Porous and Nanorod-Like Coordination Polymers Assembled from a

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Porous and nanorod-like coordination polymers assembled from a new V-shaped bis(1,2,4-triazolyl)tripyridine ligand Peng Yang, Ming-Xing Li, Min Shao, Meng-Si Wang, Shi-Xun Cao, jincang zhang, and Heng-Hua Zhang Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/cg400644k • Publication Date (Web): 14 Aug 2013 Downloaded from http://pubs.acs.org on August 16, 2013

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Crystal Growth & Design

Porous and nanorod-like coordination polymers assembled from a new V-shaped bis(1,2,4-triazolyl)tripyridine ligand Peng Yang,† Ming-Xing Li,*,† Min Shao,‡ Meng-Si Wang,† Shi-Xun Cao,§ Jin-Cang Zhang,§ Heng-Hua Zhang‡ †

Department of Chemistry, and § Department of Physics, College of Sciences, Shanghai University, Shanghai 200444, P.R. China.

‡

Laboratory for Microstructures, School of Materials Science and Engineering, Shanghai University, Shanghai 200444, P.R. China.

* Corresponding author. E-mail: [email protected] (M.-X.L.). Fax: +86-21-66134594 (M.-X.L.). RECEIVED DATE

Abstract: Six complexes based on a new rigid V-shaped ligand 2,6-bis(3-(pyrid-4-yl)-1,2,4-triazolyl)pyridine (2,6-H2bptp), namely, [Cd4(2,6-bptp)2(D-cam)(L-cam)(H2O)2]n·4nH2O (1), [Cd2(2,6-Hbptp)2(Hbtc)]n·4nH2O (2), [Zn(2,6-bptp)(H2O)]n·nH2O (3), [(Mo8O26)Cu2(2,6-H2bptp)2]n (4), [Co(2,6-H2bptp)2][Mo8O26]0.5·5H2O (5), and [(PMo12O40)Ag(2,6-H4bptp)]·2H2O (6) (D/L-H2cam = D/L-camphoric acid, H3btc = 1,3,5-benzenetricarboxylic acid), have been synthesized under hydrothermal conditions. Among these complexes, 2,6-H2bptp adopts seven types of coordination modes, all display a central tridentate chelating plane. Complex 1 possesses a 3D porous metal-organic framework that exhibits an intriguing sandwich-like motif. Complex 2 is a 1D nanorod-like coordination polymer with a square section of 1.11 × 1.06 nm2. Complex 3 exhibits a 1D zigzag chain structure, which is extended to a supramolecular double-chain by hydrogen bond. In complex 4, polyoxometalate β–Mo8O264– links Cu2(2,6-H2bptp)24+ dimer to form a 1D linear chain polymer. Complex 5 displays a 3D supramolecular architecture with nano-sized tunnels in which β -[Mo8O26]4– clusters embed. Complex 6 is a mononuclear silver complex constructed from Ag(2,6-H4bptp)3+ and [PMo12O40]3− pieces, which is further extended to a 3D supramolecular framework. The metal-organic frameworks of 1 and 2 are thermally stable up to 440 °C. Both Cd(II) complexes emit blue luminescence originating from ligand-centered emission. The complex 4 shows weak antiferromagnetic coupling in the Cu2(2,6-H2bptp)24+ dimer. Keywords: Coordination polymer, Polyoxometalate, Crystal structure, 2,6-Bis(3-(pyrid-4-yl)-1,2,4-triazolyl)pyridine, Luminescence, Magnetic property.

INTRODUCTION Design and assembly of coordination polymers and metal-organic frameworks are of rapid progress due to their unmatched structural versatility and potential applications such as luminescence, magnetism, catalysis, ferroelectric, and porous materials.1 Over the years, arduous effort has been invested in the purposeful design and controllable synthesis of these functional complexes. Amongst many strategies for constructing coordination polymers, the self-assembly of neutral N-heterocyclic ligands and polycarboxylates with metal ions under hydro(solvo)thermal condition has become one of the most effective approachs.2 Plenty of rigid N-heterocyclic ligands such as polypyridine,3 triazole4 and tetrazole5 derivatives are frequently employed to afford vast coordination

polymers. However, it is still an active field to explore valuable multidentate ligands for preparing coordination polymers with predictable structures and functional properties. To continue our study on functional coordination polymers based on N-heterocyclic ligands,6 we chose a new rigid 2,6-H2bptp (2,6-bis(3-(pyrid-4-yl)-1,2,4-triazolyl)pyridine) ligand, which consists of three pyridyl rings linked by two triazolyl groups (Scheme 1). This V-shaped N-heterocyclic ligand shows a bent backbone and equips with nine potential nitrogen donors. In some ways, 2,6-H2bptp integrates the coordination features of both polypyridine and polytriazole, which is considered as a valuable multidentate ligand. 2,6-H2bptp is a new ligand, and its coordination feature are unknown. We guess that

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2,6-H2bptp is more favors as a neutral N-heterocyclic ligand. So we use camphorate, 1,3,5-benzenetricarboxylate or terephthalate as auxiliary ligands, and successfully prepare three new coordination polymers, [Cd4(2,6-bptp)2 (D-cam)(L-cam)(H2O)2]n·4nH2O (1), [Cd2(2,6-Hbptp)2 (Hbtc)]n·4nH2O (2), and [Zn(2,6-bptp)(H2O)]n·nH2O (3). For H2bptp family, only three articles are reported currently. Tong et al. synthesized the first linear 3,5-bptp tetranuclear cobalt cluster, and the first cluster mesocate as well as a new series of octanuclear helicates based on a similar 2,6-bis(3-(pyrid-2-yl)-1,2,4-triazolyl)pyridine ligand.7 Hou et al. reported two 2D helical coordination and polymers {[Zn(2,6-bptp)(H2O)]·2H2O·CH3CN}n {[Pb(2,6-bptp)]·H2O}n prepared by 2,6-bis(3-(pyrid-3-yl)1,2,4-triazolyl)pyridine.8 These 2,6-H2bptp ligands are similar but display a little difference with our 2,6-H2bptp ligand in the respect of N-position of terminal pyridyl groups. Our new 2,6-H2bptp ligand has two terminal 4-positional pyridyl groups. The 2,6-H2bptp used by Tong or Hou has terminal 2- or 3-positional pyridyl groups, respectively. On the other hand, inorganic-organic hybrid materials fabricated by the combination of inorganic and organic building blocks have drawn much attention, since they are endowed with both advantages of inorganic and organic materials.9 As a wide class of outstanding inorganic building units, polyoxometalates (POMs) are known as bulky anions and possess abundant terminal and bridging oxygen atoms as potential active coordinate donors to combine with metal ions. The backbones of POMs are highly influenced by reaction conditions, such as pH value, solvent system, and temperature. To date, numerous coordination polymers and hybrid compounds based on POMs have been documented.10 Meanwhile, POMs are also with inherent advantage to connect with organic building blocks by hydrogen bonds. Intensive research efforts have been focused on the assembly of POMs with large organic ligands in aid of metal ions to form extended metal-organic hybrid frameworks and supramolecular systems.11 One of the remarkable approaches in the design of metal-organic hybrid compounds is to combine the POMs with mononuclear metal complex as building unit.12 Considering 2,6-H2bptp is a large-sized V-shaped multidentate ligand, its bent backbone is favorable to combine polyoxometalate clusters such as ball-shaped Keggin H3PMo12O40 or H4Mo8O26. We successfully prepared three 2,6-H2bptp polyoxometalate hybrid compounds, [(Mo8O26)Cu2(2,6-H2bptp)2]n (4), [Co(2,6H2bptp)2][Mo8O26]0.5·5H2O (5), and [(PMo12O40)Ag(2,6H4bptp)]·2H2O (6). Herein, we report the synthesis, crystal structures, thermal stability, luminescence and magnetic property of six 2,6-H2bptp complexes.

