Two- and Three-Dimensional Divalent Metal Coordination Polymers

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Two- and three-dimensional divalent metal coordination polymers constructed from a new tricarboxylate linker and dipyridyl ligands Xinhong Chang, Jian-Hua Qin, Ma Lufang, wang jiange, and Liya Wang Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/cg3008602 • Publication Date (Web): 25 Jul 2012 Downloaded from http://pubs.acs.org on July 30, 2012

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Crystal Growth & Design

Two- and three-dimensional divalent metal coordination polymers constructed from a new tricarboxylate linker and dipyridyl ligands Xin-Hong Chang,† Jian-Hua Qin,† Lu-Fang Ma,*,† Jian-Ge Wang†, and Li-Ya Wang*,†,‡ †

College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022, P. R. China.

‡

College of Chemistry and Pharmaceutical Engineering, Nanyang Normal University, Nanyang 473061, P. R. China To whom correspondence should be addressed. E-mail: [email protected]; [email protected]

ABSTRACT: Solvothermal reactions of an unsymmetrical tricarboxylic acid ligand, biphenyl-3,3′,5-tricarboxylic acid (H3L), with cobalt, nickel, and manganese salts in the presence of 1,2-bi(4-pyridyl)ethane (bpa), 1,2-bi(4-pyridyl)ethene (bpe), and 1,3-bi(4-pyridyl)propane (bpp) ligands, produced four new coordination polymers, namely, {[Co2(HL)2(bpa)2(H2O)]}n (1), {[Co(HL)(bpe)]·H2O}n (2), {[Ni(HL)(bpa)]·H2O}n (3) and {[Mn3L2(H-bpp)(OH)(H2O)2]·2H2O}n (4). Complexes 1–4 were structurally characterized by elemental analysis, infrared (IR) spectra, and X-ray single-crystal diffraction. Complex 1 exhibits a three-dimensional (3D) 4-fold interpenetrating diamondoid framework. Complex 2 is a two-dimensional (2D) layered structure with a (3, 5)-connected (42.6)(42.67.8) topology and further stacks via hydrogen bonding interactions to generate a 3D supramolecular architecture. Complex 3 shows a 3D framework assembled by mutual interpenetration of neighbouring 2D layers. Complex 4 possesses a 3D framework

composed

of

the

trinuclear

[Mn3(µ3-OH)]5+

cluster

nodes

with

a

(42.6)(42.6)(44.62.73.85.9) topology. In addition, there exist different types of helical chains in complexes 1–3. Thermo-gravimetric properties of 1–4 and magnetic properties of 4 were also investigated. This study reveals that the H3L ligand can be used as a versatile building block for the construction of metal organic frameworks. Introduction Design and fabrication of coordination polymers has attracted great attention not only because of their interesting topological structures1 but also for their potential applications in the fields of luminescence, gas storage, adsorption, nonlinear optics, magnetism, catalysis, ion-exchange, and so on.2–4 In general, there are a variety of factors to influence the topological architectures and

ACS Paragon Plus Environment


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properties of the coordination polymers, mainly including the coordination geometries of central metal ions, and the shapes, functionalities, flexibilities, symmetries, lengths, substituent groups of the organic ligands, as well as the reaction conditions. Among them, organic ligands play an important role in the construction of novel metal–organic frameworks (MOFs).5 Now, searching for new kinds of versatile polycarboxylate ligands deserves attention with regard to investigating new topologies and various functional materials. The biphenyl polycarboxylate ligands, such as biphenyl-2, 2′, 3, 3′-tetracarboxylate, biphenyl-2, 2′, 4, 4′-tetracarboxylate, biphenyl-2, 2′, 6, 6′-tetracarboxylate, biphenyl-2, 3′, 3, 4′-tetracarboxylate, biphenyl-2, 2′, 5, 5′-tetracarboxylate, biphenyl-3, 3′, 4, 4′-tetracarboxylate, biphenyl-3, 3′, 5, 5′-tetracarboxylate,6 4, 4'-biphenyldicarboxylate,7 have attracted much recent interest because their different coordination modes can lead to diverse multidimensional architectures. To date, a series of metal–organic structural motifs, including rod, bilayer, ladder, hexagonal nanotube, hourglass, and UMCM-150 isostructural analogues,8 have been deliberately designed by employing bridging biphenyl polycarboxylate. Chen etc. synthesized MOFs with high H2 adsorption based on 3,3′,5,5′-tetracarboxylate ligand.6a Serre's group obtained MOFs by 4,4'-biphenyldicarboxylate ligand, which can expand largely upon solvent adsorption without apparent bond breaking.7b In contrast, far less common has been focused on the investigation of the unsymmetrical biphenyl tricarboxylate ligands,8-9 and the coordination chemistries of biphenyl-3,3′,5-tricarboxylic acid (H3L), to the best of our knowledge, have not been reported. Utilization of unsymmetrical linkers may allow the formation of novel coordination polymers with structures and properties previously undiscovered. In order to build novel molecular architectures, we chose a long bridging unsymmetric ligand, biphenyl-3,3′,5-tricarboxylic acid, as the linker for the following reasons: (i) Multiple bridging moieties, a variety of connection modes with metal centers, are possible and provide abundant structural motifs; (ii) The carboxylate groups can act not only as hydrogen bond acceptors but also as hydrogen bond donors, depending on the degree of deprotonation; (iii) The H3L ligand can conform to the coordination geometries of the metal ions because its two phenyl rings can be rotated around the C-C single bond. Herein, we report the syntheses and crystal structures of four new complexes, namely, {[Co2(HL)2(bpa)2(H2O)]}n (1) ， {[Co(HL)(bpe)]·H2O}n (2) ， {[Ni(HL)(bpa)]·H2O}n (3) and {[Mn3L2(H-bpp)(H2O)2]·2H2O}n (4). The thermal stabilities of complexes 1–4 and magnetic


