royal Society of Chemistry 2010

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and 50 ml of Et2 O followed by cooling to 0 C generated a white precipitate which was ltered and washed with small portions of Et2 O affording 0.44 g of compound 7 (81% yield) as a white solid. M. P. > 300 C. 1 H-NMR (CDCl3 , 300 MHz, 25 C), d (ppm): 1.11 (s, 6H, p-CH3 ); 1.19 (s, 6H, p-CH3 ); 2.33 (s, 12H, o-CH3 ); 2.59 (s, 12H, o-CH3 ); 4.06 (s, 8H, Ar-CH2 -Ar); 5.21 (s, 8H, CH2 -Im); 6.78 (bs, 4H, H-Im); 7.05 (bs, 4H, H-Im); 7.22 (bs, 4H, H-Im). 13 CNMR (CDCl3 , 75 MHz, 25 C), d (ppm): 17.2; 18.0; 19.1; 22.6; 34.2; 46.8; 118.6; 128.3; 128.9; 129.3; 133.5; 133.6; 134.2; 136.4; 136.7; 138.1; 138.8. Calc (%) for C48 H54 Br2 N4 (mw = 846.78): C 68.08; H 6.43; N 6.62; found: C 67.92; H 6.21; N 6.76. Compound 8. Under argon atmosphere and at RT, to a suspension of sodium hydride (60% in oil) (60 mg, 2.5 mmol) in 30 ml of dry DMF, pyrazole (177 mg, 2.6 mmol) was added in small portions. The solution was stirred for 2 h at RT before compound 4 (500 mg, 0.64 mmol) and a spatula of NaI were added. The solution was stirred for 24 h at 95 C. After cooling to RT, the solvent was removed and the residue dissolved in 50 ml of CH2 Cl2 . The organic phase was washed with 50 ml of an aqueous saturated solution of NaHCO3 and then with 50 ml of water. The organic layer was separated and dried over MgSO4 . After ltration and removal of the solvent, the residue was dissolved in 10 ml of CH2 Cl2 and upon addition of 2 ml of MeOH and 50 ml of Et2 O a precipitate was obtained which was ltrated and washed with small portions of Et2 O affording 0.43 mg of the pure compound 8 (79% yield) as a white solid. M. P. > 300 C. 1 H-NMR (CDCl3 , 300 MHz, 25 C), d (ppm): 1.15 (s, 6H, p-CH3 ); 1.21 (s, 6H, pCH3 ); 2.35 (s, 12H, o-CH3 ); 2.62 (s, 12H, o-CH3 ); 4.09 (s, 8H, Ar-CH2 -Ar); 5.45 (s, 8H, CH2 -Pyr); 6.16 (t, 2H, J 1 = 2,0 Hz, J 2 = 1,5 Hz, H-Pyr); 6.88 (d, 2H, J = 2 Hz, H-Pyr); 7.57 (d, 2H, J = 1,5 Hz, H-Pyr); 13 C-NMR (CDCl3 , 75 MHz, 25 C), d (ppm): 17.2; 18.1; 19.0; 22.6; 34.2; 51.7; 105.1; 127.6; 128.3; 129.4; 133.6; 133.9; 134.3; 136.5; 138.0; 138.9; 139.4. Calc (%) for C48 H54 Br2 N4 (mw = 846.78): C 68.08; H 6.43; N 6.62; found: C 68.10; H 6.46; N 6.80. Compounds 9 and 10. A solution of compound 7 (203 mg, 0.24 mmol) and anhydrous Cs2 CO3 (156.0 mg, 0.48 mmol) in dry DMF (20 ml) was degassed for 20 min with argon. Under argon, Pd(PPh3 )4 (27.8 mg, 0.024 mmol) and either 4(methylthio)phenylboronic ester 5 (180.1 mg, 0.72 mmol) or 4pyridineboronic ester 6 (148.0 mg, 0.72 mmol) were added. The mixture thus obtained was placed in a microwaves oven (120 W) and was stirred at 130 C for 30 min. The solution was ltered and the solvent removed under vacuum. The residue was dissolved in CH2 Cl2 (20 ml) and washed with an aqueous solution of NaOH (1 M) (25 ml) and then with water (25 ml). The organic phase was dried over MgSO4 . After ltration and removal of the solvent, the mixture was puried by column chromatography (SiO2 , CH2 Cl2 ). Compounds 9 and 10 were obtained in 28 and 22% yields respectively. Procedure for 11 and 12. A solution of compound 8 (210 mg, 0.25 mmol) and anhydrous Cs2 CO3 (162.5 mg, 0.5 mmol) in dry DMF (20 ml) was degassed for 20 min with argon. Under argon atmosphere, Pd(PPh3 )4 (28.8 mg, 0.025 mmol) and either 4-(methylthio)phenylboronic ester 5 (187.6 mg, 0.75 mmol) or 4-pyridineboronic ester 6 (154.2 mg, 0.75 mmol) were added. The mixture was placed in a microwaves oven (120 W) and stirred at 130 C for 30 min. The solution was ltered and the solvent This journal is The Royal Society of Chemistry 2010

