Syntheses, Structures and Properties for ZnII Coordination Polymers Based on a Functional 4'-(3-Pyridyl)-3,2': 6',3"-terpyridine Ligand

Yue CHENG Xiao-Fang WANG Bei LV Huai-Ming HU

Citation:  CHENG Yue, WANG Xiao-Fang, LV Bei, HU Huai-Ming. Syntheses, Structures and Properties for ZnII Coordination Polymers Based on a Functional 4'-(3-Pyridyl)-3,2': 6',3"-terpyridine Ligand[J]. Chinese Journal of Structural Chemistry, 2016, 35(12): 1953-1959. doi: 10.14102/j.cnki.0254-5861.2011-1215 shu

Syntheses, Structures and Properties for ZnII Coordination Polymers Based on a Functional 4'-(3-Pyridyl)-3,2': 6',3"-terpyridine Ligand

English

  • The assembly of coordination polymers (CPs) with versatile structures and potential applications has made a great progress. These CPs can be gra-dually applied in more and more realms such as fluorescent sensor,g as storage,catalysis and magnetic materials,etc[1-6]. However,the regulating of CPs with charming topologies and desired pro-perties is still a big challenge[7-9]. There are many factors that can influence the construction of CPs,especially,the selection of organic ligands and syn-thetic methods[10-12].

    Terpyridyl derivatives are a kind of functional ligands to construct effectively new CPs. Many research groups have paid attention to this type of ligands and obtained lots of valuable CPs[13, 14]. Our group also studied the coordination characteristics of these ligands and properties of CPs[15, 16]. In order to furthercomplete this research,we select the rigid bridging ligand,4΄-(3-pyridyl)-3,2΄:6΄,3΄΄-terpy-ridine (L),as the main ligand to synthesize CPs with excellent properties. It is noted that L with large π conjugation structure is apt to form the π-π stacking interaction to reinforce the stability of structure. In this paper,two new CPs,namely,[ZnL( o-bdc)]n (1) and [ZnL(m-bdc)]n·nH2O (2) have been obtained and their structure,luminescence and thermal stability have also been investigated in detail.

    All chemicals and solvents purchased from commercial sources were of reagent grade and used as received without further purification. L ligand was synthesized according to the reported proce-dure[17, 18]. Infrared spectra were collected on a Bruker EQUINOX 55 Fourier transform Infrared spectrometer using KBr pellets in the range of 400~ 4000 cm-1. Elemental analyses for carbon,hydrogen and nitrogen were carried out with an elementar Vario EL elemental analyzer. Thermal gravimetry analysis (TGA) experiments were performed on a Universal V2.6 DTA system at a rate of 10 ℃/min in a nitrogenatmosphere. Powder X-ray diffraction (PXRD) measurements were measured on a Bruker D8ADVANCE X-ray powder diffractometer (Cu-,1.5418 Å). Fluorescence spectra were obtained from a Hitachi F-4500 spectrophotometer atroom temperature.

    X-ray diffraction intensity data of compounds 1 and2 were collected on a Bruker Smart APEX-II CCD diffractometer equipped with graphite-mono-chromated Mo-radiation (λ = 0.71073 Å) at 296(2) K. Data reduction was performed using the program Bruker SAINT. Empiricalabsorption correctionswere applied by the SADABS program. The structures were solved by dire ct methods of SHELXS-97 and refined by full-matrix least-squares technique on F2 with anisotropic thermal parameters to describe the thermal motionsof all non-hydrogen atoms. The hydrogen atoms were generated geome-trically and refined isotropically through the riding model. For compound 1,the final R = 0.0426,wR =0.0986 (w = 1/[σ2(Fo2) + (0.0539P)2 + 0.0000P], where P = (Fo2 + 2F 2) /3) for 2875 observed reflections (I > 2σ(I)). (Δ/σ)max = 0.001 and S = 0.992. For 2,the final R = 0.0499,wR = 0.1342 (w =1/[σ2(Fo 2) + (0.1000P2)+ 0.1259P],where P= (Fo2+ 2Fc2) /3) for 2659 observed reflections (I > 2σ(I)). (Δ/σ)max = 0.001 and S = 0.933. The selected bond distances and bond angles are given in Table 1 for 1 and Table 2 for 2.

    The synthetic method of 2 is similar to that of 1, except that auxiliary ligand is replaced by H2(m-bdc) (16.6 mg,0.1 mmol) and the mixture was heated at 160 ℃. Yellow block crystals of 2 were obtained. Yield 58% (based on L). Anal. Calcd. (%) for C56H36N8O10Zn2: C,60.50; H,3.26; N,10.08%. Found (%): C,60.33; H,3.15; N,10.01%. IR (KBr,cm-1): 3458(s),3238(m),2079(w),1616(s),1575(m),1481(m),1444(s),1390(s),1161(m),1124(s),825(m),800(m),744(m),725(m),696(m),621(s),482(m).