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properties of 4 will also be discussed. Results and Discussion Synthesis and spectral characterization The synthesis of H3L and its complexes 1–4 are shown in Scheme 1 and 2. It is essential that the organic solvents used are dried completely during the synthesis of compounds II and III in order to obtain pure product and high yield. The synthesis of III was performed under N2 atmosphere. The final product of H3L is white if the obtained crude product of IV was decolorised by refluxing in EtOH with activated carbon. The hydrothermal technique has been extensively explored as an effective and powerful tool in the self-assembly of coordination polymers, especially for the poor solubility of polycarboxylate ligands, even though its reaction mechanism is not clear. In present work, H3L ligand is almost insoluble in aqueous solution. Moreover, the mixture of metal salts and H3L with N-donor ligands always results in precipitation in aqueous solution under ambient conditions. Therefore, complexes 1–4 were synthesized under hydrothermal conditions. In the IR spectrum of complexes 1–3, the characteristic bands at around 1700 cm-1 are attributed to the protonated carboxylate groups, indicating the incomplete deprotonation of H3L. The absence of such bands in complex 4 indicates the complete deprotonation of H3L (see Figure S2). This is in agreement with the results of X-ray single-crystal analysis.

(i)

(ii) O

Br

B O CO 2C 2H 5

(I)

(III)

(II)

(iii) HOOC

COOH (iv)

COOH

COOH

(V) Scheme

1.

The

scheme

for

the

(IV) synthesis

of

biphenyl-3,3′,5-tricarboxylic

acid

(H3L).(i

=

bis(pinacolato)diborane, potassium acetate, Pd(dppf)2Cl2, 1,4-dioxane, overnight, 86% yield; ii = ethyl



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3-bromobenzoate, K3PO4, 1,4-dioxane, Pd(PPh3)4, reflux, 89% yield; iii = (1) OH-, reflux; (2) HCl, 92% yield; iv = (1) KMnO4, OH-, reflux; (2) HCl, 82% yield).

Scheme 2. Synthesis of complexes 1–4.

Descriptions of Crystal Structures {[Co2(HL)2(bpa)2(H2O)]}n (1) Single-crystal X-ray diffraction measurement reveals that complex 1 crystallizes in the orthorhombic system with Pbcm space group. The asymmetric unit possesses two crystallographically independent Co(II) ions, two partly deprotonated HL ligands, two bpa ligands, as well as one coordinated water molecule. As shown in Figure 1a, Co(II)1 is five-coordinated with a slightly distorted trigonal biyramid environment by two carboxylic O atoms (O2 and O2A, Symmetry codes: A: x, y, 0.5 – z) from two different HL ligands, two N atoms (N2 and N3B, Symmetry codes: B: 2 – x, 0.5 + y, 0.5 – z) from two different bpa ligands and one terminal water molecule. The bond angles around Co(II)1 range from 87.2(4) to 178.4(3)o, the Co(II)1-O bond lengths range from 1.957(6) to 2.175(8) Å, and the Co(II)1-N bond distances are 2.161(10) (Co(II)1-N2) and 2.063(11) (Co(II)1-N3B) Å, respectively. Each Co(II)2 center is surrounded by two nitrogen atoms (N1 and N1C, Symmetry codes: C: 2 – x, y – 0.5, 0.5 – z) from two different bpa ligands, and four carboxylic oxygen atoms (O3, O4, O3C, and O4C, Symmetry codes: C: x, 0.5 – y, –z) from two different HL ligands, forming a distorted CoN2O4 octahedron. N1 and O4C lie in the apical positions with a N1-Co(II)2-O4C bond angle of 150.3(2)o. The bond angles around Co(II)2 vary from 59.0(2) to 150.3(2) o, the Co(II)2-O/N bond distances range from 2.082(7) to 2.281(7) Å. The dihedral angle between the two phenyl rings of the HL ligand is 38.6o. Three carboxylate groups (3-, 3'-, and 5-COO–) have a dihedral angle of 8.9, 29.3, and 0.95o