removed under reduced pressure. The residue thus obtained was dissolved in CH2 Cl2 (20 ml) and washed with an aqueous solution of NaOH (1M) (25 ml) and then with water (25 ml). The organic phase was dried over MgSO4 . After ltration and removal of the solvent, the mixture was puried by column chromatography (SiO2 , CH2 Cl2 ). Compounds 11 and 12 were obtained in 32 and 38% yields respectively. Compound 9. M. P. > 300 C. 1 H-NMR (CDCl3 , 300 MHz, 25 C), d (ppm): 1.24 (s, 3H, p-CH3 ); 1.31 (s, 6H, p-CH3 ); 2.06 (s, 12H, o-CH3 ); 2.37 (s, 12H, o-CH3 ); 4.06 (AB, 8H, J = 18 Hz, Ar-CH2 -Ar); 5.24 (s, 4H, CH2 -Im); 6.81 (s, 2H, H-Im); 7.06 (s, 4H, H-Pyridine); 7.08 (s, 2H, H-Im), 8.68 and 8.71 (d, 2H, J = 5,8 Hz, H-Pyridine); 13 C-NMR (CDCl3 , 75 MHz, 25 C), d (ppm): 17.2; 18.2; 18.3; 19.3; 29.7; 33.0; 47.1; 118.8; 124.9; 125.2; 128.6; 128.8; 128.9; 130.7; 133.6; 135.1; 136.2; 136.8; 137.7; 138.4; 138.5; 150.0; 150.1; 151.9. Calc (%) for C58 H62 N6 (mw = 843,15): C 82.62; H 7.41; N 9.97; found: C 82.56; H 7.70; N 10.13. Compound 10. M. P. > 300 C. 1 H-NMR (CDCl3 , 300 MHz, 25 C), d (ppm): 1.25 (s, 6H, p-CH3 ); 1.31 (s, 6H, p-CH3 ); 2.05 (s, 12H, o-CH3 ); 2.36 (s, 12H, o-CH3 ); 3.99 and 4.10 (AB, 8H, J = 18 Hz, Ar-CH2 -Ar); 5.45 (s, 8H, CH2 -Pyr); 6.16 (t, 2H, J 1 = 2,0 Hz, J 2 = 2,2 Hz, H-Pyr); 6.87 (d, 2H, J = 2,2 Hz, H-Pyr); 7.08 (d, 4H, J = 5,5 Hz, H-Pyridine); 7.54 (d, 2H, J = 2 Hz, H-Pyr); 8.67 (bs, 4H, H-Pyridine); 13 C-NMR (CDCl3 , 75 MHz, 25 C) d (ppm): 17.2; 18.1; 18.4; 19.3; 29.7; 33.2; 51.8; 105.0; 126.6; 127.6; 129.3; 130.0; 130.2; 131.7; 133.8; 134.4; 136.2; 136.8; 137.5; 138.5; 139.3; 140.3; 140.6. Calc (%) for C58 H62 N6 (mw = 843,15): C 82.62; H 7.41; N 9.97; found: C 82.76; H 7.19; N 10.04. Compound 11. M. P. > 300 C. 1 H-NMR (CDCl3 , 300 MHz, 25 C), d (ppm): 1.23 (s, 6H, p-CH3 ); 1.33 (s, 6H, p-CH3 ); 2.08 (s, 12H, o-CH3 ); 2.36 (s, 12H, o-CH3 ); 2.56 (s, 12H, S-CH3 ); 4.02 and 4.10 (AB, 8H, J = 18 Hz, Ar-CH2 -Ar); 5.25 (s, 8H, CH2 -Pyr); 6.83 (s, 2H, H-Pyr); 7.00 (dd, 2H, J 1 = 8,7 Hz, J 2 = 1,8 Hz, H-Ph); 7.04 (dd, J 1 = 8,7 Hz, J 2 = 1,8 Hz, 2H, H-Ph); 7.08 (s, 2H, H-Pyr); 7.24 (s, 2H, H-Pyr); 7.34 (m, 4H, H-Ph); 13 C-NMR (CDCl3 , 75 MHz, 25 C), d (ppm): 17.0; 17.2; 18.1; 18.6; 19.7; 29.9; 32.9; 53.2; 105.7; 127.0; 127.8; 129.3; 130.1; 130.5; 131.7; 134.0; 134.8; 137.2; 136.4; 137.2; 138.8; 139.0; 140.9; 142.8. Calc (%) for C62 H68 N4 S2 (mw = 933.36): C 79.78; H 7.34; N 6.00; found: C 80.13; H 7.12; N 6.03. Compound 12. M. P. > 300 C. 1 H-NMR (CDCl3 , 300 MHz, 25 C), d (ppm): 1.29 (s, 6H, p-CH3 ); 1.37 (s, 6H, p-CH3 ); 2.12 (s, 12H, o-CH3 ); 2.40 (s, 12H, o-CH3 ); 2.57 (s, 12H, S-CH3 ) 3.99 and 4.10 (AB, 8H, J = 18 Hz, Ar-CH2 -Ar); 5.49 (s, 8H, CH2 -Pyr); 6.17 (t, 2H, J 1 = 2,0 Hz, J 2 = 2,2 Hz, H-Pyr); 6.90 (d, 2H, J = 2,2 Hz, H-Pyr); 7.05 (m, 8H, H-Ph); 7.37 (m, 8H, H-Ph); 7.6 (d, 2H, J = 2 Hz, H-Pyr); 13 C-NMR (CDCl3 , 75 MHz, 25 C), d (ppm): 16.9; 17.2; 18.1; 18.4; 19.3; 29.7; 33.2; 51.8; 105.0; 126.6; 127.6; 129.3; 130.0; 130.2; 131.7; 133.8; 134.4; 136.2; 136.8; 137.5; 138.5; 139.3; 140.3; 140.6. Calc (%) for C62 H68 N4 S2 (mw = 933.36): C 79.78; H 7.34; N 6.00; found: C 80.02; H 7.33; N 6.15. Crystallisation All discrete complexes 7-MX2 : (M = Co; Zn; Cu; Hg; X= Cl or Br) have been prepared as crystalline materials and have been characterised by X-ray diffraction on single crystal and by Dalton Trans., 2010, 39, 21372146 | 2143

