Hydrogen Bondings, Non-Interpenetrated and Polycate - American

Article pubs.acs.org/crystal

Metal−Organic Frameworks Based on Flexible V-Shaped Polycarboxylate Acids: Hydrogen Bondings, Non-Interpenetrated and Polycatenated Qingxiang Yang,† Xingqiu Chen,† Jiehu Cui,† Jinsong Hu,† Mingdao Zhang,† Ling Qin,† Gaofeng Wang,† Qingyi Lu,† and Hegen Zheng*,†,‡ †

State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing National Laboratory of Microstructures, Nanjing University, Nanjing 210093, P. R. China ‡ State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, P. R. China S Supporting Information *

ABSTRACT: Solvothermal reactions of 4,4′-dicarboxydiphenylamine (H2L) with 4,4′-bis(imidazol-1-yl)phenyl (BIP) and 4,4′-bis(imidazol-1-yl)diphenyl (BIBP) in the presence of cobalt(II), cadmium(II), zinc(II) salts in H2O/CH3CN or H 2 O/DMF produced five new complexes, namely, [Co2(L)2(BIP)2·3H2O]n (1), [Co(L)(BIP)·2CH3CN]n (2), [Co(L)(BIBP)·H2O]n (3), [Cd(L)(BIBP)]n (4), [Zn(L)(BIBP)]n (5). Compound 1 has binuclear Co(II) clusters, which are linked by L2− and BIP to generate a rare threedimensional (3D) non-interpenetrated cds-type framework, and displays ferromagnetic character. Compound 2 possesses unusual 3-fold 2D → 2D polycatenation of (4, 4) nets. Compound 3 reveals a (4, 4) grid topology with very strong hydrogen bondings due to the abundant uncoordinated carboxyl groups, which load in the structure like a freely dangling arm. Compound 3 also displays weak ferromagnetic character. Compounds 4 and 5 are isomorphic. H2L and BIBP ligands in 4 and 5 interact with a metal center to form wave-like 2D sheets. In addition, the thermal stabilities and photochemical properties of compounds have been studied.

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INTRODUCTION The design and synthesis of coordination polymers have received great interest with wonderful structures and properties from various molecular building blocks connected by coordination bonds and supramolecular contacts, because of their potentially wide applications in functional materials.1−4 A great many spectacular metal−organic frameworks (MOFs) have been documented, such as one-dimensional (1D) chains5 and ladders,6 two-dimensional (2D) grids,7 three-dimensional (3D) microporous networks,8 interpenetrated modes,9 and helical staircase networks.10 Among these, particular attention has been recently devoted to systems containing entanglements of individual motifs. Nevertheless, it is still a great challenge to rationally design and construct the desired compounds. The structures of MOFs built by coordination bonds and/or supramolecular contacts can dramatically change by very small tuning factors.11 Many factors, such as organic ligands,12 solvent system,13 metal ions,14 and counterions,15 are found to greatly influence the structures, rendering it difficult to predict the construction of molecular architectures. Of all these, the choice of ligands is a key factor. The donor atoms, functional groups, and relative position can directly vary framework structures. Moreover, flexible ligands also have attracted special interest because their flexible conformations are expected to produce © 2012 American Chemical Society

many intriguing architectures such as polymorph, entanglement, and so on.16 Therefore, systematic studies of diversified conditions leading to different structures in the formation of coordination polymers are important and of intense interest. A large number of mixed-ligand MOFs have been reported,17 revealing that the combination of different ligands can result in greater tunability of structural frameworks than single ligands. Mixed-ligands are thus a good choice for the construction of new polymeric structures. Diphenylene dicarboxylates have been shown to give rise to interesting structures and properties, such as 4,4′-(hexafluoroisopropylidene)bis(benzoicacid) (H2hfipbb) and 4,4′-oxybenzoic acid (H2oba).18,19 We have been interested in the study of diphenylene bis-imidazole based coordination polymers of transition metals, resulting in interesting structures.20 In continuation of this theme, we are now studying the reactions involving 4,4′-dicarboxydiphenylamine (H2L). As a dicarboxylate ligand, it possesses the following interesting structural characteristics: (a) there are two carboxyl groups with a 120° angle separated by an imino group and two benzene rings, which would Received: April 19, 2012 Revised: June 7, 2012 Published: June 14, 2012 4072

dx.doi.org/10.1021/cg300541n | Cryst. Growth Des. 2012, 12, 4072−4082

Crystal Growth & Design

Article

Scheme 1. The V-Shaped Polycarboxylate Ligand and Imidazole Ligands

Table 1. Crystallographic Data for Compounds 1−5 compound

1

2

3

4

5

formula formula weight crystal system space group a (Å) b (Å) c (Å) α (deg) β (deg) γ (deg) V (Å3) Z Dc (g cm−3) μ (Mo) Ka) (mm−1) F(000) R(int) observed data [I > 2σ(I)] [I > 2σ(I)] R1, wR2 [I > 2σ(I)] S min and max res (e·Å−3)