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Scheme 1. The 2,6-H2bptp Ligand and Its Seven Coordination Modes in Complexes 1–6

EXPERIMENTAL SECTION Materials and Methods. All reagents were obtained from commercial sources and used as received without further purification. 2,6-H2bptp was purchased from Jinan Henghua Sci. & Tec. Co. Ltd. (China). C, H, and N analyses were performed on a Vario EL III elemental analyzer. Infrared spectra were recorded with a Nicolet A370 FT-IR spectrometer using KBr pellets in 400–4000 cm–1 range. Thermogravimetric analyses were completed on a Netzsch STA 449C thermal analyzer at a heating rate of 10 °C min–1 under N2 atmosphere. Luminescence spectra of crystalline samples were measured on a Shimadzu RF-5301 spectrophotometer. Variable-temperature magnetic susceptibilities (3–300 K) were measured on a Quantum Design PPMS-9 apparatus in a magnetic field of 10 kOe. Syntheses of 1–6. [Cd4(2,6-bptp)2(D-cam)(L-cam)(H2O)2] n·4nH2O (1). A mixture of Cd(NO3)2·4H2O (30.8 mg, 0.1 mmol), 2,6-H2bptp (18.3 mg, 0.05 mmol), D-camphoric acid (20.0 mg, 0.1 mmol), triethylamine (20.3 mg, 0.2 mmol), and water (8 mL) were sealed in a 15 mL Teflon-lined reactor, which was heated at 160 °C for 72 h. Upon cooling to room temperature at a rate of 10 °C h–1, light yellow crystals of 1 were obtained in 33% yield (13.9 mg) based on 2,6-H2bptp. Anal. Calcd for C58H62N18O14Cd4 (%): C, 41.34; H, 3.71; N, 14.96. Found: C, 41.57; H, 4.02; N, 14.51. IR (KBr pellet, cm–1): 3451m, 3092w, 3046w, 2971m, 2882w, 1613s, 1577m, 1525s, 1433s, 1398s, 1285m, 1012m, 834m, 797s, 754m, 711m. [Cd2(2,6-Hbptp)2(Hbtc)] n·4nH2O (2). Cd(NO3)2·4H2O (30.8 mg, 0.1 mmol) was added into a solution containing 2,6-H2bptp (18.3 mg, 0.05 mmol), 1,3,5-benzenetricarboxylic acid (10.5 mg, 0.05 mmol), 1.5 mL NaOH solution (0.1 mol·L–1), and water (8 mL) under stirring. The


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mixture was sealed in a 15 mL Teflon-lined reactor, which was heated at 160 °C for 72 h. Upon cooling to room temperature at a rate of 10 °C h–1, colorless crystals of 2 were obtained in 35% yield (10.8 mg) based on 2,6-H2bptp. Anal. Calcd for C47H36N18O10Cd2 (%): C, 45.61; H, 2.93; N, 20.37. Found: C, 45.01; H, 3.32; N, 21.06. IR (KBr pellet, cm–1): 3427m, 3072m, 1716w, 1634m, 1615s, 1551s, 1504m, 1445m, 1376s, 1251m, 1184m, 1007m, 841s, 752s. [Zn(2,6-bptp)(H2O)] n·nH2O (3). A mixture of Zn(NO3)2·6H2O (29.7 mg, 0.1 mmol), 2,6-H2bptp (18.4 mg, 0.05 mmol), terephthalic acid (8.3 mg, 0.05 mmol), triethylamine (10.2 mg, 0.1 mmol), and H2O (8 mL) was sealed in a 15 mL Teflon-lined reactor, which was heated at 160 °C for 72 h. Upon cooling to room temperature at a rate of 10 °C h–1, colorless crystals of 3 were collected in 33% yield (7.7 mg) based on 2,6-H2bptp. Anal. Calcd for C19H15N9O2Zn (%): C, 48.89; H, 3.24; N, 27.00. Found: C, 48.43; H, 3.47; N, 26.44. IR (KBr pellet, cm–1): 3415m, 3096w, 3072w, 1674w, 1613s, 1576s, 1510m, 1448m, 1424s, 1376w, 1282w, 1197m, 1028m, 1001m, 808m, 728m. [(Mo8O26)Cu2(2,6-H2bptp)2] n (4). A mixture of CuSO4·5H2O (25.0 mg, 0.1 mmol), 2,6-H2bptp (18.3 mg, 0.05 mmol), MoO3 (14.4 mg, 0.1 mmol), and H2O (8 mL) was sealed in a 15 mL Teflon-lined reactor, which was heated at 160 °C for 72 h. Upon cooling to room temperature at a rate of 10 °C h–1, dark blue crystals of 4 were collected in 27% (13.8 mg) yield based on 2,6-H2bptp. Anal. Calcd for C38H26N18O26Mo8Cu2 (%): C, 22.31; H, 1.28; N, 12.33. Found: C, 22.05; H, 1.74; N, 12.59. IR (KBr pellet, cm–1): 3473m, 3088m, 1629s, 1567w, 1500s, 1458w, 1286m, 1185m, 1067w, 946s, 914s, 832s, 719s, 668s. [Co(2,6-H2bptp)2][Mo8O26] 0.5·5H2O (5). A mixture of CoSO4·7H2O (28.1 mg, 0.1 mmol), 2,6-H2bptp (18.3 mg, 0.05 mmol), (NH4)2MoO4 (9.8 mg, 0.05 mmol), and H2O (8 mL) was sealed in a 15 mL Teflon-lined reactor, which was heated at 160 °C for 72 h. Upon cooling to room temperature at a rate of 10 °C h–1, orange crystals of 5 were collected in 25% yield (9.2 mg) based on 2,6-H2bptp. Anal. Calcd for C38H36N18O18Mo4Co (%): C, 30.93; H, 2.46; N, 17.09. Found: C, 31.25; H, 2.13; N, 17.69. IR (KBr pellet, cm–1): 3449m, 3096m, 1636s, 1568w, 1516s, 1456m, 1288m, 1196w, 1017w, 946s, 912s, 841s, 707s, 668s. [(PMo12O40)Ag(2,6-H4bptp)]·2H2O (6). A mixture of AgNO3 (34.0 mg, 0.2 mmol), 2,6-H2bptp (18.4 mg, 0.05 mmol), H3PMo12O40 (91.2 mg, 0.05 mmol), and H2O (8 mL) was sealed in a 15 mL Teflon-lined reactor, which was heated at 160 °C for 72 h. Upon cooling to room temperature at a rate of 10 °C h–1, light yellow crystals of 6 were collected in 72% (84.1 mg) yield based on 2,6-H2bptp. Anal. Calcd for C19H19N9O42PMo12Ag (%): C, 9.77; H, 0.82; N, 5.40. Found: C, 9.62; H, 1.02; N, 5.59. IR (KBr pellet,

cm–1): 3452m, 3093w, 1640m, 1609m, 1516w, 1469w, 1062s, 957s, 974s, 795vs, 747m, 592m. X-ray Crystallography. The single-crystal X-ray diffractional data of 1–6 were collected on a Bruker Smart Apex-II CCD diffractometer with graphite monochromatic Mo Kα radiation (λ = 0.71073 Å) at room temperature. Determinations of the crystal system, orientation matrix, and cell dimensions were performed according to the established procedures. Lorentz polarization and absorption correction were applied. The structures were solved by direct methods and refined on F2 by full-matrix least-squares techniques with the SHELXTL program.13 All non-hydrogen atoms were refined anisotropically, and hydrogen atoms were located and included at their calculated positions. The crystallographic data and structural refinement results are summarized in Table 1. The selected bond distances and angles are listed in Table 2.

RESULTS AND DISCUSSION Description of Crystal Structures. Structure of [Cd4(2,6-bptp)2(D-cam)(L-cam)(H2O)2] n·4nH2O (1). The X-ray structural analysis reveals that complex 1 crystallizes in the monoclinic space group P21/c and features a three-dimensional (3D) metal-organic framework. It should be noticed that partial D-camphorate in the preparation of 1 changed into L-camphorate under hydrothermal condition. As shown in Figure 1a, the asymmetrical unit consists of four crystallographically independent Cd(II) ions, two 2,6-bptp2– ligands, one D-cam2– and one L-cam2– ligand, two coordinated water plus four lattice water molecules. Four kinds of distinct coordination geometries around Cd(II) ions are observed in 1 (Figure S1, Supporting Information). Cd1 adopts a distorted triangular-bipyramidal geometry, completed by two triazolyl N atoms, two O atoms from D-cam2– and L-cam2–, and water O1W. The N11 and O1W occupy the apical sites with a N11–Cd1–O1W bond angle of 179.3(3)°. Cd2 is seven-coordinated with a pentagon-bipyramidal geometry. Five coordination sites on equatorial plane are occupied by three central N atoms of 2,6-bptp2– and two O atoms of chelating carboxyl group. The apical sites are occupied by two terminal pyridyl N atoms of 2,6-bptp2– with a N1–Cd2–N18 bond angle of 171.1(3)°. Cd3 displays a distorted square-pyramidal geometry, coordinated by four N atoms from two 2,6-bptp2– ligands on basal plane, and by O5 of L-cam2– at apical site. Cd4 is six-coordinated with a distorted octahedral geometry. The equatorial plane is completed by two triazolyl N atoms and one chelating carboxyl group of D-cam2–. The axial positions are occupied by one carboxyl O6 and water O2W with a O6–Cd4–O2W bond angle of 152.4(4)°. In complex 1, the whole Cd–N bond distances range from 2.268(7) to 2.441(8) Å, and Cd–O bond distances vary from 2.166(6) to 2.436(6) Å.