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towards the plane of the corresponding linking phenyl rings, respectively. 3-COO– is chelated, 5-COO– is monocoordinated, and 3'- COO– remains protonated. Two carboxylic groups of each HL ligand adopt µ1-η1:η1 and µ1-η1:η0 coordination modes (scheme 3a) to bridge adjacent Co(II) ions to give alternately arranged left- and right-handed helical chains running along the crystallographic 21 axis in the c direction (Figure 1b). In addition, HL ligands and bpa ligands alternately bridge adjacent Co(II) ions to form left- and right-handed helical chains running along the crystallographic 41 axis in the a direction (Figure 1c). Moreover, the four 41 helical chains from four separate three-dimensional (3D) network segments entangle with each other, forming four strand helical structures (Figure 1d). From the topological point of view, each Co(II) ion can be considered as a 4-connected node, the HL and bpa ligands serve as linkers. The 3D framework of 1 can be abstracted into a 4-connected (66) diamond network topology (Figure 1e). Moreover, four identical diamond network segments are interlocked with each other, forming a 4-fold interpenetrated 3D architecture (Figure 1f).

(a)

(b)


(c)


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(d)

(e) Figure 1.

(f)

(a) View of local coordination environment of Co(II) ions in 1. Symmetry codes: A, x, y, 0.5 – z; B, 2

– x, 0.5 + y, 0.5 – z; C, 2 – x, y – 0.5, 0.5 – z. (b) Perspective view of the left-handed and right-handed helical chains bridged by HL ligands in 1. (c) View of the left-handed and right-handed helical chains bridged by HL and bpa ligands in 1. (d) Schematic view of four strand helical structures in 1.(e) Schematic view of the net topology of 1.(f) Schematic view of the 4-fold interpenetrated network topology of 1.

{[Co(HL)(bpe)]·H2O}n (2) Complex 2 crystallizes in the triclinic system with Pī space group. Analysis of the single crystal X-ray diffraction data indicates that the asymmetric unit of 2 consists of one crystallographically distinct Co(II) ion, one HL ligand, one bpe ligand, as well as one free lattice water molecule. As shown in Figure 2a, each Co(II) center is six coordinated with four oxygen atoms from three HL ligands and two nitrogen atoms from two bpe ligands. The coordination geometry is octahedral with two nitrogen atoms (N1, N2C) at the axial positions with a N1–Co–N2C bond angle of 175.65(16)o, and four oxygen atoms (O1, O2A, O5B, and O6B) in the equatorial plane. The bond lengths are Co–O1 = 2.050(3), Co–O2A = 2.009(3), Co–O5B = 2.144(4), Co–O6B = 2.255(4), Co–N1 = 2.167(4), Co–N2C = 2.167(4)Å. The bond angles around each Co(II) center lie in the range of 59.23(13)–175.64(16) o. The dihedral angle between the pair of phenyl rings of the HL ligand is 48.3o. The dihedral angles between the 3-, 3'-, and


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5-carboxylate groups and their corresponding linking phenyl rings are 24.1°, 35.7°, and 13.6°, respectively. 3- and 3'-COO– are bicoordinated and chelated, respectively. 5-COO– remains protonated. Two carboxylic groups of each HL ligand link neighboring Co(II) ions in µ1-η1: η1 and µ2-η1: η1 coordination modes (Scheme 3b) to form a 1D ribbonlike chain along the c-axis, in which each HL ligand links three Co(II) ions to generate an interesting meso-helical chain (Figure 2b). The adjacent 1D ribbonlike chains are further linked by bpe ligands to form a 2D layer containing cavities (Figure 2c). The lattice water molecules are bound in the cavities through intermolecular O-H···O

hydrogen-bonding

interactions(O(7)-H(1W)···O(5)#6,

2.765

Å,

154.6o;

O(7)-H(2W)...O(3)#7, 2.767 Å, 110.9o; O(7)-H(2W)...O(4)#7, 3.083 Å, 139.6o, Symmetry codes: #6: x + 1, y – 2, z + 1; #7: –x, –y + 1, –z + 1) between H2O molecules and the O atoms of the carboxylate. Furthermore, the 2D layers are combined through O-H···O hydrogen bonding between H2O molecules and the carboxylic O atoms (O(7)-H(1W)···O(5)#6, O(7)-H(2W)···O(3)#7, O(7)-H(2W)···O(4)#7) to form a 3D supramolecular framework. Each HL ligand connects three Co (II) atoms, which can be simplified as a 3-connected node. Each Co(II) ion links directly three HL ligands and the other two Co(II) ions through bpe ligands, which can be treated as a 5-connected node. From the topological point of view, 2 can be interpreted topologically as a (3,5)-connected network with the Schläfli symbol of (42.6)( 42.67.8) (Figure 2d).

