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New Heterometallic Hybrid Polymers Constructed with Aromatic Sulfonate-Carboxylate Ligands: Synthesis, Layered Structures, and Properties Teresa Kurc,† Jan Janczak,‡ Józef Hoffmann,† and Veneta Videnova-Adrabinska*,† †

Department of Chemistry, Wrocław University of Technology, 27 Wybrzeze Wyspianskiego Street, 50-370 Wrocław, Poland Institute of Low Temperature and Structural Research, Polish Academy of Science, 2 Okolna Street, P.O. Box 1410, 50-950 Wrocław, Poland

‡

S Supporting Information *

ABSTRACT: Three novel alkali metal−cadmium coordination polymers [K2 Cd(Hsb) 4 (H 2 O) 6 ]3n 1, [NaCd(sip)(DMF)2(H2O)2]2n 2, and [NaCd2(sip)2(DMF)2(H2O)2]2n· 2nHdeta·2nH2O 3 (H2sb = 4-sulfobenzoic acid, H3sip = 5-sulfoisophthalic acid) have been synthesized and characterized by single crystal X-ray diffraction and spectroscopic and thermogravimetric methods. The solid state structure of 1 consists of inorganic layers, formed from Na2O10 and CdO6, polyhedral units, bridged via the sulfonate site of the ligand. The layers are pillared by the organic portions of the ligands to form a three-dimensional framework classified as I2O1. Compounds 2 and 3 display inorganic−organic hybrid layers arranged in 3D via nonspecific (hydrophobic) interactions between the DMF ligands. The two-dimensional frameworks of the layers are classified as I1O1 (in 2) and I0O2 (in 3). The guest diethylammonium ions in 3 are arranged in hydrophobic channels along the [011] crystallographic direction and circumvented by the DMF ligands.

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INTRODUCTION Inorganic−organic hybrid compounds appear to be a superior class of materials for state-of-the-art applications and open new horizons for design and synthesis of functionalized structures. Research on them started with the Robson works on coordination polymers and have progressed considerably over the past 15 years.1 In the solid state the organic and inorganic components in them are assembled in a complementary fashion to form one-, two-, and three-dimensional (1D, 2D, and 3D) metal−organic coordination networks (MOCN),2 and in particular, metal−organic frameworks (MOF).3 The metal ions (or metal ion clusters) serve as nodes and the organic ligands as linkers. The synergistic combination of the unique characteristics of the organic and inorganic components in them can provide the compounds with unusual structures and intriguing features. The properties of the metal centers and linkers usually determine the function of the target material like pore size and surface,4 as well as some other physical characteristics such as luminescence,5 magnetism,6 conductivity,7 spin transition behavior,8 optical nonlinearity,9 and optoelectronic effects.10 The porosity of the crystalline network is particularly suited for gas storage,11 selective absorption and ion exchange,12 size, shape and enantioselective catalysis.13 MOFs can find application for energy utilization and environmental remediation, as well as for drug storage and delivery.14 Inorganic−organic hybrids have been applied as © 2012 American Chemical Society

luminescent and fluorescent materials and sensors for selective monitoring devices.15 The advantage of the inorganic−organic hybrid materials compared with the pure inorganic or pure organic materials is not disputable, if one takes into account that the connectivity patterns between the nodes and the linkers in their frameworks are realized by coordination bonds, which are weaker than covalent bonds but stronger than hydrogen bonds and other intermolecular interactions. Therefore, the design and synthesis of thermally and mechanically stable structures are achievable via supramolecular approaches. While the coordination number and geometries of the metal centers rule the inorganic building units, the number of possible O- and/or N-functionalized organic linkers is practically unlimited. Structural variations of target networks are possible by changing the starting products and the compositional rates provided that the inorganic connectors (nodes) and the organic linkers (spacers) of the network are matched in number and orientation of the binding sides. This means that the coordination and geometric preference of the metal ion should correspond to the binding capacity of the ligand’s functional groups. On the other hand, Received: February 9, 2012 Revised: March 16, 2012 Published: March 20, 2012 2613

dx.doi.org/10.1021/cg300199j | Cryst. Growth Des. 2012, 12, 2613−2624

Crystal Growth & Design

Article

collected in Table S1, Supporting Information. Fluorescent properties of 1−3 were measured on an Edinburgh Instruments analyzer model FL920 with a xenon arc lamp as a light source. In the measurements of the emission and excitation spectra, the pass width is 5.0 nm. Synthesis of Compounds. [K2Cd(Hsb)4(H2O)6]3n (1). Potassium salt of 4-sulfobenzoic acid (KHsb) (81.9 mg, 0.340 mmol) was dissolved in 1.2 mL of distilled water and mixed at 70 °C for 10 min. To the mixture was added a water solution (0.3 mL) of oxalic acid (20.7 mg, 0.340 mmol) and a water solution (0.5 mL) of Cd(NO3)2 (201.9 mg, 0.680 mmol). The obtained colorless solution was kept in a small vial covered with parafilm and left at room temperature. Small colorless crystals of parallelepiped shape appeared after 2 weeks, which were collected and washed. [NaCd(sip)(DMF)2(H2O)2]2n (2). Sodium salt of 5-sulfoisophthalic acid (NaH2sip) (150.6 mg, 0.561 mmol) was dissolved in 4.0 mL mixture of ethanol and dimethylformamide (0.5 mL ethanol, 3.5 mL DMF) in 55 °C. To this mixture was added an ethanol-DMF (0.5 mL ethanol, 1.0 mL DMF) solution of CdCl2 (137.0 mg, 0.748 mmol) and 0.12 mL of diethylamine (deta) (1.122 mmol). After all components were mixed, a feather-like precipitate was formed. The precipitate was dissolved in 1.5 mL of distilled water. The obtained colorless solution was kept in a small vial covered with parafilm and left at room temperature. Small colorless crystals of parallelepiped shape appeared after 8 days, which were collected and washed. [NaCd2(sip)2(DMF)2(H2O)2]2n·2nHdeta·2nH2O (3). Sodium salt of 5-sulfoisophthalic acid (NaH2sip) (150.2 mg, 0.561 mmol) was dissolved in 4.0 mL mixture of ethanol and DMF (0.5 mL of ethanol, 3.5 mL of DMF) in 55 °C. To the mixture was added an ethanolDMF (0.5 mL of ethanol, 1.0 mL of DMF) solution of Cd(NO3)2 (219.7 mg, 0.748 mmol) and 0.12 mL of diethylamine (1.122 mmol). The obtained colorless solution was kept in a small vial covered with parafilm and left at room temperature. Small colorless crystals of parallelepiped shape appeared after 2 weeks, which were collected and washed. The phase purity of the compounds 1−3 has was checked by powder X-ray diffraction (PXRD) measurements and the XRD patterns are given in the Supporting Information (Figure S1). X-ray Single Crystal Measurements and Crystal Structure Analysis. Single crystal X-ray diffraction measurements of 1−3 were carried out at 295 K on a four-circle KUMA KM4 diffractometer equipped with two-dimensional CCD area detector. Graphite monochromatized Mo−Kα radiation (λ = 0.71073 Å) and ω-scan technique (Δω = 1°) were used for data collection. Data collection and reduction along with absorption correction were performed using CrysAlis software package.20 The structures were solved by direct methods using SHELXS-97,21 which revealed the positions of almost all nonhydrogen atoms. The remaining atoms were located from subsequent difference Fourier syntheses. The structure was refined using SHELXL-9721 with the anisotropic thermal displacement parameters. The hydrogen atoms of 1 and 2 were refined, whereas the H atoms of 3 were constrained as riding model. Visualization of the structure was made with the Diamond 3.1 program.22 PLATON was used to analyze the relationships between the aromatic rings and to search for solvent accessible voids in the structures.23 Details of the data collection parameters, crystallographic data, and final agreement parameters are collected in Table 1. ConQuest 1.13 was used to survey the compounds in the Crystallographic Structural Database (CSD v.5.32).24,25 The Material Module of Mercury v.2.4 was used for visualization of the retrieved structures and analysis of the structural motives in them.26