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Both triazolyl groups of 2,6-H2bptp are completely deprotonated. As illustrated in Scheme 1, two independent 2,6-bptp2– ligands exhibit two types of coordination modes, heptadentate mode I and hexadentate mode II, respectively connecting five and four Cd(II) ions via two triazolyl groups and two pyridyl groups. One terminal pyridine is free. Moreover, both 2,6-bptp2– ligands display central chelating tridentate coordination via central pyridyl group and two triazolyl groups. To relieve the steric effect, two terminal pyridyl rings are twisted by 41.73° and 20.40° with respect to the central pyridyl ring for µ5-bptp2–, and 1.069° and 34.67° for µ4-bptp2–, respectively. The 2,6-bptp2– ligands connect Cd(II) ions to form a 2D [Cd4(2,6-bptp)2]n sheet (Figure 1b). Interestingly, the chiral source D-camphoric acid of 1 undergoes the racemization under hydrothermal condition, which was also observed previously,14 leading to the structure of 1 composed of both D- and L-camphorate with equal ratio. This structural variation can be clearly observed through contrasting the position changes of four different atoms around chiral C*40, C*43, C*50 and C*53 atoms. Both carboxyl groups of D/L-camphoric acid are completely deprotonated. D/L-cam2– ligands adopt two types of coordination modes, respectively, and each links to three Cd(II) ions. The L-camphorate is tridentate, while the D-camphorate is pentadentate (Figure S2, Supporting Information). Pillared by D/L-cam2– spacers, the 2D [Cd4(2,6-bptp)2]n layers parallel stack over each other with a repeating distance of 9.705(11) Å to give rise to a porous 3D metal-organic framework (Figure 1c). The potential solvent-accessible occupancy volume is 9.2% calculated using PLATON (total potential solvent area volume 579.7 Å3 per unit cell volume 6304.3 Å3). Further insight into this structure, such a connection between the D/L-cam2– and Cd(II) ions results in two kinds of [Cd2(D/L-cam)]n infinite helical chains running along the b-axis, corresponding to exhibit the left- and right-handedness (both with a pitch of 12.25(4) Å, Figure 1d). In each helical chain, tridentate L-cam2– and pentadentate D-cam2– occur alternately to link Cd(II) ion. Into the same pillar layer, the left- and right-handed helical chains are parallel arranged in pairs alternately, forming the repeating unit. Hence the complex 1 undergoes the racemization, and crystallizes in an achiral space group P21/c. Overall, the repeating [Cd2(D/L-cam)]n 1D chains interweave with the 2D [Cd4(2,6-bptp)2]n sheets via sharing the metal sites, further extend the 2D layers into a sandwich-like 3D framework (Figures 1c, and 1e). This 3D framework possesses 1D nano-sized channels with the dimensions of ca. 10.2 Å × 8.4 Å (Cd···Cd distance), and the average offset distance of 6.5 Å from the shifting of repeating units between neighboring layers.

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(a)

(b)

(c)

(d)

(e) Figure 1. (a) The coordination structure of 1. Partial

hydrogen atoms and lattice water are omitted for clarity. (b) 2D [Cd4(2,6-bptp)2]n sheet built by µ5-bptp2– (orange) and µ4-bptp2– (purple) with Cd(II) ions (blue). (c) 3D metal-organic framework constructed from 2D sheets pillared by D/L-cam2– spacers. (d) Perspective views of the 1D left-handed (red) and right-handed (green) helices of [Cd2(D/L-cam)]n chains. (e) A schematic representation of the sandwich-like 3D polymeric structure of 1.


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Structure of [Cd2(2,6-Hbptp)2(Hbtc)] n·4nH2O (2). Complex 2 is a 1D nanorod-like coordination polymer. The asymmetrical unit consists of two independent Cd(II) ions, two 2,6-Hbptp– ligands, one Hbtc2– ligand, and four lattice water molecules (Figure 2a). Cd1 adopts a distorted octahedral geometry, coordinated by four N atoms of 2,6-Hbptp– and two carboxyl O atoms. The chelating carboxyl group (O1, O2) and two pyridyl N atoms (N5, N10) locate at the equatorial plane. Two triazolyl N atoms occupy the axial positions with a N4-Cd1-N8 bond angle of 140.7(3)º. Cd2 also displays a distorted octahedral geometry. The equatorial plane is completed by two triazolyl N13 and N17 atoms, pyridyl N14, and carboxyl O5. The axial positions are occupied by carboxyl O6 and pyridyl N9 with a O6-Cd2-N9 bond angle of 138.4(3)º. All Cd–N bond distances range from 2.289(9) to 2.427(8) Å, and Cd–O bond distances vary from 2.227(9) to 2.508(8) Å. Both 2,6-Hbptp– ligands are tetradentate and adopt a coordination mode III (Scheme 1). In each 2,6-Hbptp– ligand, two triazolyl groups exhibit different coordination patterns. One triazole is charge neutral and coordinates to Cd(II) via 4-position nitrogen atom, whereas the other one is deprotonated and connects to Cd(II) via 2-position nitrogen atom. Each 2,6-Hbptp– ligand combines with two Cd(II) ions, chelating to one Cd(II) via central tridentate coordination and binding to the other Cd(II) via a terminal pyridine. The remaining terminal pyridine is uncoordinated and co-planar with the central chelating plane. In addition, the two independent 2,6-Hbptp– ligands show a little difference in terms of steric environment. The coordinated terminal pyridine is twisted by 42.0° with regard to the central pyridyl ring in one 2,6-Hbptp–, and twisted by 23.3° in the other 2,6-Hbptp–. The 2,6-Hbptp– ligands connect Cd(II) ions to form a 1D zigzag chain with a Cd···Cd distance of 9.685(2) Å. Viewed down to the a-axis, the 1D zigzag chain shows a crescent motif originating from the bent backbone of two 2,6-Hbptp– ligands (Figure 2b). In complex 2, 1,3,5-benzenetricarboxylic acid (H3btc) is partially deprotonated. The Hbtc2– ligand is tetradentate. Two carboxylate groups chelate to two Cd(II) ions which belong to different Cd-Hbptp zigzag chains. Interestingly, every two Hbtc2– ligands intercross to each other and link two Cd-Hbptp zigzag chains together (Figure 2c), forming a 1D nano-sized rod-shaped coordination polymer (Figure 2d).15 Viewed along the a-axis, the nano-rod exhibits a square section, in which four Cd(II) ions locate at four corners, with the approximate dimensions of 1.11 nm × 1.06 nm (Cd···Cd distance). Obviously, the V-shaped structure of 2,6-Hbptp– ligand plays an important role in the formation of four corners. Furthermore, the adjacent nano-rods are parallel packed and interact with each other through hydrogen bonds between lattice water and nano-rods to form a 3D supramolecule (Figure 2e).

(a)

(b)

(c)

(d)

(e)

Figure 2. (a) The asymmetric unit of 2. Partial hydrogen atoms and lattice water are omitted for clarity. (b) 1D zigzag chain of Cd-Hbptp along the a-axis (left) and down to the a-axis (right). (c) Two Hbtc2– ligands intercross to each other and link two Cd-Hbptp zigzag chains. (d) The linear nano-rod coordination polymer (left). Hbtc2– ligands are omitted for clarity (right). (e) The 3D supramolecular architecture shown parallel nano-rod arrays.