(a)

(b)



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(c)

(d) Figure 2. (a) View of local coordination environment of Co(II) atom in 2. Symmetry codes: A, –x + 1, –y, –z + 1; B, –x + 1, –y, –z; C, x – 1, y – 1, z. (b) Schematic view of the 1D ribbonlike chain in 2. (c) Polyhedral view of the 2D layer along (110) direction. (d) Schematic view of the (3,5)-connected network of 2.

{[Ni(HL)(bpa)]·H2O}n (3) Single-crystal X-ray structural analysis reveals that complex 3 crystallizes in the monoclinic system with Cc space group. The asymmetric unit of 3 is composed of one crystallographically independent Ni (II) ion, one HL ligand, one bpa ligand, as well as one free lattice water molecule. As shown in Figure 3a, each Ni (II) center is six-coordinated with a distorted octahedral geometry by four carboxylic O atoms (O1, O2, O3A and O4A, Symmetry codes: A: x + 0.5, –y – 0.5, z + 0.5) from two different HL ligands and two N atoms (N1and N2A, Symmetry codes: A: x + 0.5, –y – 0.5, z + 0.5) from two different bpa ligands. The bond angles around each Ni(II) center vary from 60.9(3) to 160.4(3) o. The Ni-N bond distances are 1.983(10) and 2.078(10) Å, and the Ni-O bond lengths range from 2.108(9) to 2.137(9) Å, respectively. The dihedral angle between two phenyl rings of the HL ligand is 51.1o. Three carboxylate groups (3-, 3'-, and 5-COO–) have a dihedral


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angle of 12.5, 9.6, and 10.9o towards the plane of the corresponding linking phenyl rings, respectively. 3- and 3'-COO– are chelated, and 5-COO– remains protonated. Two carboxylic groups of each HL ligand link neighbouring Ni(II) ions in µ1-η1: η1 and µ1-η1: η1 coordination modes (scheme 3c) to form left- or right-handed 1D chains running along the crystallographic 21 axis in the c direction (Figure 3b). The bpa ligands then link the 1D chains to form a zigzag (4, 4) 2D layer along ac plane (Figure 3d). Within the 2D layers, Ni(II) ions are bridged by HL and bpa ligands to generate another kind of left- or right-handed helical chains along the crystallographic 31 axis in the a direction(Figure 3c). The identical 2D single nets are interlocked with each other and form an interesting parallel interpenetrated 2D → 3D architecture (Figure 3e).

（a）

(b)

(c)



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(d)

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(e)

Figure 3. (a) View of local coordination environment of Ni(II) atom in 3. Symmetry codes: A, x + 0.5, –y – 0.5, z + 0.5. (b) Perspective view of the left-handed and right-handed helical chains bridged by the HL ligands. (c) View of the left-handed and right-handed helical chains bridged by the HL and bpa ligands. (d) Polyhedral view of the 2D coordination network of 3. (e) Schematic view of 3D framework of 3 built from interpenetrating 2D layers.

{[Mn3L2(H-bpp)(OH)(H2O)2]·2H2O}n (4) Single-crystal X-ray structural analysis reveals that complex 4 crystallizes in the triclinic system with Pī space group. The crystal structure of 4 exhibits a 3D network composed of the trinuclear [Mn3(µ3-OH)]5+ cluster nodes, H-bpp and L bridging ligands (Figure 4a). There are three crystallographically independent manganese atoms. The atomic valences for two manganese cations can be determined by the bond valence model.10 According to this model, the sum of all the bond valences around any ion is equal to its ionic charge or valence. Here, bond valences (s) are calculated as s = exp[(r0 − r ) / B ] ; B=0.37, r0=1.849 for Mn(II)-N pairs, r0=1.765 for Mn(II)-O pairs.11 The calculated results are listed in Table S1. Evidently, the calculated values of bond valence sum are in good agreement with the values of expected atomic valence, which indicates that all the manganese cations have a valence of 2. Mn1 center adopts a distorted octahedral geometry by coordinating to four oxygen atoms from four different L ligands (O2, O10A, O11B and O12B, Symmetry codes: A: –x, 2 – y, 1 – z; B: –1 – x, 2 – y, 1 – z), one µ3-OH(O14) and one terminal water molecule (O15). O14 and O15 lie in the axial positions with a O14–Mn–O15 bond angle of 172.44(16)o. The bond angles around Mn1 range from 55.09(16) to 172.44(16) o, and the Mn1-O bond lengths range from 2.090(4) to 2.450(5) Å. Mn2 also adopts a distorted octahedral coordination geometry, coordinated by five carboxylic oxygen atoms (O3C, O7, O8, O9A and O12B, Symmetry codes: A: –x, 2 – y, 1 – z; B: –1 – x, 2 – y, 1 – z; C: x, 1 + y, z)