dependent upon varying internal and external parameters of the synthesis, topological modifications of the frameworks are feasible, since the free metal ions have many binding sites, but not enough directional information to uniformly read the structural information of the ligand. The most commonly used organic linkers are the multidentate aromatic polycarboxylate, due to their structural rigidity, strong bonding interactions, and rich diversity of coordination modes utilized for extension of the metal ions into high-dimensional structures.16 However, recently there is a growing interest in employment of their sulfonic analogous for construction of novel metallosupramolecular structures.17,18 The replacement of the carboxylic group with a sulfonic group enhances the number of possible geometrical combination between the O-donors and allows for bridging the metal ions with new coordination modes. In particular, the 5-sulfoisophthalic acid appears to be a very attractive organic ligand, which allows for a wide variety of composition rates and metal combinations. The geometry of the functional groups is appropriate for polynuclear clustering and formation of high-dimensional frameworks. The topology of its binding sites allows for variable connectivity patterns within the same composition rate, which may lead to supramolecular isomerism. On the other hand, the different chemical nature and preference of the functional groups for metal ions allow for formation of heteropolynuclear hybrids. The soft sulfonate group preferably coordinates to late transition metal(II) ions Cd2+, Zn2+, Cu2+, lanthanide(III) ions and main group metal ions such as Pb2+. The Structural Database Cambridge v.5.32 contains 167 sulfoisophthalate metal ions complexes: 122 transition metal, 27 lanthanides, 5 earth alkaline metal, and 13 Pb(II) compounds. However, only in 86 of them the sulfonate group is binding the metal ion(s) to form at least one M-O(S) bond (in 14 Cd(II), 1 Ag, 13 Pb(II), 21 Cu(II), 5 Zn(II), 1 Ni(II), 1 Mn(II), 18 lanthanide compounds, as well as in all group 1 and group 2 metal ion sulfoisophthalates). Among them, in 33 cases the sulfonate group serves as a bidentate ligand and in 12 cases as a tridentate ligand. There are 29 cadmium sulfoisophthalate structures published in the literature, but in many of them additional bipyridyl or flexible bisimidazole ligands are also used to interlink the Cd2+ ions into a polymeric coordination network.19 Here we present the crystal structure and discuss the network organization of three novel mixed metal coordination polymers composed of potassium or sodium and cadmium ions connected by 4-sulfobenzoic acid or 5-sulfoisophthalate linkers.

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EXPERIMENTAL SECTION

Materials and Measurements. All chemicals were reagent grade, commercially available, and used as received. The TG-DTA-MS analysis was performed using a NETZSCH STA 449 F3 Jupiter coupled with a MS 403 C Aöeols mass spectrometer. The TG curves, measured in air atmosphere (80:20 N2/O2) with a gas flow of 260.3 mL/min, were combined with DTA curves and mass spectra. A crucibles of Al2O3 were used for the probe and an empty alumina crucible as reference. The initial amount of the analyzed probes was approximately 40 mg, and the registration was carried out under dynamic atmosphere, starting from 35 °C up to 800 °C with a heating rate of 5 °C per min. The simultaneously recorded mass spectra for 18, 30, 44, 46, and 64 AMU were taken every 10 °C, using a scan rate of 0.5 s/AMU. Data were processed using online connected computer system with commercial NETZSCH Proteus software. The X-ray powder diffraction patterns were measured with X-Pert PRO (PANalitical). The FT-IR spectra of the compounds were measured in KBr pellets and in nujol mulls in the region 4000−400 cm−1 using Bruker IFS-88 spectrometer with a resolution of 2 cm−1. The frequencies of the observed bands and their tentative assignments are

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RESULTS AND DISCUSSION It is well-known that the structure of coordination polymers depends upon the starting materials and the synthesis condition. Many internal and external factors may influence the final crystal network organization. The stepwise deprotonation of sulfocarboxylic acids and the different geometry and topology of the coordination sites allow for multidentate 2614



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Table 1. Crystallographic Data and Structure Refinement Summary for Compounds 1−3 compound

1

2

3

formula formula weight crystal system space group a/Å b/Å c/Å α/deg β/deg γ/deg V/Å3 Z Dcalcd/g cm−3 μ/mm−1 absorption corrections, Tmin/Tmax F(000) crystal size/mm3 temp/K λ/Å total reflns unique reflns observed reflns reflections (Rint) no. parameters R[F2 > 2σ(F2)]a wR [F2 all refln]b S Δρmax, Δρmin/e Å−3