C104H76Co4N20O23 1048.78 triclinic P1̅ 13.496(7) 13.547(5) 15.455(5) 79.840(5) 87.950(8) 60.152(5) 2407.80 2 1.446 0.756 1076.0 0.0932 6401 0.0919, 0.2615 1.073 −1.209, 2.292

C28H24O5N6Co 583.46 triclinic P1̅ 10.3104(5) 10.6393(5) 12.5964(7) 88.131(1) 74.914(1) 86.047(1) 1330.82(12) 2 1.456 0.695 602.0 0.0354 3610 0.0478, 0.0835 1.018 −0.311, 0.424

C32H26O6N5Co 635.51 monoclinic P21/c 9.9190(8) 31.530(2) 9.9180(8) 90.00 118.9700 90.00 2714.0(4) 4 1.555 0.691 1312.0 0.0557 3124 0.0903, 0.0759 1.009 −0.349, 0.354

C32H23O4N5Cd 653.96 triclinic P1̅ 9.842(2) 10.237(3) 15.175(4) 72.892(4) 84.194(4) 63.756(4) 1309.9(6) 2 1.658 0.884 660.0 0.0512 3746 0.0597, 0.1350 1.013 −1.218, 2.316

C32H23O4N5Zn 606.94 triclinic P1̅ 9.8322(17) 10.2287(17) 15.171(3) 72.934(2) 84.297(3) 63.824(2) 1308.2(4) 2 1.541 0.989 624.0 0.0693 4224 0.0663, 0.2040 1.050 −0.604, 0.790

operated at 40 kV and 40 mA. The as-synthesized samples were characterized by thermogravimetric analysis (TGA) on a Perkin-Elmer thermogravimetric analyzer Pyris 1 TGA up to 1023 K using a heating rate of 10 K min−1 under N2 atmosphere. Luminescent spectra were recorded with a SHIMAZU VF-320 X-ray fluorescence spectrophotometer at room temperature. Temperature-dependent magnetic susceptibility data were obtained on a MPMS XL-7 SQUID magnetometer under an applied field of 2000 Oe over the temperature range of 2−300 K. Syntheses of Compounds. [Co2(L)2(BIP)2·3H2O]n (1). A mixture of Co(NO3)2·4H2O (29.1 mg, 0.1 mmol), BIP (21.2 mg, 0.1 mmol), and H2L (25.7 mg, 0.1 mmol) was dissolved in 6 mL of DMF/H2O(1:2, v/ v). The final mixture was placed in a Parr Teflon-lined stainless steel vessel (15 mL) under autogenous pressure and heated at 95 °C for 3 days. Purple crystals were obtained, which were washed with mother liquid, and dried under ambient conditions (yield: 80% based on H2L). Anal. Calcd for C52H38O8N10Co2: C, 56.47, H, 3.44, N, 12.47; found C, 56.57, H, 3.41, N, 12.38. IR (KBr, cm−1): 3429(w), 3115(w), 1591(s), 1529(s), 1383(s), 1339(s), 1302(m), 1131(s), 1061(w), 960(w), 934(w), 822(m), 781(s), 729(s), 651(m), 537(m). [Co(L)(BIP)·2CH3CN]n (2). Compound 2 was prepared by a procedure similar to that for the preparation of compound 1 by using Co(NO3)2·6H2O (29.1 mg, 0.1 mmol), BIP (21.2 mg, 0.1 mmol), and H2L (25.7 mg, 0.1 mmol) in 6 mL of CH3CN/H2O (1:2, v/v). Pink crystals were obtained (Yield: 66% based on H2L). Anal. Calcd for C28H24O5N6Co: C, 57.63, H, 4.12, N, 14.40; found C, 57.73, H, 4.06, N, 14.34. IR (KBr, cm−1): 3406(m), 3156(w), 2353(w), 1613(m), 1537(s),

reduce the steric interference/hindrance; (b) this provides an opportunity to study the relative torsional displacement of the benzene rings with respect to the central nitrogen atom. To test the ability of this ligand to give new architectures and topologies, we selected H2L ligand, 4,4′-bis(imidazol-1-yl) phenyl (BIP), and 4,4′-bis(imidazol-1-yl)diphenyl (BIBP) (Scheme 1), and different bivalent metal salts to solvothermally synthesize five new coordination polymers with intriguing structures, namely, [Co2(L)2(BIP)2·3H2O]n (1), [Co(L)(BIP)·2CH3CN]n (2), [Co(L)(BIBP)(H2O)2]n (3), [Cd(L)(BIBP)]n (4), and [Zn(L)(BIBP)]n (5). These compounds have been characterized by elemental analysis, IR spectra, and X-ray crystallography. The crystal structures, topological analyses, and their thermal properties have been studied. In addition, photoluminescences for 4 and 5, and magnetic character for compounds 1 and 3 are discussed in detail.