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Table 4 Crystallographic parameters for discrete metallamacrobicycles obtained upon combining compound 7 with MX2 (M = Co, Zn, Cu and Hg, X = Cl or Br) CoCl2 Formula Formula weight Crystal system Space group a/A b/A c/A a/ b/ a/ V /A3 Z s calcd/g cm-3 m/mm-1 No. of reections R(int) No. of data I > 2s(I) Final R indices [I > 2s(I)] R indices (all data) GoF C96 H118 Br4 Cl4 Co2 N8 O5 2043.28 Triclinic P1 11.8253(9) 14.3000(11) 15.6345(12) 92.834(4) 99.430(3) 107.919(4) 2467.5(3) 1 1.375 2.117 33 489 0.0485 10 866 R1 = 0.0820 wR2 = 0.2357 R1 = 0.1285 wR2 = 0.2717 1.050 CoBr2 C49 H55 Br4 Cl3 CoN4 1184.89 Triclinic P1 11.5480(2) 14.7042(3) 15.2422(3) 92.5061(9) 92.9050(8) 110.0702(10) 2422.73(8) 2 1.624 3.857 38 997 0.0399 11 105 R1 = 0.0542 wR2 = 0.1209 R1 = 0.0854 wR2 = 0.1349 1.021 ZnBr2 C49 H55 Br4 Cl3 N4 Zn 1191.33 Triclinic P1 11.5652(2) 14.7038(4)) 15.2283(4) 92.5000(10) 92.9650(10) 110.0270(10) 2424.56(10) 2 1.632 4.007 48 230 0.0450 10 879 R1 = 0.0646 wR2 = 0.1422 R1 = 0.0861 wR2 = 0.1594 1.072 CuBr2 C49 H55 Br4 Cl3 CuN4 1189.50 Triclinic P1 11.4322(3) 14.6136(3) 15.3801(4) 91.8790(10) 93.1620(10) 109.7170(10) 2411.54(10) 2 1.638 3.972 35 032 0.0453 11 055 R1 = 0.0539 wR2 = 0.1131 R1 = 0.0868 wR2 = 0.1300 1.011 HgBr2 C49 H55 Br4 Cl3 HgN4 1326.55 Triclinic P1 11.4429(6) 14.9630(9) 15.3162(11) 92.715(2) 90.510(2) 110.905(2) 2446.1(3) 2 1.801 6.615 45 948 0.0604 11 001 R1 = 0.0564 wR2 = 0.1317 R1 = 0.0935 wR2 = 0.1576 1.009