C28H32CdK2O26S4 1103.43 triclinic P1̅ 8.0990(16) 10.192(2) 12.642(3) 99.45(3) 95.04(3) 105.71(3) 981.3(4) 1 1.867 1.080 0.7556/0.8322 558 0.19 × 0.24 × 0.28 293 0.71073 13251 4872 3865 0.024 301 0.0317 0.0726 1.001 2.698, −0.693

C14H21CdN2NaO11S 560.80 triclinic P1̅ 8.9107(14) 10.3801(17) 12.910(2) 106.42(1) 109.590(11) 98.640(2) 1038.7(3) 2 1.793 1.232 0.7672/0.8204 564 0.17 × 0.20 × 0.23 293 0.71073 14699 5210 4165 0.018 287 0.0220 0.0460 1.002 0.420, −0.321

C26H32N3Cd2NaO20S2 1018.50 triclinic P1̅ 8.936(2) 12.821(2) 17.109(3) 102.64(1) 93.32(1) 104.24(1) 1872.6(6) 2 1.810 1.806 0.7613/0.8211 1016 0.16 × 0.20 × 0.22 295 0.71073 26213 9496 4219 0.096 496 0.0605 0.1474 1.069 0.923, −0.936

R = Σ ∥Fo| − |Fc∥/ΣFo. bwR = {Σ [w(Fo2 − Fc2)2]/ΣwFo4}1/2; w = 1/[c2(Fo2) + (0.0457P)2] for 1; w = 1/[c2(Fo2) + (0.0240)2] for 2 and w = 1/[c2(Fo2) + (0.0456P)2 + 1.2923P] for 3, where P = (Fo2 + 2Fc2)/3. a

Scheme 1. Different Coordination Modes Observed in Compounds 1−3a

a

(a−e) The five different coordination fashions adopted by ligands Hsb and sip in the studied compounds. The first mode refers to the ligand entity (Hsb or sip) as a whole and is bolded. The rest of the modes refer to the sulfonate group and the carboxylic/carboxylate group(s) of the ligand. The ηxμyκz notation is used for description of the coordination modes, where: ηx − number of coordination bonds (electron pairs) donated from the ligand; μy − number of metal centers bonded to the ligand; κz − number of atoms donating coordination bonds.

system. The most important structural data, concerning the lengths of the coordination bond, are collected in Table 2. Table 3 presents the geometric parameters of the hydrogen bonds. Other important parameters concerning the geometry of the coordination bonds (Table S2) and the interactions between the aromatic rings (Tables S3 and S4) are presented in the Supporting Information. Crystal Structure of [K2Cd(Hsb)4(H 2O) 6] 3n (1). The X-ray analysis of 1 reveals a three-dimensional coordination framework consisting of inorganic layers and organic linkers. The asymmetric unit of 1 contains half of a cadmium and one potassium cations, two monodeprotonated 4-sulfobenzoate

binding with variable coordination modes. Scheme 1 presents the coordination modes observed in 1−3. It should be noted that modes (a) and (c) are not observed in other sulfonatobenzoate and sulfonatoisophthalate compounds. On the other hand, the nature of the counterion in the metal salt, used for synthesis, may also change the final outcome as is the case of crystals 2 and 3, where Cd(II) ions come from chloride or nitrate salts. The compounds 1−3 were obtained from water/ ethanol/amine solutions in mild conditions and utilizing slow evaporation methods. Description of Crystal Structures. Compounds 1−3 crystallize in the centrosymmetric space group of the triclinic 2615



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Table 2. Selected Bond Lengths (Å) 1−3 Crystal 1 Cd1O1 Cd1O13 Cd1O23 K1O2 K1O3 K1O11 Cd−O4 Cd−O5 Cd−O8 Cd−O10 Cd−O11 Cd−O6(i) Cd−O7(i) Cd−Cd(v) Cd1O6 Cd1O7 Cd1O22 Cd1O1(i) Cd1O24(i) Cd1O25(i) Cd1O32(i) Na1O2 Na1O25 Na1O32 Cd1···Na1(ii) Na1···Cd1(i) Na1···Cd1(v)

Cd1O1 Cd1O1 Cd1O13 Cd1O13 Cd1O23 Cd1O23 K1O2 K1O2 K1O3 K1O3 K1O11 K1O11 Crystal 2b Cd−O4 Cd−O5 Cd−O8 Cd−O10 Cd−O11 Cd−O6(i) Cd−O7(i) Cd−Cd(v) Crystal 3c Cd1O6 Cd1O7 Cd1O22 Cd1O1(i) Cd1O24(i) Cd1O25(i) Cd1O32(i) Na1O2 Na1O25 Na1O32 Cd1···Na1(ii) Na1···Cd1(i) Na1···Cd1(v)

Table 3. Geometry of the Hydrogen Bonds for Compounds 1−3 (Å, °)

a

Cd−O4 Cd−O5 Cd−O8 Cd−O10 Cd−O11 Cd−O6(i) Cd−O7(i) Cd−Cd(v) Cd1O6 Cd1O7 Cd1O22 Cd1O1(i) Cd1O24(i) Cd1O25(i) Cd1O32(i) Na1O2 Na1O25 Na1O32 Cd1···Na1(ii) Na1···Cd1(i) Na1···Cd1(v)

D−H···A

Cd1O1 Cd1O13 Cd1O23 K1O2 K1O3 K1O11

D···A

∠D−H···A

2.03(3) 2.38(3) 2.00(2) 2.08(3) 2.36(3) 2.4300 2.5100

2.799(3) 2.984(3) 2.87492) 2.880(3) 3.025(3) 2.748(3) 2.890(3)

160(3) 148(3) 178.2(18) 154(3) 170(4) 100.00 105.00

1.79(4) 1.81(4) 2.01(3) Crystal 2b 1.906(6) 1.871(8) 1.88(2) 2.095(13) 2.4100 2.4800 2.3300 2.4000 Crystal 3c 2.2600 2.1900 1.9600 2.5600 2.5400 2.4200 2.4400 2.5900 2.4400 2.3000 2.5300

2.637(3) 2.656(2) 2.731(2)