    A mixture of ZnCl2 (13.6 mg,0.1 mmol),L (16.0 mg,0.05 mmol),H2 (o-bdc) (16.6 mg,0.1 mmol) and H2O (10 mL) were added to a Teflon-lined reactor (25 mL). The pH value was adjustedto 5.0 with 0.5 M NaOH solution after stirring for 30 minutes and heated at 180 ℃ for 3 days under autogenous pressure,then slowly cooled to room temperature. Yellow block crystals of 1 were collected. Yield 65% (based on L). Anal. Calcd. (%) for C28H18N4O4Zn: C,62.29; H,3.36; N,10.38%. Found (%): C,62.18; H,3.13; N,10.29%. IR (KBr,cm-1): 3390(s),3078(m),2079(w),1612(s),1481(m),1390(s),1267(w),1197(m),1134(m),1024(m),835(m),802(m),702(s),642(m),472(w).

    PXRD measurements for 1 and 2 have been carried out at room temperature. The experimental PXRD patterns are in agreement with the simulated ones from single-crystal X-ray diffractions (Fig. 3) ,whichindicate that the as-synthesized materials are pure products.

    Figure 3

    Figure 3.  PXRD patternsof compounds 1 and2 simulated from X-raysingle-crystal structure and experiment

    In order to study the thermal stability of com-pounds 1 and 2,thermal gravimetric(TG) experi-ments were measured. As shown in Fig. 4,com-pound 1 maintained stable in the temperature range of 20~ 300 ℃ ,then its framework started to collapse upon further heating. The initial weight loss of 30.27% (calcd.30.40%) can be ascribed to the decomposition of (o-bdc)2- anions. The second weight loss of 57.82% (calcd.57.49%) can be assigned to the removal of L ligands. The final resi-dual weight can be attributed to zinc oxide (obsd.11.91%,calcd.12.11%). Compound 2 first lost its lattice water molecules with THE weight loss of 2.78% (calcd.3.23%) under 150 ℃. After that it began to decompose at 380 ℃ ,followed by a two-step weight loss due to the release of (o-bdc)2- anions and L ligands.

    Figure 4

    Figure 4.  TGA curvesof compounds 1 and 2

    The luminescent properties of L ligand and its zinc coordination polymers were investigated in the solid state at room temperature,and the emission spectra are shown in Fig. 5. The L ligand exhibitsan emission band at 422 nm upon excitation at 310 nm,whichcan be assigned to the π*π electronic transitions. Upon excitation at 300 nm,compounds 1 and 2 display intense emissionbands at 380 and 366 nmwhich may be ascribed to the ligand-to-metal charge transfer (LMCT). Moreover,compound 1 exhibits an intenseemission band at 417 nm which may be the intraligand transitions. The emission bands of 1 and 2 show blue shifts in comparison withL which may be attributed to the coordination interaction between L ligands and Zn2+ cations leading to the HOMO-LUMO energy gap increase. The enhancement of luminescence intensity for 1 and2 with respect to the free ligand may be due to the effectively increasing the rigidityof the coor-CHENG Y. et al.:Syntheses,Structures and Propertiesfor ZnII Coordination polymers and reducing the energy loss of nonradiative decay of the intraligand when the ligating atoms of L coordinate to the ZnII cen-ters[19-21].

    Figure 5

    Figure 5.  Solid-state emissionspectra of L and compounds1 and 2 at room temperature

    The crystal structure analysis shows that com-pound 2 features a classical 3D cds topological network. The asymmetric unit of 2 contains one ZnII ion,one L ligand,one (m-bdc)2- anion and one lattice water molecule. As depicted in Fig. 2a,Zn1 hexa-coordinates to four O atoms from the (m-bdc)2- anions and two N atoms from the L ligands,leading to an octahedral coordination geometry with slight distortion. The ligating atoms of O(1) ,O(2C),O(3B) and O(4B) occupy the equatorial plane with the Zn-Obond lengths ranging from 2.023(3) to 2.455(4) Å. While N(1) and N(3A) locate on the axis positions with the average Zn-N bond lengths of 2.163(4) Å and N(1) -Zn(1) -N(3A) bond angle of 176.04(13) °. The N atoms of L link to the Zn ions to (a) build 1D wave chains,which further form a 2D layer structure via (m-bdc)2- ions bridging to the Zn cations (Fig. 2b). It is interesting that (m-bdc)2- anions adopted a μ3-η1:η1:η2 coordination mode coordinating to ZnII of three different chains. Simultaneously,(m-bdc)2- bridges to ZnII cations,thus generating another kind of loop chains. Finally,theseloop chains connect to distinct 2D layers to form a 3D architecture. The carboxylates of co-ligands play a key role in expanding the structures. Topologically,the dinuc-lear ZnII units sharing the same carboxylate groups of (m-bdc)2- anions can be assigned as 4-connected nodes,and L ligands and (m-bdc)2- ions as linkers,so the framework of 2 can be simplified as a classical cds network with point symbol of {65.8}.