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Table 5 Crystallographic parameters for 1-D coordination networks obtained upon combining the compound 8 with MX2 (M = Co, Zn; X = Cl or Br). For (8-CoBr2 )n , (8-ZnCl2 )n and (8-ZnBr2 )n the solvents are disordered and the Squeeze command was used CoCl2 Formula Formula weight Crystal system Space group a/A b/A c/A a/ b/ a/ V /A3 Z s calcd/g cm-3 m/mm-1 No. of reections R(int) No. of data I > 2s(I) Final R indices [I > 2s(I)] R indices (all data) GoF C48 H54 Br2 Cl2 CoN4 976.60 Monoclinic P21 /n 13.0585(9) 26.0298(18) 16.2349(11) 90 101.517(2) 90 5407.3(6) 4 1.200 1.926 2004 0.0637 12 429 R1 = 0.0768 wR2 = 0.1960 R1 = 0.1490 wR2 = 0.2146 1.032 CoBr2 C48 H54 Br4 CoN4 1065.52 Orthorhombic Pca21 18.3656(4) 16.0416(4) 17.5199(6) 90 90 90 5161.6(2) 4 1.371 3.462 23 482 0.0540 9338 R1 = 0.0951 wR2 = 0.2445 R1 = 0.1267 wR2 = 0.2672 1.256 ZnCl2 C48 H54 Br2 Cl2 N4 Zn 983.04 Orthorhombic Pbca 21.629(2) 18.9786(18) 34.265(3) 90 90 90 14065(2) 8 0.928 1.586 70 819 0.1083 15 804 R1 = 0.1077 wR2 = 0.2648 R1 = 0.2206 wR2 = 0.2901 1.091 ZnBr2 C48 H54 Br4 N4 Zn 1071.96 Orthorhombic Pbca 21.8030(10) 19.3128(9) 33.4302(14) 90 90 90 14076.7(11) 8 1.012 2.644 130 795 0.0845 16 242 R1 = 0.0867 wR2 = 0.1729 R1 = 0.2001 wR2 = 0.1911 1.020

elemental analysis. These compounds are insoluble in common solvents and for that reason were not further characterised. 7-MX2 : in a crystallisation tube (15 cm height, 0.4 cm diameter), single-crystals were obtained at room temperature after ca. 3 days upon slow diffusion of 1.5 ml of a MeOH solution containing 3 mg of the metallic salt into 1 ml of a CHCl3 solution containing 1 mg of compound 7. 7-CoCl2 : calc. for C48 H54 Br2 Cl2 CoN4 (MW = 976.62): C 59.03; H 5.57; N 5.74; found C 58.83; H 5.76; N 6.00. 7-CoBr2 : calc. for C56 H64 Br6 CoN8 (MW = 1065.52): C 54.40; H 5.11; N 5.26; found C 54.56; H 5.02; N 5.55.
2144 | Dalton Trans., 2010, 39, 21372146