170(3) 178(5) 175(4)

2.727(2) 2.678(2) 2.701(2) 2.846(2) 2.731(2) 2.687920 3.215(3) 2.795(3)

175(2) 165.5(19) 174(2) 152(2) 100.00 105.00 160.00 104.00

3.085(11) 2.957(10) 2.857(11) 2.915(9) 2.921(10) 2.739(8) 3.152(11) 3.428(14) 2.807(12) 2.727(12) 3.363(12)

151.40 142.40 174.00 103.00 105.00 100.00 133.00 145.00 103.00 106.00 145.00

H···A Crystal 1a

intralayer interactions O1−H2O···O22(vi) O2−H3O···O22(vii) O2−H4O···O13(iii) O3−H5O···O1(i) O3−H6O···O11(ii) C13−H13···O15 C26−H26···O2 interlayer interactions O15−H15O···O2(viii) O25−H25O···O3(iv) O1−H1O···O14(v)

Cd−O4 Cd−O5 Cd−O8 Cd−O10 Cd−O11 Cd−O6(i) Cd−O7(i) Cd−Cd(v)

O10−H1O···O7(iii) O10−H2O···O9(v) O11−H3O···O2(vi) O11−H4O···O10(v) C2−H2···O4 C6−H6···O2 C9−H9···O2(vi) C11−H113···O8

Cd1O6 Cd1O7 Cd1O22 Cd1O1(i) Cd1O24(i) Cd1O25(i) Cd1O32(i) Na1O2 Na1O25 Na1O32 Cd1···Na1(ii) Na···Cd1(i) Na1···Cd1(v)

N31−H311···O21(vi) N31−H311···O23(vi) N31−H312···O3(viii) C6−H6···O2 C22−H22···O23 C26−H26···O26 C41−H41···O51 C33−H331···O3(i) C43−H431···O41 C52−H521···O51 C52−H523···O22(viii)

a Symmetry codes: (ii) −x, 1 − y, −z; (iii) 1 − x, 1 − y, −z; (iv) 1 − x, 1 − y, 1 − z. bSymmetry code: (i) x, 1 + y, z; (ii) 1 + x, y, z; (iii) −x, 1 − y, 1 − z; (iv) 1 − x, 1 − y, 1 − z; (v) 1 − x, 2 − y, 1 − z. c Symmetry code: (i) 1 + x, y, z; (ii) −1 + x, y, z; (iii) −x, 1 − y, −z; (v) 1 − x, 2 − y, 1 − z.

moieties (L1 and L2), and three aqua ligands (Figure 1a). The Cd ion occupies a special position 1̅ (at 0,0,0) and demonstrates an elongated octahedral geometry formed from four sulfonate O-atoms (O13, O13(i), O23, O23(i)) (symmetry code (i) −x, −y, −z) from four sulfobenzoate ligands, two of which are symmetry unique, and two water O-atoms (O1 and O1(i)) (all symmetry codes are consistent with those given in the tables and used in the figures). The Cd−O distances are limited between 2.2745 Å and 2.2971 Å. The potassium ion is seven coordinated and surrounded by four sulfonate O-atoms (O11, O21, O12(ii), O21(iii)) from four different Hsb ligands, two of which are unique, one carboxylic O-atom (O24(iv)) from a fifth ligand, as well as, by two independent water O-atoms (O2 and O3). The coordination polyhedron KO7 is best described as monocapped trigonal prism. Two inversion related prisms share an edge (O21O21(iii)) to form a polyhedron K2O12 (Figure 1b). The CdO6 and K2O12 polyhedrons are bridged via the sulfonate groups to form inorganic monolayers parallel to (ab) (Figure 1c). The aromatic portions of the ligands are arranged from both sides of the monolayers and serve as pillars between them. An analysis of the connectivity patterns reveals that only the sulfonate sites of L1 and L2 are employed in bridging the metal ions and the 2D network of the monolayer is pure inorganic. Each sulfonate group S(11)O3 and S(21)O3 interconnects

Symmetry codes: (i) −x, −y, −z; (ii) −x, 1 − y, −z; (iii) 1 − x, 1 − y, −z; (iv) 1 − x, 1 − y, 1 − z; (v) −x, −y, 1 − z; (vi) 1 − x, −y, −z; (vii) x, 1 + y, z. (viii) −1 + x, −1 + y, −1 + z. bSymmetry codes: (iii) −x, 1 − y, 1 − z; (v) 1 − x, 2 − y, 1 − z; (vi) 1 + x, 1 + y, z. cSymmetry codes: (i) 1 + x, y, z; (vi) x, −1 + y, z; (viii) 1 − x, 2 − y, −z. a

three metal centers (two K and one Cd) to extend them into 2D coordination network with two different coordination modes: η3μ3κ3 and η3μ3κ2. The S(21)O3 group employs only two oxygen atoms: μ2-O21 atom to interlock two close potassium centers (K−K(iii) of 3.7915(16) Å) into a dimer, and O23 atom to bridge the K-dimer with a cadmium center. The other group S(11)O3 uses all three O-sites and serves to extend the potassium dimers into ribbons along the a axis and to bridge them with Cd centers. In fact the potassium ribbons are formed from two alternating coordination ring motifs: the interlocking R2,2(4) motif and the bridging R2,4(8) motif.27 The Cd ions crisscross the K-ribbons into a grid 2D framework forming a heteromeric R2,4(8) motifs. The distances between the metal centers in the 2D frameworks are 3.7915(16) Å for K−K(iii) in the interlocking ring R2,2(4), 5.906 Å for K−K(ii) in the homomeric R2,4(8) ring and 5.7127 Å (Cd−K), and 6.0777 Å (Cd−K(iii)) in the heteromeric R2,4(8) ring. The twodimensional framework of the monolayer is grid and big rings R4,8(16) generated in there (Figure 2b). 2616



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Figure 1. Structural details of 1. (a) The asymmetric unit with the numbering scheme (the thermal ellipsoids are plotted with 50% probability); (b) the coordination environment and geometry of Cd(II) and K(I) metal ion centers. Symmetry codes: (i) −x, −y, −z; (ii) −x, 1 − y, −z; (iii) 1 − x, 1 − y, −z; (iv) 1 − x, 1 − y, 1 − z; (c) the arrangement of CdO6 and K2O12 units in the monolayer.