Structure of [Zn(2,6-bptp)(H2O)] n·nH2O (3). Complex 3 is a 1D zigzag chain coordination polymer. The asymmetric unit contains one independent Zn(II) ion, one 2,6-bptp2–



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ligand, one coordinated water as well as one lattice water molecule (Figure 3a). Zn(II) adopts a distorted square-pyramidal geometry, coordinated by four N atoms of 2,6-bptp2– on the basal plane and water O1W at apical position with a O1W–Zn1–N5 bond angle of 114.8(2)º. The Zn–N bond distances range from 2.026(5) to 2.179(5) Å, and Zn–O1W distance is 1.984(5) Å. In the complex 3, two triazolyl groups of 2,6-H2bptp are completely deprotonated. The 2,6-bptp2– ligand is tetradentate and adopts a coordination mode IV (Scheme 1). Both triazolyl groups coordinate to Zn(II) via 2-position nitrogen atom. The central pyridyl group and two triazolyl groups coordinate to Zn1 to form two five-membered chelating rings. Three pyridyl rings of 2,6-bptp2– are essentially co-planar with two triazolyl rings. One terminal pyridine coordinates to Zn1A, while the other one is free. The previously reported {[Zn(bptp)(H2O)]·2H2O·CH3CN}n is a 2D zinc coordination polymer.8 The pentadentate 2,6-bptp2– ligand chelates to a Zn(II) via the central pyridyl group and two triazolyl groups, and links two Zn(II) ions via two terminal 3-positional pyridyl groups. Our new 2,6-H2bptp ligand is a little different with terminal 4-positional pyridyl groups. Furthermore, each 2,6-bptp2– ligand links to two zinc ions to form a 1D zigzag chain with a Zn···Zn separation of 10.236(1) Å (Figure 3b). Between the adjacent 1D chains, there are two strong hydrogen bonds linking the coordinated water O1W with pyridyl N9 and triazolyl N7, which extend the 1D chains to supramolecular doublechains structure. The double-chains are further parallelly stacked to form a 3D supramolecular architecture (Figure 3c). (a)

(b)

(c)

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architecture built by double-chains. Structure of [(Mo8O26)Cu2(2,6-H2bptp)2] n (4). Viewing the structures of 1–3, 2,6-H2bptp is a large-sized V-shaped rigid ligand which trends to take central tridentate coordination with metal ions to form chelating basal plane. Based on this structural feature, we assume to use POMs as bulky anion ligand to coordinate the metal center along axial direction, in order to construct metal-organic frameworks with diverse structures. Moreover, POMs are also easy in H-bonding combination with N-heterocyclic ligand to construct inorganic–organic hybrid compound. Complex 4 is a 1D linear chain coordination polymer constructing from Cu2(2,6-H2bptp)24+ building block and Mo8O264− anion. The asymmetric unit contains one independent Cu(II) ion, one 2,6-H2bptp and half [Mo8O26]4– ligand (Figure 4a). Cu(II) adopts a square-pyramidal geometry, coordinated by four 2,6-H2bptp N atoms on the basal plane and the terminal O1 atom of [Mo8O26]4– at apical position with a O1–Cu1–N5 bond angle of 99.8(3)º. The Cu–N bond distances range from 1.962(9) to 2.043(9) Å, and Cu–O1 distance is 2.332(8) Å. The Mo8O264– anion is a typical β–structure octamolybdate which is built up from eight edge-sharing MoO6 octahedra with four kinds of oxygen atoms (six µ2-O, four µ3-O, two µ5-O, and twelve terminal Ot).16 The Mo-O bond distances vary from 1.686(9) to 2.435(7) Å. In complex 4, 2,6-H2bptp is a neutral tetradentate ligand and adopts a coordination mode V (Scheme 1). The central pyridyl group and two triazolyl groups coordinate to Cu1 to form two five-membered chelating rings. One terminal pyridine coordinates to Cu1A, while the other terminal pyridine is free. To increase the steric stabilization, the coordinated terminal pyridyl ring is twisted by 51.3(3)° with respect to the central pyridyl ring, whereas the uncoordinated terminal pyridine is nearly co-planar with the central pyridine (dihedral angle 8.3(3)º). As shown in Figure 4b, Cu1 and Cu1A are connected by two 2,6-H2bptp ligands to form a Cu2(2,6-H2bptp)24+ dimer. Cu2(2,6-H2bptp)24+ dimers are parallel arranged, and further linked by β -Mo8O264– clusters along c-axis to form a 1D linear coordination polymer (Figure 4c). These 1D linear chains are parallelly packed and interact with each other through hydrogen bonds, which leads to the formation of a 3D supramolecular architecture (Figure 4d). (a)

Figure 3. (a) The asymmetric unit of 3. Hydrogen atoms and lattice water are omitted for clarity. (b) The 1D zigzag chain along the c-axis. (c) The 3D supramolecular


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Crystal Growth & Design relative to the central pyridyl ring, however, the other 2,6-H2bptp is essentially co-planar. Every two [Co(2,6-H2bptp)2]2+ cations are chargebalanced by one β -Mo8O264– anion. The parallel pyridyl groups between adjacent [Co(2,6-H2bptp)2]2+ units show weak face-to-face π···π stacking interaction with a centroid-to-centroid distance of 3.75 Å. Meanwhile, there exist six hydrogen bonds between [Co(2,6-H2bptp)2]2+, β-[Mo8O26]4– and lattice H2O molecules (Table S1). These π···π stacking and H-bonding interactions assemble the [Co(2,6-H2bptp)2]2+ cations to form a 3D supramolecular architecture with nano-sized tunnels (1.551 × 1.517 nm2), in which β -[Mo8O26]4– clusters are embedded (Figure 5b).

(b)

(c) (a)

(d)

(b)

Figure 4. (a) The asymmetric unit of 4. Partial hydrogen atoms are omitted for clarity. (b) Cu2(2,6-H2bptp)24+ dimer. (c) 1D linear chain along c-axis. (d) Perspective views of the 3D supramolecular architecture of 4.

Structure of [Co(2,6-H2bptp)2][Mo8O26] 0.5·5H2O (5). Complex 5 consists of one [Co(2,6-H2bptp)2]2+ cation, half β-[Mo8O26]4– anion, and five lattice water molecules in the asymmetric unit (Figure 5a). Co1 is surrounded by six nitrogen atoms from two 2,6-H2bptp ligands to complete a slightly distorted octahedral geometry. Six Co−N bond distances range from 1.897(4) to 1.931(4) Å. Three bond angles along opposite positions are 173.49(18), 162.90(19), and 162.51(19)º, respectively. Both 2,6-H2bptp are neutral tridentate ligand and adopt a coordination mode VI (Scheme 1). In every 2,6-H2bptp, the central pyridyl group and two triazolyl groups coordinate to Co(II) center to form two five-membered chelating rings, whereas two terminal pyridyl groups are uncoordinated. Two 2,6-H2bptp ligands are nearly perpendicular to each other, and coordinate to Co1 to form a [Co(2,6-H2bptp)2]2+ cation. Further insight into this cation, two 2,6-H2bptp ligands show a little difference. In one 2,6-H2bptp, two terminal pyridyl rings are twisted by 25.9(2)º and 9.3(2)º

Figure 5. (a) The asymmetric unit of 5. Partial hydrogen atoms and lattice water are omitted for clarity. (b) The 3D supramolecular architecture of 5. Structure of [(PMo12O40)Ag(2,6-H4bptp)]·2H2O (6). The asymmetric unit of complex 6 is comprised of one Ag(2,6-H4bptp)3+ cation plus one Keggin PMo12O403− anion ligand, together with two lattice water molecules (Figure 6a). Ag(I) locates at the center of the planar square geometry, coordinated by three N atoms of 2,6-H4bptp2+ and O2 atom from PMo12O403−. Ag−N bond distances range from 2.358(6) to 2.472(6) Å, and Ag−O2 distance is 2.559(5) Å, all in normal ranges.17 The bond angles of N1−Ag1−O2 and N6−Ag1−N2 are 144.2(2), 139.5(2)º respectively. Recently, supramolecular interaction between Ag(I) ion and bulky polyoxometalates has attracted much attention. For instance, Niu et al. reported six supramolecular systems assembling from PMo12O403− and



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silver(I)-Schiff base on the basis of Ag···O weak interaction.18 In complex 6, the weak interaction between Ag(I) and bridging atom O5 of Keggin anion is also observed. The Ag···O5 distance is 2.731 Å. It should be noticed that two terminal pyridyl groups of 2,6-H2bptp undergo protonation in 6. 2,6-H4bptp2+ displays a central chelating tridentate coordination mode VII (Scheme 1). To reduce the steric hindrance, two terminal pyridine rings are twisted by 45.01° and 37.78° with respect to the central pyridyl ring. The arched Ag(2,6-H4bptp)3+ building block surrounds the ball-shaped Keggin PMo12O403− cluster in order to maintain the charge balance. Based on hydrogen bonding interactions (Table S1), the bulky PMo12O403− clusters are stacked closely to form a 3D porous supramolecular architecture, in which Ag(2,6-H4bptp)3+ pieces are embedded into the cavities (Figure 6b). (a)

(b)

Figure 6. (a) The asymmetric unit of 6. Partial hydrogen atoms and lattice water O1W are omitted for clarity. (b) View of the 3D supramolecular architecture.