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EXPERIMENTAL SECTION

Materials and Methods. The reagents and solvents employed were commercially available and used as received. IR absorption spectra of the compounds were recorded in the range of 400−4000 cm−1 on a Nicolet (Impact 410) spectrometer with KBr pellets (5 mg of sample in 500 mg of KBr). C, H, and N analyses were carried out with a Perkin−Elmer 240C elemental analyzer. Powder X-ray diffraction (PXRD) measurements were performed on a Bruker D8 Advance X-ray diffractometer using Cu−Kα radiation (λ = 1.5418 Å), in which the X-ray tube was 4073



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Figure 1. (a) Coordination environment of the Co(II) ion in 1. The hydrogen atoms are omitted for clarity. Symmetry codes: (#1) 1 − x, 1 − y, 1 − z; (#2) 1 − x, 2 − y, 1 − z; (#3) x, −1 + y, z; (#4) −x, 3 − y, 2 − z; (#5) −1 − x, 4 − y, 2 − z; (#6) 1 + x, −1 + y, z; (#7) −1 + x, 2 + y, 1 + z. (b) The wave-like chians of Co2(L)2. (c) Perspective of the 3D framework of 1 along the c axis (guest molecules are omitted). 1518(s), 1497(s), 1394(w), 1247(s), 1121(m), 1069(s), 966(w), 942(w), 839(m), 812(w), 772(s), 734(s), 656 (m), 526(m). [Co(L)(BIBP)(H2O)2]n (3). A mixture of Co(NO3)2·4H2O (29.1 mg, 0.1 mmol), BIBP (28.8 mg, 0.1 mmol), and H2L (25.7 mg, 0.1 mmol) was dissolved in 6 mL of DMF/H2O (1:3, v/v). The final mixture was placed in a Parr Teflon-lined stainless steel vessel (15 mL) under autogenous pressure and heated at 95 °C for 3 days. Purple crystals were obtained (yield: 54% based on H2L). Anal. Calcd for C32H26O6N5Co: C, 60.38, H, 4.09, N, 11.01; found C, 60.27, H, 4.11, N, 11.10. IR (KBr, cm−1): 3134(w), 3075(w), 1685(s), 1634(s), 1602(w), 1553(s), 1512(s), 1448(m), 1375(s), 1268(s), 1240(s), 1128(w), 1103(m),

1064(m), 963(w), 938(w), 877(m), 836(w), 798(m), 760(s), 722(m), 663(m), 523(m). [Cd(L)(BIBP)]n (4). A mixture of Cd(NO3)2·4H2O (30.1 mg, 0.1 mmol), BIBP (28.8 mg, 0.1 mmol), and H2L (25.7 mg, 0.1 mmol) was dissolved in 6 mL of DMF/H2O (1:3, v/v). The final mixture was placed in a Parr Teflon-lined stainless steel vessel (15 mL) under autogenous pressure and heated at 95 °C for 3 days. Pale brown crystals were obtained (yield: 47% based on H2L). Anal. Calcd for C32H23O4N5Cd: C, 58.72, H, 3.52, N, 10.70; found C, 58.87, H, 3.41, N, 10.66. IR (KBr, cm−1): 3454(w), 3116(w), 1553(s), 1519(s), 1384(s), 1240(s), 4074



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1123(m), 1067(s), 1015(w), 964(w), 930(w), 855(m), 824(s), 745(s), 653(m), 531(m). [Zn(L)(BIBP)]n (5). A mixture of Zn(NO3)2·4H2O (29.7 mg, 0.1 mmol), BIBP (28.8 mg, 0.1 mmol), and H2L (25.7 mg, 0.1 mmol) was dissolved in 6 mL of DMF/H2O (1:3, v/v). The final mixture was placed in a Parr Teflon-lined stainless steel vessel (15 mL) under autogenous pressure and heated at 95 °C for 3 days. Light brown crystals were obtained (yield: 50% based on H2L). Anal. Calcd for C32H23O4N5Zn: C, 63.05, H, 3.79, N, 11.55; found C, 59.97, H, 3.81, N, 11.50. IR (KBr, cm−1): 3299(w), 3111(w), 1591(s), 1516(s), 1386(s), 1249(s), 1171(m), 1124(w), 1062(s), 960(w), 930(w), 845(m), 815(s), 786(s), 680(m), 529(m). Crystal Structure Determination. X-ray crystallographic data of 1−5 were collected at room temperature using epoxy-coated crystals mounted on glass fiber. All measurements were made on a Bruker Apex Smart CCD diffractometer with graphite-monochromated Mo−Kα radiation (λ = 0.71073 Å). The structures of compounds 1−5 were solved by direct methods, and the non-hydrogen atoms were located from the trial structure and then refined anisotropically with SHELXTL using full-matrix least-squares procedures based on F2 values.21 The hydrogen atom positions were fixed geometrically at calculated distances and allowed to ride on the parent atoms. The distribution of peaks in the channels of 1 was chemically featureless to refine using conventional discrete-atom models. To resolve these issues, the contribution of the electron density by the remaining water molecule was removed by the SQUEEZE routine in PLATON.22 The number of solvent molecules in 1 was obtained by element analysis. The relevant crystallographic data are presented in Table 1, while the selected bond lengths and angles are given in Supporting Information, Table S1.