The organic portions of L1 and L2 are arrayed from both sides of the monolayer and follow the symmetry relationships dictated by the coordination network. The opposite positioned carboxylic sites are used to interconnect the monolayers (Figure 2c). The carboxylic group of L2 serves to donate a K−O bond toward the potassium ion of the next layer (K1−O24(iv) of 2.8165(17) Å) and additionally participates in a hydrogen bond (O25−H25O···O3(iv) of 2.656(2) Å) toward a water molecule form the next layer. The carboxylic group of the other ligand L1 is not bonded to a metal, but it forms two interlayer water−carboxylic hydrogen bonds (O1−H1O···O14(v) of 2.731(2) Å and O15−H15O···O2(viii) of 2.637(3) Å).

Figure 2. Structural organization and connectivity patterns in 1. (a) The coordination modes of the unique ligands (the thermal ellipsoids are plotted with 50% probability); (b) the 2D inorganic coordination network; (c) the hybrid 3D framework viewed along the a-direction. All hydrogen atoms except those of the carboxylic groups are omitted and the nonbonding ligands L1 are deleted from the interlayer region on the right side of the picture.

The aromatic portions of the ligands are arranged in the interlayer region and form two differently oriented stacks with offset face-to-face (OFF) interactions between the symmetry 2617



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unique rings (Table S3). In addition π···πring interactions are observed between neighboring inversion related stacks, which are established between the carboxylic double bond and the aromatic ring of the ligand (C17−O14···Cg1(ix), where Cg1 is the ring centroid of L1, symmetry code (ix) −x, −y, −1 − z) (Table S4). The molecular configurations the unique ligands are stabilized by two C−H···O hydrogen bonds. In addition, the 2D network of the monolayer is stabilized by four hydrogen bonds (O1− H2O···O22(vi), O2−H3O···O22(vii), O2−H4O···O13(iii), and O3−H6O···O11(ii)), formed between the aqua ligands and the sulfonate groups and one hydrogen bond (O3−H5O···O1(i)), formed between two aqua ligands (Table 3). Crystal Structure of [NaCd(sip)(DMF)2(H2O)2]2n (2). The crystal structure of 2 is layered with metal ions and sulfoisophthalic acid moieties arranged into a monolayer and dimethyformamide (DMF) molecules protruding in the interlayer region. The asymmetric unit of 2 contains one cadmium and one potassium ions, one sulfoisophthalate trianion (sip), two DMF and two coordinated water molecules. The cadmium(II) ion is seven coordinated and surrounded by two different carboxylate groups of two sip moieties, two independent water molecules, and one DMF molecule. The coordination polyhedron is best described as a pentagonal bipyramid with four carboxylate (O4, O5, O6(i), O7(i)) and one water (O11) oxygen atoms as equatorial ligands. Two more O-atoms (O10 and O8), coming from another water molecule and a DMF molecule, serve as axial ligands (Figure 3a). The equatorial plane of the CdO7 polyhedron is almost coplanar with the aromatic ring of the sip ligand. The sodium ion is five coordinated with two sulfonate (O3(ii) and O3(iii)) and two carboxylate (O5 and O6(iv)) oxygen atoms from four sip ligands and one O-atom (O9) from a DMF molecule. The τ-descriptor of 0.45 suggests that the coordination polyhedron is intermediate between a square pyramid and a trigonal bipyramid with an O3(ii) pivot atom that best describes the Berry pseudo rotation. Two NaO5 polyhedrons share two corners (O3(ii) and O3(iii)) to form a Na2O8 dimeric unit (Na− Na(iv) of 3.7587(12) Å) and additionally two more corners (O5 and O6) with two neighboring CdO7 bipyramids to form a polymeric ribbon {Na2Cd2O18}n along the b-axis. The distances between the metal centers in the tetrameric unit are 3.7587(12) Å (Na−Na(iv)), 4.1167(10) Å (Cd−Na(v)), 4.5629(11) Å (Na− Cd), and 5.4410(11) Å (Cd−Cd(v)), while the closest interdistance between the metal centers of two ribbons is 5.2669(7) Å (Cd−Cd(ix), symmetry code (ix) −x, 2 − y, 1 − z). The metal ribbons are interlinked via the aromatic rings of the ligands in order to form a monolayer parallel to the (ab) crystallographic plane (Figure 3b). The auxiliary DMF ligands, arrayed from both sides of the monolayers are protruding into the interlayer region and the monolayers are arranged in the third direction with hydrophobic interactions created between their methyl groups (Figure 3c). As far as the connectivity patterns inside the monolayer are concerned, they are realized via all three functional groups of the ligand, incorporating also the aromatic ring. So, unlike the pure inorganic 2D network of the metal layer in crystal 1, the two-dimensional framework in 2 is hybrid. The sip trianion acts as η8μ6κ5 ligand, binding two cadmium and four sodium ions, to extend them in two crystallographic directions. The sulfonate group of the ligand is used to catenate, in η2μ2κ fashion, two neighboring sodium ions, interlocking them into a dimer with an R2,2(4) ring motif. The carboxylate groups of the ligand adopt η3μ2κ2 modes to bis-bidentately bind the Cd ions,

Figure 3. Structural organization and packing patterns of 2. (a) The coordination polyhedrons and the environment of Cd(II) and Na(I) metal centers. Symmetry codes: (i) x, 1 + y, z; (ii) 1 + x, y, z; (iii) −x, 1 − y, 1 − z; (iv) 1 − x, 1 − y, 1 − z; (b) a view of the monolayer consisting of {Na2Cd2O18}n polymeric ribbons, interconnected by the aromatic rings; (c) a side view of two monolayers visualizing the interlayer relationships. All H atoms (except the DMF H8 atom) are removed from the pictures.

extending them into chains along the b-axis, and to bind two sodium ions, extending the sodium dimer in a-direction via a 10-member chelate ring R2,3(10) (Figure 4a). The 2D framework of the monolayer can be disentangled into two identical polar nets, which are antiparallely interpenetrated. The single net displays big R4,7(26) rings, where the cadmium ions of the opposite net fit (Figure 4b). The two inversion related nets are intertwined via three ring motifs: R2,2(4), R4,4(8), and R2,3(10) to form the 2D framework of the monolayer (Figure 4c). The eight-member rings R4,4(8) interweave the 2618