    Figure 2

    Figure 2.  (a) Coordination environment of ZnII ion in 2. Hydrogenatoms are omitted for clarity (Symmetry codes:A = x,1-y,0.5+z; B = 0.5+x,0.5+y,z; C = -x,1-y,2-z). (b) View of the 2Dlayer structure. (c) View of the 3Darchitecture. (d) View of the topological network

    X-ray single-crystaldiffraction analysis reveals that compound 1 is a 1D coordination chain. The asymmetric unit of 1 consists of one ZnII ion,one L ligand,and one (o-bdc)2- anion. As shown in Fig. 1a, Zn(1) is four-coordinated by two O atoms (O(1) and O(3B)) from (o-bdc)2- anions andtwo N atoms (N1A and N(4) ) from L ligands,resulting in tetrahedral geometry. The Zn-N bond distances are 2.029(3) and 2.081(3) Å,and Zn-O bond distances are 1.937(2) and 1.941(2) Å,all in agreement with those in the similar ZnII compounds[17]. Four pyridyl rings ofL ligand are non-coplanar,and the outer pyridyl rings ar e twisted with respect to the central pyridyl ring.The dihedral angles regarding to the central pyridyl (N(2) ) are 18.71° (N1) ,10.91° (N(3) ) and 20.65° (N(4) ),respectively. The carboxylatesof (o-bdc)2- anions bond to two ZnII i ons,forming the loop units of [Zn2(o-bdc)2]. Then these units build 1D chains via L ligands bridging to the ZnII cations (Fig. 1b). Unfortunately,two carboxylate groups chelate to Zn2+ leading to closed circles,which has no effect on the extension of structure. Finally,adjacent 1D chains construct a 2D structure through π-π stacking interaction (Fig. 1c). There is π-π stacking interaction between pyridyl (N(4) ) rings belonging to different chains with the centroid-centroid distance of 3.654 Å and centroid-plane distance of 3.648 Å,which contributes to stability of the structure.

    Figure 1

    Figure 1.  (a) Coordination environment of ZnII ion in 1. The hydrogen atoms are omitted for clarity (Symmetry codes:A = x,-1+y,z; B = 1-x,1-y,1-z). (b) View of the 1Dchain. (c) View of the 2D supramolecularstructure and π-π stacking interaction

    Table 1

    Table 1.  英文标题
    DownLoad: CSV
    Angle (°) Angle (°) Angle (°) O(3) #1-Zn(1) -O(1) 118.73(10) O(3) #1-Zn(1) -N(1) #2 104.98(11) O(1) -Zn(1) -N(1) #2 120.69(11)
    Bond Dist Bond Dist Bond Dist
    Zn(1) -O(3) #1 1.937(2) Zn(1) -O(1) 1.941(2) Zn(1) -N(1) #2 2.029(3)
    Zn(1) -N(4) 2.081(3) N(1) -Zn(1) #3 2.029(3) O(3) -Zn(1) #1 1.937(2)
    O(3) #1-Zn(1) -N(4) 92.40(11) O(1) -Zn(1) -N(4) 101.85(11) N(1) #2-Zn(1) -N(4) 114.90(11)
    Symmetry transformation: #1: -x+1,-y+1,-z+1; #2: x,y-1,z; #3 x,y+1,z

    Table 2

    Table 2.  SelectedBond Lengths (Å)and Bond Angles (°) for 2
    DownLoad: CSV
    Angle (°) Angle (°) Angle (°) O(1) -Zn(1) -O(2) #1 124.63(12) O(1) -Zn(1) -O(3) #2 136.26(13) O(2) #1-Zn(1) -O(3) #2 99.10(13)
    Bond Dist. Bond Dist. Bond Dist.
    Zn(1) -O(1) 2.023(3) Zn(1) -O(2) #1 2.044(3) Zn(1) -O(3) #2 2.054(3)
    Zn(1) -N(1) 2.156(4) Zn(1) -N(3) #3 2.169(4) Zn(1) -O(4) #2 2.455(4)
    O(1) -Zn(1) -N(1) 90.40(13) O(2) #1-Zn(1) -N(1) 87.71(14) O(3) #2-Zn(1) -N(1) 91.16(14)
    O(1) -Zn(1) -N(3) #3 90.16(14) O(2) #1-Zn(1) -N(3) #3 88.74(14) O(3) #2-Zn(1) -N(3) #3 91.15(14)
    N(1) -Zn(1) -N(3) #3 176.04(13) O(1) -Zn(1) -O(4) #2 79.66(12) O(2) #1-Zn(1) -O(4) #2 155.66(13)
    O(3) #2-Zn(1) -O(4) #2 56.61(12) N(1) -Zn(1) -O(4) #2 90.96(15) N(3) #3-Zn(1) -O(4) #2 93.00(15)
    Symmetry transformation: #1: -x,-y+1,-z+2; #2: x+1/2,y+1/2,z; #3: x,-y+1,z+1/2