Coordination Modes of 2,6-H2bptp Ligand. As illustrated in Scheme 1, 2,6-H2bptp adopts seven types of coordination modes, and acts as hepta-, hexa-, tetra-, or tri-dentate ligand in the six complexes. All the complexes incorporate a central chelating plane, which leads to a steric hindrance site. To enhance the steric stability, terminal pyridine rings rotate to reduce this impediment. Unexpectedly, the bidentate bridging coordination mode of 2,6-H2bptp has not been observed. Two terminal pyridyl

Page 8 of 20

groups are either free or monodentate coordination in 1−6. However, it was observed that both terminal pyridyl N atoms could coordinate to metal ions in {[Zn(bptp)(H2O)]·2H2O·CH3CN}n and {[Pb(bptp)]·H2O}n complexes.8 Interestingly, two 1,2,4-triazole groups of 2,6-H2bptp exhibit a great coordination diversity. In coordination mode I, one triazole shows N1N2N4-bridge bonding mode, and the other one is a N1N2-bridge. In mode II, one triazole adopts N1N4-bridging mode, and the other one exhibits a N1N2-bridge. In mode III and mode V, one triazole is N2-coordinate, while the other one is N4-coordinate. In mode IV and mode VI, both triazoles are N2-coordinate, however, the triazole groups are anion in IV but neutral in VI. In mode VII, both neutral triazoles are N4-coordinate. These bonding modes can be observed in many reported 1,2,4-triazole complexes.19 Synthesis and Infrared Spectra. The complexes 1−6 are successfully prepared by hydrothermal reactions at 160 °C. A mixture of Cd(NO3)2, 2,6-H2bptp, D-H2cam and triethylamine in a molar ratio of 2:1:2:4 gives rise to the 3D porous metal-organic framework 1. While a mixture of Cd(NO3)2, 2,6-H2bptp, H3btc and NaOH in a molar ratio of 2:1:1:3 yields the 1D nanorod-like coordination polymer 2. In an attempt to prepare Zn(II) complex using 2,6-H2bptp and terephthalic acid as ligands, a 1D zigzag chain complex 3 without carboxylate ligand is afforded. When using POMs to replace polycarboxylates as auxiliary ligands, the 1D linear chain coordination polymer 4 and mononuclear silver complex 6 are prepared. Both 2,6-H2bptp complexes contain POMs as inorganic ligands. Under similar hydrothermal condition, the supramolecular framework 5 is obtained, in which β -[Mo8O26]4– clusters are embedded into the nano-sized tunnels. In this work, metal-organic hybrid frameworks with high-dimensions have not been achieved, probably due to the space steric hindrance generated by bulky POMs. Crystal structural analyses indicate that the steric configuration of various ancillary polycarboxylate/POM ligands and different proportion of added inorganic/organic base may have a significant impact on the coordination modes of 2,6-H2bptp and the final structures of complexes. The existence of 2,6-H2bptp ligand in the six complexes is confirmed by IR spectroscopy (Figure S3). The bands occur at about 3090, 1630 and 1510 cm−1 are assigned to the stretching vibrations of C−H, C=C and C=N bonds of 2,6-H2bptp, respectively. The bands near 834, 797, 754 and 711 cm−1 can be assigned to δ(C−H) bending vibrations of pyridyl groups. In the IR spectrum of 1, two types of D/L-cam2− ligands display νas(COO−) bands at 1613 and 1525 cm−1, and νs(COO−) bands at 1433 and 1398 cm−1.20 The C−H stretching vibrations of methyl and methylene occur at 2971 and 2882 cm−1. The Hbtc2− ligand in 2 is partially deprotonated. Its νas(COO−) and ν(COO−) bands


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occur at 1551 and 1376 cm−1 respectively. The ν(COOH) characteristic peak occur at 1716 cm−1 which indicates that one carboxyl group of Hbtc2− keeps protonation. The IR spectra of 4 and 5 exhibit two groups of strong bands near 945 and 710 cm−1, which attribute to the stretching vibrations of terminal Mo=O and bridging Mo−O−Mo in β-[Mo8O26]4−. While the characteristic bands of Mo=O and Mo−O−Mo in Keggin [PMo12O40]3− occur at 957 and 795 cm−1 for complex 6.21 Thermogravimetric Analysis. In order to investigate the thermal stabilities of 2,6-H2bptp ligand and its complexes, the thermal behaviors of coordination polymers 1−3 and Ag(I) polyoxometalate complex 6 are chosen to be tested by TG-DSC (Figure S4). The experiments are performed on solid samples consisting of numerous single crystals in 20−800 °C range under N2 atmosphere. For complex 1, a weight loss of 5.5% in 40−220 °C range is consistent with the removal of four lattice water and two coordinated water molecules (calcd 6.4%). The dehydrate metal-organic framework of 1 is quite stable under 440 °C, and then decomposes continuously in 440−800 ºC range. The final residue is CdO (obsd 31.0%, calcd 30.5%). The complex 2 loses 6.1% weight in 40−100 °C range, corresponding to the loss of four lattice water molecules (calcd 5.8%). Similar to the TG curve of 1, the anhydrous complex of 2 is also quite stable up to 440 °C, and then successive pyrolysis process continues to 800 ºC without stop. Complex 3 loses coordinated and lattice water molecules in 50–220 ºC range with a weight-loss of 8.2% (calcd 7.7%). After 380 ºC, the further weight-loss is assigned to the decomposition of Zn-bptp residue. Complex 6 displays a weight-loss of 16.8% in 80–520 ºC range, corresponding to the expulsion of two lattice water molecules and 2,6-H4bptp2+ ligand (calcd 17.3%). After that, the polyoxometalate intermediate begins to slowly collapse up to the final 800 °C. Photoluminescence. Considering the conjugated structure of rigid 2,6-H2bptp ligand and the varied luminescent behaviors of d10 transition metal complexes, we determined the luminescent properties of Cd(II) complexes 1 and 2, Zn(II) complex 3, and Ag(I) polyoxometalate complex 6 in the solid state at room temperature (Figure 7). When excited with 415 nm light, the Cd(II) complexes 1 and 2 are strong blue luminescent emitters with an emission maximum at 459 and 468 nm, respectively. Two emission bands with maximum at 458 and 468 nm are also observed in the emission spectra of 3 and 6. To understand the emission mechanism, the luminescence of 2,6-H2bptp ligand is determined for comparison. With the similar excitation at 415 nm, 2,6-H2bptp exhibits a broad emission peak centered at 468 nm, assigned to the intraligand π*→π transition. The similar emission energy between tested complexes and 2,6-H2bptp ligand indicates that the luminescent mechanism

of these emission.