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RESULTS AND DISCUSSION Structure of [Co2(L)2(BIP)2·3H2O]n (1). The structure of 1 is a 3D non-interpenetrated framework. X-ray analysis reveals that 1 crystallized in triclinic space group P1̅. The asymmetric unit of 1 contains two independent Co(II) cations, two L2− ligands, two BIP ligands, and three lattice water molecules. As shown in Figure 1a, Co1 and Co2 centers adopt similar trigonalbipyramidal geometry with {CoO3N2} coordination environment, while the coordinated bonds and angles are slightly different. The Co1 center is five coordinated by three carboxylic O atoms from three H2L ligands [Co1−O4 = 2.035(4) Å, Co1− O3 = 2.086(4) Å and Co1−O2 = 2.093(5) Å] and two nitrogen atoms from two BIP ligands [Co1−N1 = 2.113(5) Å and Co1− N3 = 2.118(5) Å]. The Co2 center is also five coordinated by three carboxylic O atoms from three H2L ligands and two nitrogen atoms from two BIP ligands but show different bond lengths: Co2−O8 = 2.027(4), Co2−O7 = 2.087(4), Co2−O6 = 2.112(4), Co2−N7 = 2.105(5), Co2−N5 = 2.106(5). The O/ N−Co−O/N bond angles are in the range 87.02(18)−178.1(2) °. Two L2− connect two Co(II) atoms to achieve a 28-membered [Co2(L)2] metallocyclic ring exhibiting maximum dimension of 12.731 × 8.989 Å (corresponding to the Co···Co distance and O···O separation). These rings are further connected through their corners forming 1D wave-like ladder-chain structures (Figure 1b). BIP double lines linking the parallel [Co2(L)2] chains in two different directions give rise to a 3D framework net, as shown in Figure 1c. To simplify the rather intricate structure of compound 1, the two parallel BIP ligands and L2− anions are considered as one linker, respectively. Thus, the Co2(COO)2 cluster can be reduced to a 4-connected nodes connecting to surrounding Co2(COO)2 cluster, as shown in Figure 2a. Closer examination of the structure of 1 reveals that the framework adopts the CdSO4 (cds) topology, a 4-connected 658 net,23 as shown in Figure 2b. It is interesting to note that unlike other cdstype MOFs, 1 is a rare example of a cds-type framework that is not interpenetrated. Most cds-type frameworks are inter-

Figure 2. (a) Schematic view of the simplified of Co2(COO)2 cluster in 1. (b) Schematic view of the 658 topology of CdSO4-type structure of 1 (carboxyl linkers are in blue, and N-linkers are in red).

penetrated due to the self-duality of the cds net.24 The cds topology can be derived from the NaCl structure by deleting onethird of the connections between the nodes. The cds topology has significantly fewer connections than the NaCl structure, but it has the same number of nodes. As a result, the cds net appears to be more flexible compared to the rigid nature of the NaCl topology. Structure of [Co(L)(BIP)(H2O)·2CH3CN]n (2). When using CH3CN/H2O instead of DMF/H2O as solvent, we obtained complex 2 possessing unusual 3-fold 2D → 2D polycatenation of (4, 4) nets. X-ray analysis reveals that 2 crystallized in triclinic space group P1̅. As depicted in Figure 3a, compound 2 contains one crystallographically independent Co(II) cation, one L2− ligand, one BIP ligand, one coordinated H2O molecule, and two free CH3CN molecules. The Co(II) center is five coordinated by two carboxylic O atoms from two H2L ligands and one O atom from water, and two nitrogen atoms from two BIP ligands to form a slightly distorted trigonal-bipyramidal geometry. The Co−O lengths are in the range of 2.0489(17)−2.1825(18) Å and Co−N lengths are 2.0893(18)−2.124(2) Å. As shown in Figure 3b, the BIP ligand links neighboring Co(II) ions to form an infinitely 1D zigzag chain. The Co···Co distances are 13.595(6) Å. The L2− anions link these zigzag chains to form ladder-like 2D sheets. In this sheet, each 50-membered macrocycle is formed by four Co(II) ions, two L2− anions, and two BIP ligands with a dimension of 23.105 × 17.466 Å (diagonal distances), which exhibits a deeply corrugated character. The 2D sheet contains a larger channel (to see clearly, the purple rod was added), and the 4075



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Figure 4. (a) and (b) 3-fold 2D → 2D parallel interlock structure and the rotaxane-like motif in 2 in different directions.