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from four different L ligands and one µ3-OH- group. O14 and O7 locate on the axial positions with a O14–Mn2–O7 bond angle of 154.43(18)o. The bond angles around Mn2 range from 58.07(17) to 154.43(18) o, and the Mn2-O bond lengths range from 2.060(4) to 2.262(5) Å. Mn3 atom is bound to one terminal water molecule (O13), one µ3-OH- group, one nitrogen atom from terminal H-bpp ligand, as well as three carboxylic oxygen atoms (O1, O4C and O5D, Symmetry codes: C: x, 1 + y, z; D: –x, –y, 2 – z) from three L ligands to obtain a distorted octahedral environment. The axial positions are filled with O1 and O4C with a O1–Mn3–O4C bond angle of 177.0(2)o. The Mn3–O/N coordination bond distances range from 2.139(5) to 2.311(6) Å. The distances of Mn···Mn bridged by the µ3-OH- group are 3.241 (Mn1…Mn2), 3.679 (Mn1…Mn3), and 3.776 Å (Mn2…Mn3), respectively. The H3L in 4 are completely deprotonated, exhibiting two kinds of coordination modes, as shown in Scheme 3d, e. In the first mode, three carboxylic groups of 3-, 3'-, and 5-COO– act as µ2-η1: η1, µ1-η1: η1, and µ2-η2: η1 modes to bridge five Mn(II) ions, respectively. In the second mode, three carboxylic groups of 3-, 3'-, and 5-COO– act as µ2-η1: η1, µ1-η1: η0, and µ2-η1: η1 modes to bridge five Mn(II) ions together, respectively. On the basis of these connection modes, L ligands connect Mn1 and Mn2 ions to form a 2D double layer and link Mn3(II) ions to generate a 1D chain (Figure 4b and 4c). The 2D double layers and 1D chains are further connected alternately by O2，O3 and O14 to extend into a 3D framework (Figure 4d). From the topological point of view, three-core Mn unit can be considered as a node, which connects six L ligands. Moreover, each L ligand links three three-core Mn units, which can be considered as a 3-connected node. Overall the 3D framework of 4 can be abstracted into a (3, 6)-connected (42.6)(42.6)(44.62.73.85.9) topology (Figure 4e). As to the L ligand in mode 1, the dihedral angle between the two phenyl rings is 11.7o, three carboxylate groups (3-, 3'-, and 5-COO–) have a dihedral angle of 26.1, 12.1, and 9.4o towards the plane of the corresponding linking phenyl rings, respectively. Compared with mode 1, the dihedral angle between two phenyl rings of the L ligand is 31.5o, three carboxylate groups (3-, 3'-, and 5-COO–) have a dihedral angle of 1.6, 8.3, and 14.1o towards the plane of the corresponding linking phenyl rings in mode 2, respectively. In 4, the bpp ligand adopts a unidentate coordination mode and the unligated N2 atom acts as the hydrogen-bonding acceptor forming N-H···O hydrogen bonding with the bond distance of 2.7



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Å. Obviously, this unusual binding fashion of bpp will be sustained by the carboxylic group via the formation of such hydrogen bond. Otherwise, bpp would prefer the bridging mode as that of bpe and bpa in 1–3.

(a)

(b)

(c)

(d)

(e)

Figure. 4. (a) View of local coordination environment of Mn(II) ions in 4. Symmetry codes: A: –x, 2 – y, 1 – z; B: –1 – x, 2 – y, 1 – z; C: x, 1 + y, z; D: –x, –y, 2 – z). (b) Perspective view of the 2D layer of 4. (c) Perspective view of 1D chain of 4. (d) Perspective view of 3D framework of 4 with alternating 2D layers and 1D chains. (e)


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Schematic illustration of the (3, 6)-connected topology of 4. M O

M O

O

O

HOOC

O M O

O M

(a)

O

M

O

M

M O

(c)

(b) O

M O

M O M

COOH

M O

O

M

O

COOH O

O O M

O

(d)

M

O

O M

O M

O (e)

M

Scheme 3. Binding modes of carboxylate ligands.

Thermal Properties and PXRD

TG curves for complexes 1-4 are shown in Figure S1, Supporting Information. The TG curve of 1 shows the weight loss (2.91%) at 130.0-169.3 oC, corresponding to the loss of a coordinated water molecule (calcd: 2.69 %). The removal of the organic components occurs in the range 357.3-568.2 oC. For complex 2, a gradual weight loss between 105.7 and 166.6 o

C is attributed to the release of a lattice water molecule (observed, 3.69%; calculated, 3.31%).