    In summary, two new zinc coordination polymers have been synthesized via introducing the dicar- boxylate auxiliary ligands. The syntheses, structures, characterizations and properties of 1 and 2 have been discussed in detail. In addition, the solid-state emission spectra and thermal stabilities have been investigated.

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  • Figure 1  (a) Coordination environment of ZnII ion in 1. The hydrogen atoms are omitted for clarity (Symmetry codes:A = x,-1+y,z; B = 1-x,1-y,1-z). (b) View of the 1Dchain. (c) View of the 2D supramolecularstructure and π-π stacking interaction

    Figure 2  (a) Coordination environment of ZnII ion in 2. Hydrogenatoms are omitted for clarity (Symmetry codes:A = x,1-y,0.5+z; B = 0.5+x,0.5+y,z; C = -x,1-y,2-z). (b) View of the 2Dlayer structure. (c) View of the 3Darchitecture. (d) View of the topological network

    Figure 3  PXRD patternsof compounds 1 and2 simulated from X-raysingle-crystal structure and experiment

    Figure 4  TGA curvesof compounds 1 and 2

    Figure 5  Solid-state emissionspectra of L and compounds1 and 2 at room temperature

    Table 1.  英文标题

    Angle (°) Angle (°) Angle (°) O(3) #1-Zn(1) -O(1) 118.73(10) O(3) #1-Zn(1) -N(1) #2 104.98(11) O(1) -Zn(1) -N(1) #2 120.69(11)
    Bond Dist Bond Dist Bond Dist
    Zn(1) -O(3) #1 1.937(2) Zn(1) -O(1) 1.941(2) Zn(1) -N(1) #2 2.029(3)
    Zn(1) -N(4) 2.081(3) N(1) -Zn(1) #3 2.029(3) O(3) -Zn(1) #1 1.937(2)
    O(3) #1-Zn(1) -N(4) 92.40(11) O(1) -Zn(1) -N(4) 101.85(11) N(1) #2-Zn(1) -N(4) 114.90(11)
    Symmetry transformation: #1: -x+1,-y+1,-z+1; #2: x,y-1,z; #3 x,y+1,z
    下载: 导出CSV

    Table 2.  SelectedBond Lengths (Å)and Bond Angles (°) for 2

    Angle (°) Angle (°) Angle (°) O(1) -Zn(1) -O(2) #1 124.63(12) O(1) -Zn(1) -O(3) #2 136.26(13) O(2) #1-Zn(1) -O(3) #2 99.10(13)
    Bond Dist. Bond Dist. Bond Dist.
    Zn(1) -O(1) 2.023(3) Zn(1) -O(2) #1 2.044(3) Zn(1) -O(3) #2 2.054(3)
    Zn(1) -N(1) 2.156(4) Zn(1) -N(3) #3 2.169(4) Zn(1) -O(4) #2 2.455(4)
    O(1) -Zn(1) -N(1) 90.40(13) O(2) #1-Zn(1) -N(1) 87.71(14) O(3) #2-Zn(1) -N(1) 91.16(14)
    O(1) -Zn(1) -N(3) #3 90.16(14) O(2) #1-Zn(1) -N(3) #3 88.74(14) O(3) #2-Zn(1) -N(3) #3 91.15(14)
    N(1) -Zn(1) -N(3) #3 176.04(13) O(1) -Zn(1) -O(4) #2 79.66(12) O(2) #1-Zn(1) -O(4) #2 155.66(13)
    O(3) #2-Zn(1) -O(4) #2 56.61(12) N(1) -Zn(1) -O(4) #2 90.96(15) N(3) #3-Zn(1) -O(4) #2 93.00(15)
    Symmetry transformation: #1: -x,-y+1,-z+2; #2: x+1/2,y+1/2,z; #3: x,-y+1,z+1/2
    下载: 导出CSV
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  • 收稿日期:  2016-03-24
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