It is well-known that the most important driving forces in crystal engineering are coordination-bonding and hydrogenbonding interactions. Extended networks assembled by both coordination and hydrogen bonds is one of the important strategies to construct supramolecular networks.25 In principle, higher dimensionality networks can be obtained by the assembly of lower dimensionality polymers (or molecules) via hydrogen bonding interactions. Notably, significant hydrogen bonding interactions exist between the layers which are the most important factor for compounds from assembling into high dimensional coordination polymers. In compound 2, the 3-fold 2D → 2D interpenetration layers are held together into threedimensional (3D) supramolecular structures via hydrogen bonding between carboxyl oxygen atoms/imide nitrogen atoms and oxygen atoms from the coordinated water (Figure 5). The N5···O5 distance (3.065 Å) and N5−H5···O8 angle (176.09°) are both within the ranges of those reported hydrogen bonds. Furthermore, the other uncoordinated carbonyl oxygen atom O1 and the atom O4 interact with the oxygen atoms of the coordinated water in two directions to form an interesting 3D supramolecular structure with the O5···O1 distance of 2.652 Å, O5−H5···O1 angle of 159.39°, the O5···O4 distance of 2.739 Å and O5−H5···O4 angle of 144.78° (Figure 5). It is remarkable that these intramolecular hydrogen bonds are the most important factors to make compound 2 transform into high dimensional coordination polymers. Structure of [Co(L)(BIBP)(2H 2O)]n (3). The crystal structure of 3 was solved in the space group P21/c. As depicted in Figure 6a, the structure contains one crystallographically independent Co(II) ion, one L2− ligand, one BIBP ligand, and two coordinated water molecules. The Co(II) ion has a distorted octahedral geometry with two carboxylic O atoms from two L2− anions, two nitrogen atoms from two BIBP ligands in the equatorial plane, and two coordinated water in the axial position. The Co−O lengths are 2.046(3)−2.256(3) Å and the Co−N lengths are 2.089(3)−2.095(3) Å. The H2L displays an unusual mode of coordination with two carboxyl groups deprotonated, but only one O atom from one carboxyl group coordinates to Co atom, another carboxyl group is free (Scheme 2c). In Figure 6b, each Co atom is connected by H2L, BIBP, and coordinated water to form a 2D square sheet. In this sheet, the four BIBP ligands and four Co atoms and two L anions afford a square with 64membered metallocyclic ring. The L2− anions share Co atom and fill in the grids with the other one uncoordinated carboxylate like a freely dangling arm. The grid motif has the dimension of 31.50

Figure 3. (a) Coordination environment of the Co(II) ion in 2. The hydrogen atoms are omitted for clarity. Symmetry codes: (#1) 1 − x, 1 − y, −z; (#2) −x, 2 − y, −z; (#3) −1 + x, −1 + y, z. (b) the zigzag chain of [(BIP)Co] and the 2D sheet of 2. (c) Views of the ladder-like 2D framework with large channel by L2−, BIP, and Co ions in different directions.

size is about 15.317 × 7.211 Å2 (Figure 3c). As expected, the large dimensions and corrugated nature of the net allow them to interpenetrate in an extensive and unusual fashion. The Co(II) ions can be regarded as 4-connected nodes with all crystallographically independent L2− ligands and BIP acting as 2connected linkers. Therefore, the whole structure can be reduced as a (4, 4) 2D net. The large channel within each sheet allows them to interpenetrate between the adjacent sheets in a “parallel interpenetration” fashion, resulting in a finite polycatenation (Figure 4a,b). Each net was simultaneously penetrated by the two neighboring ones (“upper” and “lower”) to avoid large voids, and their mean planes are parallel and offset. In other words, as shown in Figure 4a, each window (pink) of the net is simultaneously catenated by the other two ones (yellow and sky-blue) and vice versa. Therefore, the 3-fold 2D → 2D parallel can also be regarded as being caused by the nets’ polycatenation. 4076



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Figure 5. Schematic representation the 3D framework of 2 via the hydrogen bonding (pink dash line).