7-ZnBr2 : calc. for C56 H64 Br6 N8 Zn (MW = 1072.00): C 53.78; H 5.08; N 6.10; found C 54.01; H 5.15; N 5.88. 7-CuBr2 : calc. for C56 H64 Br6 CuN8 (MW = 1070.13): C 53.87; H 5.09; N 5.24; found C 53.78; H 5.11; N 5.54. 7-HgBr2 : calc. for C56 H64 Br6 HgN8 (MW = 1207.18): C 47.76; H 4.51; N 4.64; found C 47.79; H 4.63; N 4.90. (8-MX2 )n : in a crystallisation tube (15 cm height, 0.4 cm diameter), single-crystals were obtained at room temperature after ca. 3 days upon slow diffusion of 1.5 ml of a MeOH solution containing 3 mg of the metallic salt into 1 ml of a CHCl3 solution containing 1 mg of the compound 8. This journal is The Royal Society of Chemistry 2010

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Table 6 Crystallographic parameters for coordination networks obtained upon combining 11 with MX2 (X = Cl or Br) and tecton 12 with ZnCl2 . For (11-CoCl2 )n and (11-CoBr2 )n the solvents are disordered and the Squeeze command was used (11-CoCl2 )n Formula Formula weight Crystal system Space group a/A b/A c/A a/ b/ a/ V /A3 Z s calcd/g cm-3 m/mm-1 No. of reections No. of data I > 2s(I) R(int) Final R indices [I > 2s(I)] R indices (all data) GoF C62 H68 Cl2 CoN4 S2 1063.15 Monoclinic P21 /c 15.8582(6) 13.8304(6) 32.7069(12) 90 91.618(2) 90 7170.6(5) 4 0.985 0.405 45 269 16 440 0.0439 R1 = 0.1026 wR2 = 0.3039 R1 = 0.1480 wR2 = 0.340 1.263 (11-CoBr2 )n C62 H68 Br2 CoN4 S2 1152.07 Monoclinic P21 /c 16.0135(18) 14.0197(13) 32.858(4) 90 92.339(3) 90 7370.7(13) 4 1.038 1.406 58 445 16 440 0.0685 R1 = 0.0970 wR2 = 0.2566 R1 = 0.1446 wR2 = 0.2766 1.068 (12-ZnCl2 )n C234 H260 Cl16 N24 O4 Zn8 4562.82 Monoclinic C2/c 12.6081(13) 32.110(4) 13.8506(15) 90 94.815(4) 90 5587.6(11) 1 1.356 1.095 42 137 6425 0.0471 R1 = 0.0910 wR2 = 0.3180 R1 = 0.1311 wR2 = 0.2921 1.254

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(10-[ZnCl2 ]2 )n : in a crystallisation tube (15 cm height, 0.4 cm diameter), single-crystals were obtained at room temperature after ca. 3 days upon slow diffusion of 1.5 ml of a MeOH solution containing 3 mg of the metallic salt into 1 ml of a 1,2dichloroethane solution containing 1 mg of the compound 10. (12-CoX2 )n (X = Cl, Br): in a crystallisation tube (15 cm height, 0.4 cm diameter), single-crystals were obtained at room temperature after ca. 3 days upon slow diffusion of 1.5 ml of a MeOH solution containing 3 mg of the metallic salt into 1 ml of a 1,2-dichloroethane solution containing 1 mg of the compound 12. Crystallography Data were collected at 173(2) K on a Bruker APEX8 CCD Diffractometer equipped with an Oxford Cryosystem liquid N2 device, using graphite-monochromated Mo Ka (l = 0.71073) radiation. The structures were solved using SHELXS-97 and rened by full matrix least-squares on F 2 using SHELXL-97.21 The hydrogen atoms were introduced at calculated positions and not rened (riding model). All hydrogen atoms have been calculated except those connected to disordered atoms. In some cases, because of the disorder of the solvent molecules, the squeeze command20 was used. In several cases, the diffraction power of crystals generated was also rather low. Consequently, in some cases, the R factors obtained are rather high. However, this should not affect signicantly the structural descriptions of the networks reported.

are acknowledged for nancial support and for a scholarship to J. E.

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Acknowledgements
Universit de Strasbourg, the International Centre for Frontier e Research in Chemistry (FRC), Strasbourg, Institut Universitaire de France, the CNRS and the Ministry of Education and Research This journal is The Royal Society of Chemistry 2010

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