complexes

originates

from ligand-centered

Figure 7. Emission spectra of 2,6-H2bptp ligand and complexes 1, 2, 3 and 6. Magnetic Property. The temperature dependence of magnetic susceptibilities of the Cu(II) complex 4 was measured in 3−300 K range with a Quantum Design PPMS-9 magnetometer in an applied magnetic field of 10 kOe. The data are shown in Figure S5 as plots of χMT and χM−1 verse T. The χMT value is about 0.40 emu·K·mol−1 at 300 K, which is close to the value expected for spin-only value of Cu2+ ion (0.38 emu·K·mol−1 with g = 2.0). The χMT value decreases gradually upon cooling of the sample, and a value of 0.34 emu·K·mol−1 is reached at 3 K. The data can be fitted to the Curie-Weiss law, yielding C = 0.425 emu·K·mol−1 and θ = –1.39 K. The results show the occurrence of weak antiferromagnetic interaction between the 2,6-H2bptp bridged Cu(II) centers in the Cu2(2,6-H2bptp)24+ dimer, which is isolated by large β–octamolybdate clusters. CONCLUSIONS Based on rigid V-shaped 2,6-H2bptp ligand, four coordination polymers and two supramolecular complexes have been successfully synthesized and structurally characterized. 2,6-H2bptp is a new N-heterocyclic ligand and displays seven types of coordination modes in 1–6. Different reaction conditions can influence the protonation and deprotonation of 2,6-H2bptp ligand, thus affecting the overall structures of complexes. Complex 1 possesses a 3D porous metal-organic framework and exhibits an intriguing sandwich-like motif. Complex 2 is a 1D nanorod-like coordination polymer. Both Cd(II) complexes are blue luminescent emitters, which are thermally stable up to 440 °C. These research results reveal that 2,6-H2bptp is a valuable large-sized V-shaped multidentate ligand. The further study for 2,6-H2bptp coordination system are under way. ASSOCIATED CONTENT Supporting Information. Additional crystallographic data for complexes 1−6 in CIF format, TGA, IR and



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magnetic data in PDF format. CCDC–936143 for 1, –936144 for 2, –906198 for 3, –906192 for 4, –906194 for 5, and –906193 for 6. This information is available free of charge via the Internet at http://pubs.acs.org. AUTHOR INFORMATION Corresponding Author: *E-mail: [email protected] (M.-X.L.). Fax: +86-21-66134594 (M.-X.L.). Notes: The authors declare no competing financial interest. ACKNOWLEDGMENTS Financially supported by the National Natural Science Foundation of China (21171115), and the Innovation Program (12ZZ089) of Shanghai Municipal Education Commission.

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Zhu, S. R. Cryst. Growth Des. 2009, 9, 4626. (c) Yang, P.; He, X.; Li, M. X.; Ye, Q.; Ge, J. Z.; Wang, Z. X.; Zhu, S. R.; Shao, M.; Cai, H. L. J. Mater. Chem. 2012, 22, 2398. (7) (a) Lin, W. Q.; Leng, J. D.; Tong, M. L. Chem. Commun. 2012, 48, 4477. (b) Bao, X.; Liu W.; Liu J. L.; Gómez-Coca S.; Ruiz E.; Tong, M. L. Inorg. Chem. 2013, 52, 1099. (8) Han, G.; Mu, Y.; Wu, D.; Jia, Y.; Hou, H.; Fan, Y. J. Coord. Chem. 2012, 65, 3570. (9) (a) Hong M. C. Cryst. Growth Des. 2007, 7, 10. (b) Cheetham, A. K.; Rao, C. N. R.; Feller, R. K. Chem. Commun. 2006, 4780. (c) Perry, J. J. IV; Perman, J. A.; Zaworotko, M. J. Chem. Soc. Rev. 2009, 38, 1400. (d) Wee, L. H.; Wiktor, C.; Turner, S.; Vanderlinden, W.; Janssens, N.; Bajpe, S. R.; Houthoofd, K.; Tendeloo, G. V.; Feyter, S. D.; Kirschhock, C. E. A.; Martens, J. A. J. Am. Chem. Soc. 2012, 134, 10911. (10) (a) Banerjee, A.; Raad, F. S.; Vankova, N.; Bassil, B. S.; Heine, T.; Kortz, U. Inorg. Chem. 2011, 50, 11667. (b) Jin, H.; Qi, Y.; Wang, E.; Li, Y.; Wang, X.; Qin, C.; Chang, S. Cryst. Growth Des. 2006, 6, 2693. (c) Dang, D. B.; Zheng, G. S.; Bai, Y.; Yang, F.; Gao, H.; Ma, P. T.; Niu, J. Y. Inorg. Chem. 2011, 50, 7907. (11) (a) Zhang, S. W.; Zhao, J. W.; Ma, P. T.; Chen, H. N.; Niu, J. Y.; Wang, J. P. Cryst. Growth Des. 2012, 12, 1263. (b) Banerjee, A.; Raad, F. S.; Vankova, N.; Bassil, B. S.; Heine, T.; Kortz, U. Inorg. Chem. 2011, 50, 11667. (c) Tian, A. X.; Ying, J.; Peng, J.; Sha, J. Q.; Su, Z. M.; Pang, H. J.; Zhang, P. P.; Chen, Y.; Zhu, M.; Shen, Y. Cryst. Growth Des. 2010, 10, 1104; (d) Liu, B.; Yu, Z. T.; Yang, J.; Hua, W.; Liu, Y. Y.; Ma, J. F. Inorg. Chem. 2011, 50, 8967. (12) (a) Jin, H.; Qi, Y. F.; Wang, E. B. Li, Y. G.; Wang, X. L.; Qin, C.; Chang, S. Cryst. Growth Des. 2006, 6, 2693. (b) Sha, J. Q.; Liang, L. Y.; Sun, J. W.; Tian, A. X.; Yan, P. F.; Li, G. M.; Wang, C. Cryst. Growth Des. 2012, 12, 894. (c) Li, M. X.; Chen, H. L.; Geng, J. P.; He, X.; Shao, M.; Zhu, S. R.; Wang, Z. X. CrystEngComm, 2011, 13, 1687. (d) Wang, X. L.; Qin, C.; Wang, E. B.; Su, Z. M. Chem. Commun. 2007, 4245. (13) Sheldrick, G. M. SHELXTL. Version 6.1, Bruker AXS Inc., Madison, Wisconsin, USA, 2000. (14) (a) Luo, F.; Ning, Y.; Luo, M.; Huang, G. CrystEngComm, 2010, 12, 2769. (b) Zhang, J.; Yao, Y. G.; Bu, X. Chem. Mater. 2007, 19, 5083. (15) Chen, L. F.; Zhang, J.; Ren, G. Q.; Li, Z. J.; Qin, Y. Y.; Yin, P. X.; Cheng, J. K.; Yao, Y. G. CrystEngComm, 2008, 10, 1088. (16) Meng, J. X.; Lu, Y.; Li, Y. G.; Fu, H.; Wang, E. B. Cryst. Growth Des. 2009, 9, 4116. (17) Yang, H. X. ; Cao, S. Y.; Lu, J.; Xu, B.; Lin, J. X. ; Cao, R. Inorg. Chem. 2010, 49, 736. (18) Dong, D. B.; Zheng, Y. N.; Bai, Y.; Guo, X. Y.; Ma, P. T.; Niu, J. Y. Cryst. Growth Des. 2012, 12, 3856. (19) (a) Haasnoot, J. P. Coord. Chem. Rev. 2000, 200−202, 131. (b) Klingele, M. H.; Brooker, S. Coord. Chem. Rev. 2003, 241, 119. (20) Deacon, G. B.; Phillips, R. J. Coord. Chem. Rev. 1980, 33, 227. (21) Jin, H.; Zhou, B.; Wang, C.; Su, Z.; Zhao, Z.; Zhang, Y.; Zhu, C. J. Solid State Chem. 2006, 179, 1674.