× 17.40 Å (diagonal distances). Considering the Co atoms as four-connected nodes and BIBP as linker reveals a (4, 4) grid topology (Figure 6c). These sheets in 3 are stacked in an ABAB fashion. There are strong (O−H···O) hydrogen bonds between these sheets, which involve the coordinated water from one sheet and the arm dangling free carboxyl groups from another sheet, and vice versa (Figure 6d). The distances of O2···O5 and O1···O6 are 2.571 Å and 2.722 Å, respectively. The angles of O2−H2WB···O5 and O1−H1WB···O6 are 167.67° and 177.81°, respectively. And also hydrogen bonds exist in each single layer. The distance of O1···O4 (2.689 Å) and O2···O4 (2.731 Å) and the angle of O1−H1WB···O4 (162.16°) and O2−H2WB···O4 (164.32°) are both within the ranges of those reported hydrogen bonds. Obviously, these H-bonded interactions increase the stability of the whole crystal structure of 3, as it does not decompose until 435 °C. This suggests that the hydrogen bonds between carboxyl group and coordinated water play an important role in increasing the dimension and sustaining the stability of the whole structure. Structures of [Cd(L)(BIBP)]n (4) and [Zn(L)(BIBP)]n (5). Crystallographic analysis reveals that compounds 4 and 5 are isomorphous. Hence, only the crystal structure of 4 is described here in detail. X-ray analysis reveals that 4 crystallized in triclinic space group P1̅. The compound 4 consists of one crystallographically independent Cd(II) ion, one L2− anion, and one BIBP ligand. As shown in Figure 7, Cd(II) are six coordinated by four carboxylic O atoms from two H2L and two nitrogen atoms from two BIBP ligands to form a distorted octahedral geometry. The Cd−O lengths are in the range of 2.302(4)−2.408(3) Å and Cd−N lengths are 2.274(4)−2.319(4) Å, which are all similar to the values found in other Cd(II) compounds.26 The L2− anion coordinates to two Cd atoms by adopting chelating bidentate coordination modes (Scheme 2d). L2− anions link neighboring Cd atoms to form an infinitely 1D zigzag chain. The Cd···Cd distances are 15.175 Å. The BIBP ligands link these zigzag chains to form a wave-like 2D sheet (Figure 8). In this sheet, two L ligands and two BIBP ligands connect four Cd(II) atoms to achieve a 58-membered [Cd2(L)2(BIBP)2] metallocyclic ring exhibiting a maximum dimension of 30.94(4) × 9.84(2) Å) (diagonal distances). The Cd(II) ions can be regarded as 4connected nodes with all crystallographically independent L2− and BIBP ligands acting as linkers. Therefore, the whole structure

can be reduced as a (4, 4) sheet. The sheets are stacked in ABAB fashion and perform 3D supermolecular structure via hydrogen bonds (Figure 9). The structure of compounds 1−5 showed that the different structures are evidently affected by the configuration of L2− anions. The configuration of L2− anions can be described in two aspects. As shown in Figure 10, first, it can slightly adjust the angles to meet the requirement of coordination. The angles can be assessed by comparing the C···Ncore···C angle defined by the central nitrogen atom and the carbon atoms of the carboxyl groups. On the other hand, the two carboxyl groups are typically rotated with respect to the benzene rings. For compounds 1−5, the dihedral angle between the phenyl rings (A and B) are 10.0°, 24.6°, 40.2°, 52.0°, and 56.0°, respectively, which confirm that H2L ligand can adjust the corresponding angles from 10° and 56° in order to meet the requirement of coordination. As shown in Table 2, with the coordination modes change from bismonodentate and monodentate of compound 1 to monodentate of compound 2, the C···Ncore···C angles are almost the same, but the dihedral angles increase (from 10° to 25°). Comparing to compounds 1 and 2, compounds 4 and 5 take the chelate coordination mode and the BIBP is longer than BIP, so the C···Ncore···C angles slightly decrease, and the dihedral angles increase to 52° and 56°. Compound 3, which takes monodetate coordination mode with only one carboxyl group coordination, prefers the dihedral angle of 40°. H2L ligand is undoubtedly an ideal flexible polycarboxylate ligand. Thermal Analysis and PXRD Patterns. To characterize the compounds more fully in terms of thermal stability, their thermal behaviors were studied by TGA (Supporting Information, Figure S1). For compound 1, a rapid weight loss of 4.75% (calcd 4.88%) is observed from 50 to 175 °C, which is attributed to the loss of water, and the structure decomposes at 388 °C. In the case of 2, a gradual weight loss is attributed to the release of the lattice acetontrile molecule with a weight loss of 14.54% (calcd 14.05%), and then the network collapses at 400 °C. Compound 3 had a weight loss of 5.60% (calcd 5.66%) at 286 °C, which is attributed to the loss of two coordinated water molecules, and the framework collapses at 435 °C. The TGA study of compounds 4 and 5 show no weight loss from room temperature to 400 °C, suggesting that the frameworks are thermally stable. Above 400 °C, a rapid weight loss is observed which is due to the 4077