The decomposition of the anhydrous composition is observed from 350.7 to 537.5 oC. For complex 3, a gradual weight loss is observed from 29.1 to 114.3 oC which is attributed to the loss of a lattice water molecule, with a weight loss of 3.64 % (calcd 3.32 %), then the structure was decomposed since 396.4 oC. Complex 4 lost water molecules from 100.2 oC. Water completely lost at 234.2 oC. 8.16 % weight loss corresponds to coordinated and lattice water molecules (calculated, 7.06%). The complex 4 decomposes vigorously from 327.9 oC. In order to check the phase purity of 4, the X-ray powder diffraction (XRPD) pattern was checked at room temperature. As shown in Figure S3, Supporting Information, the peak positions of the simulated and experimental XRPD patterns are in agreement with each other, demonstrating the good phase purity of 4. Magnetic Properties The magnetic susceptibilities, χM, of 4 were measured in the 2–300 K temperature range, and shown as χMT versus T plots in Figure 5. From the magnetic point of view, complex 4 can be



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considered as trinuclear Mn(II) units, in which three Mn(II) ions are linked by the µ3-OH group. The experimental χMT value at 300 K is 12.98 cm3 K mol-1, which is slightly lower than the spin-only value (13.13 cm3 K mol-1) expected for three uncoupled high-spin Mn(II) ions. As the temperature lowers, the χMT value decreases gradually, which indicates the presence of an antiferromagnetic interaction in 4. Temperature dependence of the reciprocal susceptibilities (1/χM) obeys the Curie–Weiss law above 50 K with θ = – 49.8 K, C = 14.93 cm3⋅K/mol and R = 8.35×10−4. Taking into account the above consideration, the experimental magnetic data can be properly fitted using the following equation, where N, g, β and k have their usual meanings. χM =

Ng 2 β 2 A KT B

(1)

A = 1 + 20exp[3J/KT] + 105exp[8J/KT] + 210exp[15J/KT] + 330exp[24J/KT] + 429exp[35J/KT] + 455exp[48J/KT] + 340exp[63J/KT] B = 1 + 4exp[3J/KT] + 9exp[8J/KT] + 10exp[15J/KT] + 10exp[24J/KT] + 9exp[35J/KT] + 7exp[48J/KT] + 4exp[63J/KT] The least-squares analysis of magnetic susceptibility data led to J = – 3.05 cm−1, g = 2.17, and R = 4.5 × 10−3. The moderately negative θ value and the J value indicate the presence of antiferromagnetic interaction among the adjacent Mn(II) ions in 4.

Figure 5. Temperature dependence of χMT for 4. Open points are the experimental data, and the solid line represents the best fit obtained from the Hamiltonian given in the text.

Conclusions In summary, four new coordination polymers based on the designed biphenyl-3, 3′, 5-tricarboxylic acid

ligand have been prepared and characterized, which show diverse


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architectures such as a 3D → 3D interpenetrating network (1), a 2D coordination network consisting of meso-helical chains (2), a parallel interpenetrated 2D→3D architecture (3), and a 3D framework consisting of three-core Mn units (4). According to the above structural description, H3L(1-3) and L(4) ligands in 1–4 exhibit five distinct kinds of bridging modes as shown in Scheme 3. Moreover, the dihedral angles between the two phenyl rings of carboxylate groups and correspondingly linking phenyl rings for 1–4 are different. These factors lead to helical structures in 1 and 3, a meso-helical structure in 2, and a non helical structure in 4. In addition, the thermal behaviors of 1–4 and magnetic properties of 4 have also been investigated. This study reveals that H3L ligand can be used as a good polydentate bridging ligand for the formation of multidimensional coordination polymers exhibiting a great structural diversity. Further research for the construction of new architectures of MOFs with more transition metals is underway in our lab.

Experimental Section Materials

and

physical

measurements:

5-bromo-1,3-dimethylbenzene

(I),

ethyl

3-bromobenzoate, Pd(dppf)2Cl2, Pd(PPh3)4, bis(pinacolato)diborane, were purchased without further purification. Elemental analyses of C, N, and H were performed on an EA1110 CHNS-0 CE elemental analyzer. IR (KBr pellet) spectra were recorded on a Nicolet Magna 750FT-IR spectrometer. Thermogravimetric measurements were carried out in a nitrogen stream using a Netzsch STA449C apparatus with a heating rate of 10 ˚C min–1. Variable-temperature magnetic susceptibilities were measured using a MPMS-7 SQUID magnetometer. The powder X-ray diffraction (PXRD) patterns were recorded with a Rigaku D/Max 3III diffractometer with a scanning rate of four degrees per minute. Synthesis of 4,4,5,5-tetramethyl-2-(1,3-dimethylphenyl)-1,3-dioxolane (II). The mixture of I (100 mmol, 18.4 g), bis(pinacolato)diborane (11.8 mmol, 3.0 g), potassium acetate (0.29 mmol, 28.0 g), Pd (dppf)2Cl2 (7.0 mmol, 5.0 g), and dried 1,4-dioxane (500 mL) at 100 ˚C overnight and afterward extracted with ethyl acetate (200 mL × 3). The organic layer was decolored with activated carbon, and dried by anhydrous Na2SO4. The crude product was obtained from concentration under a vacuum and purified by column chromatography (silica gel,