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arranged in pairs between the metal ribbons with offset face-toface (OFF) interactions. Four intramolecular C−H···O hydrogen bonds and four intralayer O−H···O hydrogen bonds stabilize the two-dimensional framework of the monolayer (Table 3). Crystal Structure of [NaCd2(sip)2(DMF)2(H2O)2]2n· 2nHdeta·2nH2O (3). The impact of the counterion on the final composition rate and the resultant metal−organic frameworks is demonstrated in compound 3. The metal− ligand ratio and all other synthesis conditions are identical for 2 and 3 with the exception of the applied salt. Cadmium nitrate instead of cadmium chloride has been used for synthesis of 3. The obtained compound also demonstrates a layered structure with metal ions and acid moieties (sip) arranged inside the monolayers and DMF molecules protruding into the interlayer regions. However, the molecular organization inside the layers and between them is quite different from that in 2. The asymmetric unit of 3 contains two cadmium and two halves of sodium ions, two unique totally deprotonated sulfoisophthalate moieties, two DMF and two water molecules in the role of ligands, as well as, two solvated diethylammonium ions and two crystalline water molecules. Both cadmium ions are seven coordinated with bipyramidal geometries but distinct coordination environments (Figure 5a). Cd1 is surrounded by two bidentate (chelating) carboxylic groups and two sulfonate groups of four different sip ligands (two of which are unique), and one aqua ligand. The carboxy O-atoms (O6, O7, O24(i), O25(i)) and the water O32(i) atom act as equatorial ligands, while the sulfonate O-atoms (O22 and O1(i)) as axial ligands. Cd2 ion also coordinates bis-bidentately to two carboxylic groups (O4(iii), O5(iii), O26, O27) of two unique sip ligands, but the sulfonate O-ligands are replaced from its coordination sphere. Two DMF molecules play the role of an equatorial and axial ligand, and another aqua ligand occupies the second axial position in the Cd2 polyhedron. The two independent sodium ions are located in special positions at the inversion centers and display octahedral geometries with quadratic elongations. The Na1 octahedron is formed from two sulfonate (O2 and O2(iv)) and two carboxy (O25 and O25(iv)) oxygen atoms located on four different ligands, two of which are unique, as well as two aqua ligands (O32 and O32(iv)) (symmetry code (iv) −x, 2 − y, 1 − z). The sulfonate ligands act as axial and the carboxylic groups as equatorial ligands. The Na2 octahedron is formed from four carboxy oxygen atoms (O4, O4(iii), O27, and O27(iii)) of four different sip ligands, two of which are unique, and two axial aqua ligands. The NaO6 octahedrons are combined with CdO7 bipyramids via edge-sharing and corner-bridging to form two different trimeric clusters: NaCd2O16 and NaCd2O14. The Na1 octahedron in NaCd2O16 shares two pairs of edges (O25, O32, and O25(iv), O32(iv)) with two neighboring inversion related Cd1(ii) and Cd1(v) bipyramids. In addition, the sodium and cadmium ions in the trimer Cd1−Na1−Cd1 are bridged by the sulfonate sites of two inversion related sip1 ligands. The other trimer NaCd2O14 is formed by sharing of pair of opposite triangle faces (O4(iii), O27 O31 and O4, O27(iii), O31(iii)) between the Na2 octahedron and two inversion related Cd2 bipyramids. The metal clusters are interlinked in two dimensions by the help of the aromatic portions of sip ligands (Figure 5b). Each unique benzene ring is binding three different metal clusters, two NaCd2O16 and one NaCd2O14 to arrange them into a layer. The 2D framework is a ladder type and can be disentangled into two undulate interpenetrated networks, interweaved at the metal ions. Both sip moieties act as seven-dentate ligands and

Figure 4. Structural organization and connectivity patterns of 2. (a) The coordination mode of the ligand. Symmetry codes: (ii) 1 + x, y, z; (iii) −x, 1 − y, 1 − z; (iv) 1 − x, 1 − y, 1 − z; (vii) −1 + x, y, z; (viii) x, −1 + y, z; (ix) −1 − x, 1 − y, 1 − z; (b) a single noncentrosymmetric 2D coordination net; (c) the hybrid framework of the monolayer.

Cd chains into ribbons, the four-member rings R2,2(4) interlock the sodium ions in the ribbons, and the 10-member rings R2,3(10) expand the ribbons. The aromatic rings are 2619



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interconnect two sodium and three cadmium ions, but they use two different coordination modes: η7μ5κ6 (sip1) and η7μ5κ5 (sip2) (Figure 6a). Consequently, the functional groups in

Figure 5. Structural details of 3. (a) The coordination environment of the metal ions. Symmetry codes: (i) 1 + x, y, z; (iii) −x, 1 − y, −z; (iv) −x, 2 − y, 1 − z; (b) the 2D organization of the metallic clusters in the layer; (c) a side view of two layers demonstrating the channels formed between the DMF molecules and the guest diethylammonium ions occupying the channels. The H-atoms are removed for clarity. Color codes: NaCd2O16 trimer: green-purple-green; NaCd2O14 trimer: blueviolet-blue.

Figure 6. Structural details and connectivity patterns in 3. (a) The coordination modes of sip1 and sip2; (b) the Cd(1) chain with pendant arms of Cd(2); (c) the 2D net formed by sip1; (d) the 2D net formed with sip2. 2620