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Photochemical Properties of 4 and 5. Luminescent compounds are of great interest due to their various applications in chemical sensor, photochemistry, and light emitting diodes (LEDs).27 The luminescent properties of free ligands H2L, BIBP, 4 and 5 in the solid state at room temperature are investigated, as depicted in the Supporting Information (Figure S7). Emissions of the free H2L ligand were observed with the emission peak at 417 nm and 480 nm (λmax = 357 and 340 nm), and free BIBP ligand were observed with the emission peak at 407 nm (λmax = 340 nm) (Figure S7 inset), which could be attributed to the π* → π or π* → n transitions. For 4 and 5, excitation of the microcrystalline samples at 360 nm resulted intense fluorescent emissions (Figure S7), with similar maximum peaks observed in the blue region (483 nm and 523 nm for 4, 485 nm and 525 nm for 5), which may be attributed to the ligand-to-metal change transfer. Magnetic Properties of 1 and 3. The temperature dependence of the magnetic susceptibility of 1 in the forms of χMT versus T and the plot of M versus H are shown in Figure 11. At room temperature the value of product χMT (2.80 cm3 K mol−1) is significantly greater than the spinonly value for a highspin Co(II) center (1.875 cm3 K mol−1 for S = 3/2 and assuming g = 2.0). Upon cooling, the χMT value decreases continuously, reaching a minimum value of 2.04 cm3 K mol−1 at 8 K, and then this situation has an upturn reaching 2.36 cm3 K mol−1 at 1.8 K, suggesting the ferromagnetic coupling between Co(II) ions. The larger room-temperature χMT value and the phenomenon from 300 to 8 K can be ascribed to the significant orbital contribution of Co(II) ions with 4T1g state of the octahedral Co(II) centers.28 The plot of M versus H of 1 at 2 K is shown in Figure 11 (inset). The magnetizations increase quickly at low field and trends to saturation at high field with the M value of 2.59 NμB, which is consistent with the saturation value concurring in the theoretical range (2−3 NμB) expected for Co(II) compounds. Though they have similar structures, compounds 1 and 3 show different magnetic properties. For compound 3, the temperature dependence of the magnetic susceptibility (χMT versus T) is shown in Figure 12. At room temperature the value of product χMT is 2.86 cm3 K mol−1. The χMT value gradually decreases as the temperature decreases, until 12 K, where there is a slight standstill and it finally reaches a value of 2.07 cm3 mol−1 K, seemingly indicating ferromagnetic coupling between the Co(II) ions in 3. The continuous decrease suggests that the weak antiferromagnetic interaction exists between dinuclear units. Comparing the structures of two compounds, it is observed that an unusual near face-to-face π−π alignment of two imidazole rings, in which a ring carbon atom lies just over the equivalent atom of the other ring with strong carbon−carbon contacts (3.734 Å for 1 and 3.585 Å for 3). This π−π stacking can obviously mediate the magnetic interaction between Co(II) ions based on spin-polarization mechanism as shown in Figure 13. Compounds 1 and 3 have the same spin polarization, the intradinuclear Co(II) centers show ferromagnetic coupling, but the adjacent Co(II) centers connected by the π−π interaction display antiferromagnetic interaction.29 Since the π−π interaction of 3 is stronger than 1, 1 can exhibit obvious ferromagnetic coupling, but for 3, the ferromagnetic phenomenon is overlaid by the strong antiferromagnetic interaction between the adjacent Co(II). Therefore, a decrease was observed in the plot of χMT versus T below 12 K. From the plot of χMT versus T, the antiferromagnetic interaction between the adjacent Co(II) in 1 can be ignored and then the coupling between Co(II) ions can be given by the

Figure 6. (a) Coordination environment of the Co(II) ion in 3. The hydrogen atoms are omitted for clarity. Symmetry codes: (#1) 1 − x, 2 − y, 1 − z; (#2) −1 + x, 1.5 − y, 0.5 + z; (#3) 2 − x, 0.5 + y, 1.5 − z. (b) The 64-membered metallocyclic ring in 3. (c) Schematic representation of the (4, 4) network in 3, showing the dangling arms. (d) Perspective views of the hydrogen bonds (yellow dashed lines), translating the ABAB stacked layers into 3D frameworks.

collapses of the network. To confirm that the crystal structures are truly representative of the bulk materials, PXRD experiments were carried out for 1−5. The PXRD experimental and computer-simulated patterns of the corresponding compounds in the Supporting Information (Figures S2−S6) show that the bulk synthesized materials and the measured single crystals are the same. 4078



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Scheme 2. (a−d) Crystallographically Established Coordination Modes of Carboxylic Groups in Compounds 1−5

Figure 7. Coordination environment of the Cd(II) ion in 4. The hydrogen atoms are omitted for clarity. Symmetry codes: (#1) x, y, 1 + z; (#2) −1 + x, y, 1 + z.