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ethylacetate/petroleum ether, 6 v %). Yield 86 %. Anal. (%) calcd. for C14H21BO2: C, 72.44; H, 9.12. Found: C, 72.38; H, 9.06. 2.2.2. Synthesis of 5-(ethyl 3'-carboxylphenyl)-1,3-dimethylbenzene (III). The mixture of II (100 mmol, 23.2 g), ethyl 3-bromobenzoate (100 mmol, 22.8 g), and K3PO4 (200 mmol, 42.4 g) were mixed in 1,4-dioxane (500 mL), and the mixture was deaerated using N2 for 10 min. Pd(PPh3)4 (1 mmol, 1.3 g) was added to the stirred reaction mixture and the mixture was heated to reflux for ca. one week under N2 atmosphere. The crude product of III was obtained after 1,4-dioxane was removed under a vacuum. Recrystallization from methanol offered the pure product. Yield 89 %. Anal. (%) calcd. for C17H18O2: C, 80.28; H, 7.13. Found: C, 80.16; H, 7.09. 2.2.3. Synthesis of 5-(3'-carboxylphenyl)-1,3-dimethylbenzene (IV). The mixture of III (0.10 mol, 25.4 g) and 10 g NaOH in 500 mL H2O was refluxed for 2 hours, and then cooled to room temperature. The solution was neutralized with concentrated HCl. White powder was obtained with the yield of 92 %. Anal. (%) calcd. for C15H14O2: C, 79.62; H, 6.24. Found: C, 79.58; H, 6.20. 2.2.4. Synthesis of biphenyl-3,3',5-tracarboxylic acid (H3L) (V). The mixture of IV (100 mmol, 22.6 g), KOH (220 mol, 12 g), and 600 mL H2O was heated to reflux. KMnO4 (880 mol, 140.0 g) was added in portions to the refluxing solution. Refluxing was continued for 12 hours. After cooling to room temperature, the mixture was filtered and the residual manganese dioxide was washed with the solution of hydroxide sodium. The combined filtrates were acidified with concentrated hydrochloric acid. The white solid precipitate was filtered off, washed several times with water, and dried to afford V (82 %). Anal. (%) calcd. for C15H10O6: C, 62.94; H, 3.52. Found: C, 62.91; H, 3.46.

Preparation of complexes 1–4. {[Co2(HL)2(bpa)2(H2O)]}n (1). A mixture of H3L (0.1 mmol, 28.6 mg), bpa (0.1 mmol, 18.9 mg), Co(OAc)2·4H2O (0.1 mmol, 24.9 mg), KOH (0.3 mmol, 16.8 mg), and H2O (12 mL) was placed in a Teflon-lined stainless steel vessel, heated to 140 oC for 4 days, and then cooled to room temperature over 24 h. Traces of red crystals of 1 were obtained. Anal. (%) calcd. for C216H164Co8N16O52: C, 60.51; H, 3.85; N, 5.22. found: C, 60.26; H, 4.01; N, 5.37. IR (cm-1): 3061 m, 1705 m, 1614 s, 1537 s, 1402 m, 1299s, 1240s, 1070 m, 1027 s, 835 s, 759s, 693 m.