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Table 1. Crystal Data and Structure Refinement for Complexes 1− −6 1 formula

2

C58H62N18O14Cd4

fw 1684.86 cryst syst Monoclinic space group P21/c a (Å) 13.570(1) b (Å) 12.255(1) c (Å) 38.232(4) 90 α (deg) 97.443(1) β (deg) 90 γ (deg) V [Å3] 6304.3(12) Z 4 1.775 Dc (g cm−3) F(000) 3360 1.411 µ (mm−1) reflns/unique 32352 / 11165 Rint 0.0537 data/restraints/parameters 11165 / 3 / 809 GOF on F2 1.088 R1, wR2 (I >2σ(I)) 0.0647, 0.1825 R1, wR2 (all data) 0.0900, 0.1987 largest diff. peak 2.689, −3.254 and hole (e Å−3)

3

4

5

C47H36N18O10Cd2

C19H15N9O2Zn

1237.74 Triclinic P-1 9.685(2) 15.572(4) 17.089(4) 79.553(3) 74.687(3) 75.355(3) 2386.8(10) 2 1.722 1240 0.972 15143 / 10618 0.0591 10618 / 0 / 696 1.041 0.0892, 0.2300 0.1843, 0.2785

466.77 Monoclinic C2/c 19.141(3) 13.357(2) 15.726(2) 90 103.586(2) 90 3908.1(9) 8 1.587 1904 1.296 12113 / 4454 0.0650 4454 / 0 / 281 1.047 0.0680, 0.2024 0.1193, 0.2379

C19H13N9O13 Mo4Cu 1022.68 Triclinic P-1 11.121(4) 11.668(4) 11.743(4) 68.637(4) 77.481(4) 80.178(4) 1378.3(7) 2 2.464 982 2.613 8430 / 6020 0.0406 6020 / 0 / 415 1.040 0.0722, 0.1871 0.1060, 0.2117

1.445, -0.918

2.639, −0.566

3.192, −1.907

6

C38H36N18O18 Mo4Co 1475.54 Triclinic P-1 10.257(1) 13.333(2) 18.309(3) 105.250(2) 93.841(2) 95.042(2) 2395.7(6) 2 2.046 1458 1.453 15271 / 10728 0.0247 10728 / 0 / 712 1.082 0.0518, 0.1003 0.0710, 0.1191

C19H19 N9O42P Mo12Ag 2335.55 Monoclinic C2/c 30.221(2) 18.739(1) 17.536(1) 90 102.794(1) 90 9684.5(9) 8 3.204 8784 3.547 24966 / 8562 0.0318 8562 / 2 / 765 1.067 0.0466, 0.0937 0.0597, 0.1046

0.856, −0.914

2.657, −2.668

Table 2. Selected Bond Distances (Å) and Angles (deg) for Complexes 1− −6a 1 Cd(1)-O(1W) Cd(1)-O(7)#2 Cd(1)-O(1) Cd(1)-N(11)#3 Cd(1)-N(2) Cd(2)-O(2) Cd(2)-O(1) Cd(2)-N(3) N(11)#3-Cd(1)-O(1W) O(7)#2-Cd(1)-O(1) O(7)#2-Cd(1)-N(2) O(6)-Cd(4)-O(2W)

2.322(6) 2.199(6) 2.230(6) 2.296(7) 2.323(6) 2.340(7) 2.436(6) 2.400(7) 179.3(3) 131.3(3) 130.0(3) 152.4(4)

Cd(2)-N(8) Cd(2)-N(1)#4 Cd(2)-N(5) Cd(2)-N(18)#5 Cd(3)-O(5) Cd(3)-N(13) Cd(3)-N(15) Cd(3)-N(7) N(1)#4-Cd(2)-N(18)#5 N(3)-Cd(2)-N(5) N(8)-Cd(2)-N(5) O(4)#6-Cd(4)-N(6)

Cd(1)-O(2) Cd(1)-N(5) Cd(1)-O(1) Cd(1)-N(10)#2 O(2)-Cd(1)-N(5) N(4)-Cd(1)-N(8)

2.230(8) 2.328(8) 2.508(8) 2.293(10) 148.7(3) 140.7(3)

Cd(1)-N(4) Cd(1)-N(8) Cd(2)-N(9) Cd(2)-N(14) N(10)#2-Cd(1)-O(1) O(5)#1-Cd(2)-N(14)

Zn(1)-O(1W) Zn(1)-N(5) O(1W)-Zn(1)-N(5) O(1W)-Zn(1)-N(8) N(5)-Zn(1)-N(8)

1.984(5) 2.113(4) 114.76(19) 93.5(2) 74.91(17)

Zn(1)#1-N(1) Zn(1)-N(3) N(1)#2-Zn(1)-N(5) N(1)#2-Zn(1)-N(8) N(1)#2-Zn(1)-N(3)

Cu(1)-N(9)#1 Cu(1)-N(5) N(9)#1-Cu(1)-N(3) N(9)#1-Cu(1)-O(1) N(5)-Cu(1)-N(6)

1.962(9) 1.974(9) 97.1(4) 92.1(3) 79.6(3)

Cu(1)-N(3) Cu(1)-N(6) N(3)-Cu(1)-N(6) N(6)-Cu(1)-O(1) N(3)-Cu(1)-O(1)

2.407(7) 2.384(7) 2.419(7) 2.393(7) 2.166(6) 2.367(7) 2.317(7) 2.268(7) 171.1(3) 67.7(2) 68.6(2) 135.4(4)

Cd(3)-N(14) Cd(4)-O(4)#6 Cd(4)-O(2W) Cd(4)-O(6) Cd(4)-N(6) Cd(4)-O(3)#6 Cd(4)-N(16)

2.304(7) 2.408(11) 2.366(9) 2.241(7) 2.441(8) 2.252(9) 2.302(7)

O(5)-Cd(3)-N(7) N(15)-Cd(3)-N(13) N(7)-Cd(3)-N(14) O(3)#6-Cd(4)-N(16)

98.6(3) 140.2(3) 125.8(3) 149.8(3)

2.347(9) 2.427(8) 2.297(10) 2.289(9) 134.4(3) 155.7(3)

Cd(2)-O(6)#1 Cd(2)-N(17) Cd(2)-N(13) Cd(2)-O(5)#1 O(6)#1-Cd(2)-N(9) N(17)-Cd(2)-N(13)

2.509(8) 2.315(9) 2.421(8) 2.227(9) 138.4(3) 141.7(3)

2.026(5) 2.146(5) 141.8(2) 102.98(19) 99.31(19)

Zn(1)-N(8) O(1W)-Zn(1)- N(1)#2 O(1W)-Zn(1)-N(3) N(5)-Zn(1)-N(3) N(8)-Zn(1)-N(3)

2.179(5) 103.41(19) 100.2(2) 75.46(17) 150.33(18)

1.981(9) 2.043(9) 159.6(4) 88.2(3) 96.0(3)

Cu(1)-O(1) N(9)#1-Cu(1)-N(5) N(9)#1-Cu(1)-N(6) N(5)-Cu(1)-N(3) N(5)-Cu(1)-O(1)

2.332(8) 168.0(4) 102.7(4) 79.9(4) 99.8(3)

2

3

4



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

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5 Co(1)-N(14) Co(1)-N(5) N(14)-Co(1)-N(4) N(14)-Co(1)-N(16) N(14)-Co(1)-N(13) N(4)-Co(1)-N(16) N(4)-Co(1)-N(13)

1.897(4) 1.900(4) 100.19(18) 81.19(18) 81.42(18) 91.22(19) 89.96(19)

Co(1)-N(4) Co(1)-N(16) N(14)-Co(1)-N(5) N(14)-Co(1)-N(7) N(4)-Co(1)-N(5) N(4)-Co(1)-N(7) N(5)-Co(1)-N(16)

Ag(1)-N(1) Ag(1)-O(2) N(6)-Ag(1)-N(2) N(2)-Ag(1)-O(2)

2.358(6) 2.559(5) 139.5(2) 83.18(18)

Ag(1)-N(6) N(1)-Ag(1)-N(6) N(1)-Ag(1)-O(2)

1.899(4) 1.907(4) 173.49(18) 96.71(18) 81.48(18) 162.90(19) 92.51(18)

Co(1)-N(7) Co(1)-N(13) N(5)-Co(1)-N(7) N(16)-Co(1)-N(7) N(7)-Co(1)-N(13) N(5)-Co(1)-N(13) N(16)-Co(1)-N(13)

1.911(5) 1.931(4) 81.44(19) 88.85(19) 95.09(19) 104.92(18) 162.51(19)

2.461(6) 70.3(2) 144.21(19)

Ag(1)-N(2) N(1)-Ag(1)-N(2) N(6)-Ag(1)-O(2)

2.472(6) 69.7(2) 135.50(19)

6

a

Symmetry transformations used to generate equivalent atoms. For 1: #2 x-1, y+1, z; #3 x, y+1, z; #4 -x, y-1/2, -z+3/2; #5 -x+1, -y+1, -z+2; #6 x+1, y, z. For 2: #1 -x+2, -y+2, -z; #2 x-1, y, z. For 3: #1 x, -y+2, z+1/2; #2 x, -y+2, z-1/2. For 4: #1 -x+1,-y+2,-z.