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them adopt somewhat different coordination modes: η2μ2κ2, η3μ2κ2, η2μκ2 in sip1 and ημκ, η3μ2κ2, η3μ2κ2 in sip2. Each of the sip ligands extends the cadmium ions into a chain with pendant arms (Figure 6b). Pairs of inversion related chains (Cd-sip1 or Cd-sip2) are intertwine at Na2 to form rope ladders, which are interlaced by Na1 to form two slightly different 2D networks sip1 and sip 2 (Figure 6c,d). The connectivity pattern in the nets are the same along the ladders, and different between them. The interlinking sodium ions Na1 and Na2, are located in special positions (at inversion centers) between pairs of cadmium ions and display different environment. In both networks (sip1 and sip2) the Na2 ions are arranged along the ladders and surrounded by two pendant carboxy sites, used to chelate the Cd2 ion, forming thus a trimeric unit Cd2−Na2− Cd2. Thirty-two ring motifs R4,8(32) are closed between four metal ions and four sip ligands along the ladders. The Na1 ions are arranged between the ladders and are bonded to the carboxy O-sites of opposite ropes in sip2-net and to sulfonate O-sites in sip1-net. So, Na1 and Cd1 ions are bridged in η2μ2κ fashion in net2 and in η2μ2κ2 fashion in net1, which leads to generation of two different ring motifs: R4,8(20) in net2 and R4,8(24) in net1. The two nets are interweaved at the metal centers and interlocked via the μ2-O sites of the aqua ligands (Figure 7a). The two interweaving motifs M1 (Cd1−Na1−Cd1

R2,2(4) rings, one pair of bridging motifs R2,2(8), and three different pairs of R2,3(6) rings. The interdistances between the metal centers are 3.7119(10) Å for Na1···Cd1(ii), Na1···Cd1(v) and 7.4237(16) Å for Cd1(ii)···Cd1(v). Only the carboxylate sites are partaking in M2 and the metal ions of the Cd2−Na2− Cd2 trimer are interlocked with three pairs of R2,2(4) rings and bridged by four pairs of R2,3(6) and one pair of R2,2(8) rings, which is reflected in the shorter intermetallic distances: 3.2892(9) Å for Na2···Cd2, Na2···Cd2(iii)) and 6.5785(14) Å for Cd2···Cd2(iii). Yet the intermetallic distances established between cadmium ions of neighboring a-translation trimers are closer (6.0851(13) Å for Cd2···Cd2(ix) along the ladder and 6.0173(12) Å for Cd1···Cd1(v) between the ladders) (symmetry codes: (v) 1 − x, 2 − y, 1 − z; (ix) 1 − x, 1 − y, −z). Offset face-to face interactions are established between the aromatic portions of the unique ligands inside the layer. The solid state configurations of the ligands are stabilized by three C−H···O hydrogen bonds, two of which (C6−H6···O2, C22− H22···O23) are established between the aromatic rings and the sulfonate groups and the third one (C26−H26···O26) is formed between the aromatic ring and the carboxylic group. There are no interlayer hydrogen bonds or other specific interactions in this structure. The layers are arranged with hydrophobic interactions between the DMF ligands, which protrude into the interlayer region to form hydrophobic channels along the [011] direction. The geometry of the DMF ligands and hence the size and geometry of the channels are congealed by several C−H···O hydrogen bonds. Two intramolecular bonds (C43−H431···O41 and C52−H521···O51), created between one of the methyl groups and the oxygen site of the DMF ligands and another bond (C52−H523···O22(viii)), formed between a methyl group and a sulfonate site, effectively prevent the methyl groups from rotation. The diethylammonium ions are arranged along the channels. Three N−H···O, and one C−H···O hydrogen bonds are established between the cation and the sulfonate oxygen site of the sip ligands, which probably restrain the disorder of the guest ions. The solvated water molecules are arranged in small channels generated inside the layers along the a-direction. Vibrational Properties. The IR spectra, measured for 2 and 3, are compatible with their crystal structures and manifest well the peculiarities of the compounds. They differ significantly in the spectral range higher than 2500 cm−1, but they are very similar in the range 2000−400 cm−1 (Figure S2). The first region covers the stretching vibrations νaOH of the water molecules and the νC−H stretching of the aromatic rings, as well as the stretching vibrations νCH3, νCH2 (of the auxiliary DMF ligand) and νNH2 arising from the protonated diethylamine. The number and the position of the νaOH bands, observed in this region, manifest the different functions of the water molecules (as metal ligands or as solvated molecules) and reflect the role they play (as hydrogen-bond donors and/or acceptors) in the structure. On the other hand the similarity of the IR spectra in the region of the internal vibrations reflects the identity of the components (metal ligands) incorporated in the crystal network. The small differences observed in the band positions and intensities of the stretching vibrations of the ligands’ functional groups (νCOO−, νSO3−) are most probably issued from the differences in their connectivity patterns. The wavenumbers and intensities of all observed bands, together with their tentative assignments are given in Table S1. Thermal Properties. From the analysis of the thermal curves (Figures S3−S4), it appears that the crystal network in

Figure 7. Structural details and connectivity patterns in 3. (a) The 2D framework; (b) the interweaving motifs M1 and M2 of the framework. Symmetry codes: (i) 1 + x, y, z; (ii) −1 + x, y, z; (iii) −x, 1 − y, −z; (iv) −x, 2 − y, 1 − z; (v) 1 − x, 2 − y, 1 − z; (ix) 1 − x, 1 − y, −z.

trimer) and M2 (Cd2−Na2−Cd2 trimer) of the 2D framework are shown in Figure 7b. Both the sulfonate and the carboxylate groups are involved in M1 and the metal centers in Cd1−Na1− Cd1 trimer are interconnected via one pair of interlocking 2621