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{[Co(HL)(bpe)]·H2O}n. (2). 2 was synthesized in the similar way as that described for 1, except that bpa was replaced by bpe (0.1 mmol, 18.1 mg). Traces of red crystals of 2 were obtained. Anal. (%) calcd. for C27H20CoN2O7: C, 59.67; H, 3.68; N 5.16. found: C, 59.82; H, 3.61; N, 5.23. IR (cm-1): 3039 m, 1712 m, 1605 s, 1410 s, 1249 m, 1015 m, 828 s, 753 m, 691 m. {[Ni(HL)(bpa)]·H2O}n (3). 3 was synthesized in the similar way as that described for 1, except that Co(OAc)2·4H2O was replaced by Ni(OAc)2·4H2O (0.1 mmol, 24.8 mg). Traces of blue crystals of 3 were obtained. Anal. (%) calcd. for C27H22NiN2O7: C, 59.45; H, 4.04; N, 5.14. found: C, 59.56; H, 4.10; N, 5.02. IR (cm-1): 3063 m, 1708 m, 1614 s, 1526s, 1424 s, 1402 m, 1316 m, 1223 m, 1029 m, 837 s, 762 s,690 s. [Mn3L2(OH)(H-bpp)(H2O)2]·2H2O (4). 4 was synthesized in the similar way as that described for 1, except that bpa and Co(OAc)2·4H2O was replaced by bpp (0.1 mmol, 20.1 mg) and Mn(OAc)2·4H2O (0.1 mmol, 24.2 mg), respectively. Colorless block crystals of 4 were obtained. Anal. (%) calcd. for C43H38Mn3N2O17: C, 50.64; H, 3.73; N, 2.75. found: C, 50.48; H, 3.79; N, 2.66. IR (cm-1): 3090 w, 1615 s, 1574 m, 1526 m, 1406 s, 1364 m, 1219 m, 1070 s, 1009 m, 907 m, 812 m, 762 s, 712 s, 677 s. X-ray crystallography: Single crystal X-ray diffraction analyses of 1–4 were carried out on a Bruker SMART APEX II CCD diffractometer equipped with a graphite monochromated MoΚα radiation (λ = 0.71073 Å) by using φ/ω scan technique at room temperature. The structures were 12

solved by direct methods with SHELXS-97, and refined by the full-matrix least-squares method on F2 with anisotropic thermal parameters for all non-H atoms (SHELXL-97).13 The empirical absorption corrections were applied by the SADABS program.14 The hydrogen atoms were assigned with common isotropic displacement factors and included in the final refinement by use of geometrical restrains. The crystallographic data and selected bond lengths and angles for 1–4 are listed in Table 3 and Table S2–S5. Crystallographic data for the structural analysis have been deposited with the Cambridge Crystallographic Data Center. CCDC reference numbers: 888252 for 1, 888253 for 2, 888254 for 3, and 888255 for 4.



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Page 18 of 21

Table 3. Crystallographic data and details of diffraction experiments for complexes 1–4.

Formula

1

2

C216H164Co8N16O52

C27H20CoN2O7

3 C27H22N2NiO7

4 C43H38Mn3N2O17

Mr

4287.07

543.38

545.18

1019.57

Crystal system

Orthorhombic

Triclinic

Monoclinic

Triclinic

Space group

Pbcm

Pī

Cc

Pī

a (Å)

7.300(9)

9.909(4)

19.623(9)

9.503(9)

b (Å)

19.11(2)

11.996(2)

12.731(6)

11.211(10)

c (Å)

34.17(4)

12.106(2)

11.297(5)

20.271(18)

α (°)

90

119.497(2)

90

76.345(12)

β (°)

90

97.858(3)

116.725(5)

86.308(12)

γ (°)

90

103.503(3)

90

83.617(12)

V (Å )

4765(10)

1162.8(6)

2520.7(19)

2084(3)

Z

1

2

4

2

1.494

1.552

1.437

1.625

3

–3

ρ (g cm ) -1

µ (mm )

0.770

0.791

0.819

0.976

T (K)

296(2)

296(2)

296(2)

296(2)

Rint

0.1093

0.0419

0.0435

0.0590

Goof R [I > 2σ(I)] R (all data) a

1.060

1.041

1.017

1.023

R1 = 0.1091

R1 = 0.0610

R1 = 0.0631

R1 = 0.0675

wR2 = 0.2297

wR2 = 0.1605

wR2 = 0.1570

wR2 = 0.1605

R1 = 0.1402

R1 = 0.0959

R1 = 0.0933

R1 = 0.1309

wR2 = 0.1803

wR2 = 0.1975

wR2 = 0.2479

wR2 = 0.1835

R1 = Σ(Fo - Fc)/ΣFo; wR2 = {Σ[w(Fo -Fc ) ]/ Σ[w(Fo2)2]}1/2 b

2

2 2

Acknowledgements. This work was supported by the National Natural Science Foundation of China (21073082, 21071074), Program for New Century Excellent Talents in University （NCET-11-0947）and Program for Science & Technology Innovation Talents in Universities of Henan Province (2011HASTIT027). The authors also thank Jinan Henghua Sci. & Tec. Co. Ltd. for synthesizing of H3L ligand. Supporting Information Available: Crystallographic data in CIF format and TGA figures. This information is available free of charge via the Internet at http: //pubs. acs. org.

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Graphical Abstract: Title: Two- and three-dimensional divalent metal coordination polymers constructed from a new tricarboxylate linker and dipyridyl ligands

Key Topic: By

the

use

of

an

unexplored

unsymmetrical

tricarboxylic

acid

ligand,

biphenyl-3,3′,5-tricarboxylic acid, four new 2D and 3D coordination polymers have been synthesized and structurally characterized. Moreover, thermal behaviors of 1-4 and magnetic properties of 4 have also been investigated.


Two- and Three-Dimensional Divalent Metal Coordination Polymers

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