For Table of Contents Use Only

Porous and nanorod-like coordination polymer assembled from a new V-shaped bis(1,2,4-triazolyl)tripyridine ligand Peng Yang, Ming-Xing Li,* Min Shao, Meng-Si Wang, Shi-Xun Cao, Jin-Cang Zhang, Heng-Hua Zhang Six complexes based on a new V-shaped 2,6-bis(3-(pyrid-4-yl)-1,2,4-triazolyl)pyridine ligand were synthesized. 2,6-H2bptp adopts seven types of coordination modes. [Cd4(2,6-bptp)2(D-cam)(L-cam)(H2O)2]n·4nH2O possesses a 3D porous metal-organic framework and exhibits an intriguing sandwich-like motif. [Cd2(2,6-Hbptp)2(Hbtc)]n·4nH2O is a 1D nanorod-like coordination polymer. Both Cd(II) complexes are thermally stable up to 440 °C, and emit blue luminescence.


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


Supporting Information

Porous and nanorod-like coordination polymer assembled from a new V-shaped bis(1,2,4-triazolyl)tripyridine ligand Peng Yang,† Ming-Xing Li,*,† Min Shao,‡ Meng-Si Wang,† Shi-Xun Cao,§ Jin-Cang Zhang,§ Heng-Hua Zhang‡ †

Department of Chemistry, and §Department of Physics, College of Sciences, Shanghai University, Shanghai 200444, P.R. China. ‡

Laboratory for Microstructures, Shanghai University, Shanghai 200444, P.R. China. * Corresponding author. E-mail: [email protected].

Figure S1. Four kinds of coordination geometries around Cd(II) ions in complex 1.

Figure S2. Coordination modes of L-cam2–(left) and D-cam2–(right) in complex 1



100 90

402.40

80

3500

3000

2000

532.01 710.62 701.34

754.28 2500

796.96

1456.13 1432.50 1398.04 1366.63

1612.67

-0 4000

834.01

2882.14

10

1541.01 1525.32

20

1576.88

3450.62

30

2970.78

40

1285.34

50

3092.44 3046.36

%Transmittance

60

1218.32 1182.99 1125.37 1087.10 1011.52

70

1500

1000

500

Wav enumber s (cm-1)

[Cd4(2,6-bptp)2(D-cam)(L-cam)(H2O)2]n·4nH2O (1)

100 90

80

1615.44

10

525.75 723.63

795.11 751.53

20

1445.43 1375.91

1504.12 1634.11

30

1550.61

3426.96

40

1183.77

3071.90

50

841.22

1251.17

60

1006.57

1716.23

1104.71

70

%Transmittance

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

Page 14 of 20

-0 4000

3500

3000

2500

2000

Wav enumber s (cm-1)

[Cd2(2,6-Hbptp)2(Hbtc)]n·4nH2O (2)


1500

1000

500

Page 15 of 20

100 90

3414.69

10

752.22 728.10 705.08

1575.80

3095.88 3071.59

20

807.61

40

30

1028.00 1000.69

1281.93

1509.94 1447.85 1424.21

50

1613.14

% Trans mittance

60

1375.79

1673.52

70

1196.50

80

-0 4000

3500

3000

2500

2000

1500

1000

500

Wav enumbers (cm-1)

[Zn(2,6-bptp)(H2O)]n·nH2O (3)

100 90

80

520.19

560.54 832.42

718.54 667.51

946.07

3088.46

1066.93

914.25

10

3473.19

20

1628.97

30

1500.36

1567.47

40

1457.80 1413.90

50

1285.54

60

1184.77

70

%Transmittance

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


0 4000

3500

3000

2500

2000

Wav enumber s ( cm- 1)

[(Mo8O26)Cu2(2,6-H2bptp)2]n (4)


1500

1000

500


100

1017.21

90

10

1636.47

3448.98

20

1515.72

3095.67

30

0 4000

3500

3000

2500

2000

1500

Wav enumbers (cm-1)

[Co(2,6-H2bptp)2][Mo8O26]0.5·5H2O (5)

[(PMo12O40)Ag(2,6-H4bptp)]·2H2O (6) Figure S3. The IR spectra of complexes 1−6.


668.68 1000

912.04 841.39

40

945.74

50

1456.22

1567.92

60

707.38

1288.49

70

1195.86

80

%Trans mittance

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

Page 16 of 20

500

Page 17 of 20

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


[Cd4(2,6-bptp)2(D-cam)(L-cam)(H2O)2]n·4nH2O (1)

[Cd2(2,6-Hbptp)2(Hbtc)]n·4nH2O (2)



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

[Zn(2,6-bptp)(H2O)]n·nH2O (3)

[(PMo12O40)Ag(2,6-H4bptp)]·2H2O (6) Figure S4. Thermal analysis curves of 1−3 3 and 6.


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


Figure S5. Temperature dependence of χMT and χM−1 for [(Mo8O26)Cu2(2,6-H2bptp)2]n (4)

Table S1. Selected H-Bond Distances (Å) and Angles (°) for Complexes 2− −6

2 Donor− −H···Acceptor O4W−H4WB···N16 O1W−H1WA···N15 O4−H4A···N4 O4−H4A···N3 N7−H7···N18 N11−H11···O1W

D− −H 0.85 0.85 0.82 0.82 0.86 0.86

H···A 2.53 2.21 2.65 1.82 2.12 2.34

A···D 3.16(6) 2.927(14) 3.350(14) 2.624(13) 2.734(14) 2.957(14)

∠D− −H···A 132.0 141.5 144.7 167.8 127.4 128.9

Symmetry code: -x+1, -y+1, -z+1 -x+1, -y+2, -z+1 -x+1, -y+2, -z -x+1, -y+2, -z x+1, y-1, z x+1, y, z

A···D 2.678(7) 2.987(7) 2.699(6)

∠D− −H···A 154.9 179.0 152.5

Symmetry code: x, -y+1, z+1/2 x, -y+1, z+1/2 -x+1/2, -y+3/2, -z

A···D 2.825(12)

∠D− −H···A 139.0

Symmetry code: x, y+1,z

A···D 2.999(6) 2.994(10) 2.918(6) 3.193(7) 3.024(13) 2.808(7)

∠D− −H···A 152.0 161.1 151.5 127.5 140.7 138.4

Symmetry code: x+1, y,z x+1, y,z -x+1, -y+1,-z+1 -x+1, -y+1,-z+1 -x+1, -y+1,-z+1 x, y-1,z

3 Donor− −H···Acceptor O1W−H1WA···N9 O2W−H2WB···N6 O1W−H1WB···N7

D− −H 0.82 0.86 0.86

H···A 1.91 2.12 1.91

D− −H 0.86

H···A 2.12

4 Donor− −H···Acceptor N8−H8···O12

5 Donor− −H···Acceptor O1W−H1WB···O4 O1W−H1WA···O2W O5W−H5WB···O7 O5W−H5WB···O9 O2W−H2WA···O5W O3W−H3WB···N10

D− −H 0.84 0.86 0.85 0.85 0.89 1.08

H···A 2.23 2.16 2.14 2.60 2.28 1.91



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

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6 Donor− −H···Acceptor N9−H9A···O18 N9−H9A···O2W N8−H8···O31 N8−H8···O6 N3−H3A···O29 N5−H5A···O2W N5−H5A···O15 O2W−H2WB···O34 O2W−H2WB···O12 O2W−H2WA···O15

D− −H 0.86 0.86 0.86 0.86 0.960(2) 0.960(2) 0.960(2) 0.85 0.85 0.85

H···A 2.45 2.13 2.40 2.24 2.03(12) 2.54(9) 1.89(5) 2.61 2.37 2.34

A···D 3.096(12) 2.890(12) 2.945(9) 2.976(9) 2.846(9) 3.156(11) 2.776(9) 3.325(12) 3.102(12) 2.967(12)

∠D− −H···A 132.7 147.7 122.2 143.4 142(15) 122(8) 152(9) 142.0 144.3 130.9


Symmetry code: -x+1/2, y+1/2, -z+3/2 x, -y+1, z+1/2 x, -y+1, z-1/2 -x, -y+1, -z+1 x, -y, z-1/2 -x+1/2, y-1/2, -z+1/2 -x+1/2, y-1/2, -z+3/2 -x+1/2, y+1/2, -z+1/2 x, -y+1, z-1/2 x, y, z-1

Porous and Nanorod-Like Coordination Polymers Assembled from a

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