Figure 9. Views of the (4, 4) sheets of 4 (top) and the 3D framework through ABAB fashion via hydrogen bond (pink dash line) (bottom).

χ =

Ng 2β 2 1 + 9e−2x kT 4(1 + e−2x)

(1)

3

Figure 8. Top (top) and side (bottom) views of the 2D sheet in 4. Hydrogen atoms have been omitted for clarity.

− 2x Ng 2β 2 4 + x (1 − e ) χ⊥ = kT 4(1 + e−2x)

(2)

χ ′ = (χ + 2χ⊥ )/3

(3)

χ′ ⎛⎜ 2zJ ⎞⎟ 1− χ′ ⎝ Ng 2μB2 ⎠

(4)

χ=

mean field approximation (zJ). The magnetic susceptibility from 1.8 to 300 K can be fit by following eqs 1−4 for S = 3/2 systems with dominant ZFS effects. From the plot of χMT versus T, we can see that strong antiferromagnetic interaction between the adjacent Co(II) exists in 3. For the lack of a perfect model with more parameters to fit this plot, we just try to fit 12 to 300 K by following eqs 1−4.

where x is D/(kBT) and D is the magnitude of the ZFS. We obtained the best agreement between model and experiment (g = 2.46, D = −45.7 cm−1, zJ = 0.23 cm−1, R = 1.5 × 10−3 for 1 and g = 2.47, D = 40.5 cm−1, zJ = 0.55 cm−1, R = 2.2 × 10−4 for 3). The ZFS values are in good agreement with the previously reported values.30 4079



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Figure 10. The configurations of L2− in compounds 1−5. Hydrogen atoms have been omitted for clarity.

Table 2. Relation between Coordination Environment and the Dihedral Angle of L2− metal ions N-ligand coordination mode C···Ncore···C angle (°) dihedral angle (°)

1

2

3

4

5

Co(II) BIP bismonodentate and monodentate 131.47 10

Co(II) BIP momodentate 131.80 25

Co(II) BIBP momodentate 125.93 40

Cd(II) BIBP chelate 128.54 52

Zn(II) BIBP chelate 128.96 56

Figure 12. Temperature dependence of χMT for 3 (inset: partial of χMT versus T). The solid line represents the theoretical fitting with the following parameters: g = 2.47, D = 40.5 cm−1, zJ = 0.55 cm−1.

Figure 11. Temperature dependence of χMT for 1 (inset: field dependence of magnetization for 1 at 1.8 K). The solid line represents the theoretical fitting with the following parameters: g = 2.49, D = −53.5 cm−1, zJ = 0.20 cm−1.

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carboxyl groups deprotonated, only one O atom coordinates to metal central; thus very strong hydrogen bondings exist in 3, which make it more stable comparing to other four compounds. Compounds 4 and 5 are a wave-like 2D sheet. The sheets are stacked in ABAB fashion and perform 3D supermolecular structure via hydrogen bonds. These results demonstrate that the noncoordinated carboxyl groups of H2L can be well used as the structure-directing tool and can produce various H-bonding in the synthesis of unusual coordination frameworks. Though compounds 1 and 3 have a similar structure, they show different magnetic properties. The magnetic and photochemical properties reveal that they are potential multifunctional materials. Subsequent works will be focused on the structures and properties of a series of coordination complexes constructed by H2L with more auxiliary ligands and metal ions.

CONCLUSION In summary, five new compounds have been synthesized by the assembly of H2L, BIBP, and BIP ligands under solvothermal conditions. It was found that the H2L ligand can change the C···Ncore···C and the dihedral angle between the phenyl rings to meet the requirement of coordination, and the carboxylic groups display rich coordinated fashion. The structure of 1 is a 3D noninterpenetrated framework, which is a rare example of a cds-type framework. When using CH3CN/H2O instead of DMF/H2O as solvent, we obtained compound 2 possessing unusual 3-fold 2D → 2D polycatenation of (4, 4) nets. This indicates that the solvent can significantly affect the final sturctrues. Compound 3 reveals a (4, 4) grid topology. With four O atoms from two 4080



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Figure 13. Representation of the spin polarization in 1 (a) and 3 (b) bound between two transition metal centers.

■

ASSOCIATED CONTENT

S Supporting Information *

Crystallographic data in CIF format, selected bond lengths and angles, and patterns of photochemistry, TGA and PXRD. This material is available free of charge via the Internet at http://pubs. acs.org.

■

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Fax: 86-25-83314502. Notes

The authors declare no competing financial interest.

■

ACKNOWLEDGMENTS This work was supported by grants from the Natural Science Foundation of China (Nos. 91022011; 20971065; 21021062) an d National B asic Research Program of China (2010CB923303; 2007CB925103).

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Hydrogen Bondings, Non-Interpenetrated and Polycate - American

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