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compound 1 is stable up to 515 °C and then it undergoes a total destruction. The compound loses four water molecules (two solvated and two coordinated), which are released in the temperature range 82−182 °C (found, 9.50 wt %; calcd, 9.79 wt %). The ion currents in this range display peaks only for ions with m/z = 18, which are assigned to H2O+. The MS peaks of ions with m/z = 18, 44 and 64, observed in the range from 180 to 515 °C, testify to the gradual destruction of the material. In addition, the differential thermal analysis (DTA) shows that a strongly endothermic reaction takes place at 520 °C, which indicates that the crystalline network of the compound collapses. The first weight loss in compound 2 is observed in the region 80−180 °C and attributed to the release of the coordination water molecules (found, 6.83 wt %; calcd, 6.42 wt %). The second weight loss, observed in the range 180−419 °C, is related with the loss of the DMF ligands (found, 25.61 wt %; calcd, 26.03 wt %). The destruction of the material takes place in the range 420−490 °C. The ion currents of m/z = 18 (H2O+) appeared in all three steps. The MS peaks of ions with m/z = 30 (NO+ or CH3NH+) were found only in the second process, whereas peaks of ions m/z = 44 (CO2+ or (CH3)2N+) and 46 (NO2+ or (CH3)2NH2+) were observed in the second and third steps and finally MS peak of ion m/z = 64 (SO2+) were observed only in the last process. Differential thermal analysis (DTA) shows a strong endothermic reaction at 490 °C, indicating for the total collapse of the crystalline net. The decomposition of compound 3 can be described as a three-step process according to the TGA curve. The two-step weight loss in the temperature range 80−160 °C is connected with the stepwise release of the solvated and coordinated water molecules (found, 3.65 wt %; calcd, 3.53 wt %). The sharp weight loss, observed in the range 180−215 °C, is related with the loss of DMF ligands, diethylammonium ion and water molecules (found, 29.60 wt %; calcd, 27.35 wt %). MS peaks of ions with m/z = 30 (NO+ or CH3NH+), m/z = 44 (CO2+ or (CH3)2N+) and 46 (NO2+ or (CH3)2NH2+) have been observed in this region. A further decomposition occurs in the temperature range 340−500 °C. The observed peaks for m/z = 64 (SO2+) and m/z = 44 (CO2+ or (CH3)2N+) are connected with decomposition of the organic ligand. The small endothermic peak at 182 °C is attributed to the loss of DMF ligands and Hdeta molecule. The strong endothermic reactions at 398 and 494 °C are indicative for the breakdown of crystal framework. Luminescent Properties of Compounds 1−3. Coordination polymers constructed from d10 metal ion centers and conjugated organic ligands can be promising candidates for photoactive crystalline materials with potential application as light-emitting diodes (LED). The photoluminescent properties of 1−3 as well as of the potassium and sodium salt of the ligand molecules (KHsb and NaH2sip) were investigated at room temperature in the solid state and their emission spectra are shown in Figure 8. The sodium salt of 5-sulfoisophthalic acid displays photoluminescent emission at 322 nm upon excitation at 298 nm and the potassium salt of 4-sulfobenzoic acid displays an emission at 450 nm upon excitation at 327 nm (attributable to the π → π* and/or n → π* transition). Compound 2 exhibits photoluminescent emission with a maximum at 408 nm upon excitation at 325 nm. In the case of 3, a similar photoluminescence with a maximum of emission at 410 nm upon an excitation at 332 nm was observed. The emissions of 2 and 3 occur at much longer wavelength (the red shift is higher than 50 nm) than that of the free ligand (320 nm). The large

Figure 8. (a) The solid-state photoluminescence spectra of KHsb (λex = 327 nm) and compound 1 (λex = 330 nm) recorded at room temperature. (b) The solid-state photoluminescence spectra of NaH2sip (λex = 298 nm), compound 2 (λex = 325 nm), and compound 3 (λex = 332 nm) recorded at room temperature.

bathochromic shifts in 2 and 3 indicate that the aromatic rings of sip ligands are effectively interacting with the metal ions and/ or with each other through π-stacking interactions. It has been reported that the Cd(II) coordination complexes with aromatic carboxylate ligands may possess LMCT photoluminescent property.28 In addition, the similarity of fluorescence spectra of 2 and 3 in the peak profiles is indicative of the slight influence of the diethylammonium ion on the electronic structures. Similar bathochromic shifts are observed also in other metal complexes with the same ligand.29,30 Compound 1 exhibits a photoluminescent emission with maximum at 466 nm upon excitation at 330 nm, which is only slightly shifted toward higher wavelengths compared to the emission of the potassium salt of 4-sulfobenzoic acid ligand. This indicates that the emission band in 1 arises neither from metal-to-ligand nor from ligand-to-metal charge transfer, but simply is connected with the intraligand transition. It is worth noting the large Stokes shift in this case. The blue emissions observed for 2 and 3 in the solid state imply that the compounds may be potentially applicable as materials for blue-light-emitting diode devices.31

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CONCLUSIONS It should be noted that both the coordination modes with which the sip ligands bind to the metal ions, as well as the tangled motifs of the metallic clusters, are rare. A search in Cambridge Database (v.5.32) utilizing ConQuest v.1.3 and the Material Module of Mercury v.2.4 revealed that the coordination mode adopted by sip in compound 2 (Scheme 1c) has not been observed previously, while the coordination modes, adopted by sip1 and sip2 in 3 (Scheme 1d,e), are observed only in two Pb(II) compounds (UCINAI and TEXRAQ). As far as the two 2622



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interweaving motifs are concerned, motif M2 was retrieved in 10 more compounds (JIPLUQ, LELGEO, NIDCOS, NOJCOF, PEHNIA, SAGJOA, YOCCOI, ALOLIX, EKOPUQ, UQEPAI), seven of which are alkali metal or earth alkaline metal ion complexes, one lead, one europium and one holmium−sodium complexes. On the other hand, the mixed motif (M1-C,S) was not found at all, but its modified version, involving only carboxylic groups (M1-C,C) was found in 80 crystals and the sulfonate analogue of (M1-S,S), involving only sulfonate groups was observed in three crystals. From the above search, it becomes obvious that the coordination sphere of the metal ion should possess some flexibility to satisfy the above motifs.

ASSOCIATED CONTENT

S Supporting Information *

Crystallographic date files in CIF format, tables containing selected angles, π−π interactions between the aromatic rings, and π−π interactions between the carboxylic double bond and the aromatic ring, band positions and assignments of vibration modes, observed in the FT-IR spectra, as well as, figures presenting the PXRD, FT-IR spectra, TG-DTA curves, and MS peaks for compounds 1−3 are included as Supplementary Tables and Supplementary Figures. This information is available free of charge via the Internet at http://pubs.acs.org.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Notes

The authors declare no competing financial interest.

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REFERENCES

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Finally, using the classification proposed by Cheetham,32 the presented hybrid structures can be described as I2O1 (1), I1O1 (2), and I0O2 (3), with respect to the organic and inorganic connectivity in them. So, compound 1 displays a mixed inorganic−organic 3D framework; compound 2 demonstrates mixed inorganic−organic layers, and compound 3 is layered coordination polymer.

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Article

ACKNOWLEDGMENTS

We gratefully acknowledge financial support from the Polish Ministry of Science and High Education (Grant No S10064/ Z0304, Department of Chemistry of Wrocław University of Technology, statutory activity). 2623



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