Ni(II) Coordination Polymers Constructed from the Flexible

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Crystal Growth & Design

Ni(II) Coordination Polymers Constructed from the Flexible Tetracarboxylic Acid and Different N-donor Ligands: Structural Diversity and Catalytic Activity Lu Liu, a,b Chao Huang, a Xiaonan Xue, a Ming Li, a Hongwei Hou*, a Yaoting Fan a a

The College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou, Henan, 450001, P. R. China

b

School of Chemistry and Chemical Engineering, Henan Institute of Science and Technology, Xinxiang, Henan, 453003, P. R. China

* To whom correspondence should be addressed. Fax: (86) 371-67761744; E-mail: [email protected]

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ABSTRACT: To seek the effect condition of the complexes on the manufacture of the biaryl compounds,

seven

Ni(II)

complexes,

{[Ni2(L)(dpp)2(H2O)]·4H2O}n

(2),

namely,

{[Ni(L)0.5(bpa)(H2O)]·2H2O}n

{[Ni(L)0.5(pbmb)(H2O)]·H2O}n

(1), (3),

{[Ni2(L)(bmp)2(H2O)]·7H2O}n (4), {[Ni(L)0.5(pbib)1.5]·2H2O}n (5), {[Ni2(L)(pbib)1.5]·3H2O}n (6) and [Ni(L)0.5(beb)2(H2O)]n (7) (bpa = 1,2-bis(4-pyridyl)ethane, dpp = 1,3-di(4-pyridyl)propane, pbmb = 1,1′-(1,3-propane)bis-(2-methylbenzimidazole), bmp = 1,5-bis(2-methylbenzimidazol) pentane, pbib = 1,4-bis(imidazol-1-ylmethyl)benzene, beb = 1,4-bis(2-ethylbenzimidazol-1ylmethyl) benzene), have been gained through hydro(solvo)thermal reactions of 5,5'-(hexane-1,6diyl)-bis(oxy)diisophthalic acid ligand (H4L) with Ni(II) metal ions under the regulation and control of six N-donor ligands. 3-fold interpenetrating complex 1 belongs to a (4,4)-connected 3D bbf net with a vertex symbol of (64·82)(66) topology. 3-fold interpenetrating complex 2 presents a (4,4,4)connected 3D bbf net with a Schäfli symbol of (66)2(64·82) topology. 3 features a (3,4)-connected 3,4L13 topology with a Schäfli symbol of (4·62)(42·62·82) topology. 4 possesses a (4,4,4)-connected mog Moganite 3D network fabric and the vertex symbol is (4·64·8)2(42·62·82). 5 takes on a (4,5)connected architecture and the point symbol is (4·69)(42·66·82). 6 is a (4,7)-connected framework and the Schäfli symbol is (45·5)(47·53·611). 7 has a (4,4)-connected 4,4L28 topology and the Point (Schäfli) symbol is (42·64)(4·64·8). A systematic structural comparison of 1–7 signifies that their frameworks can be regulated through varied conformations of the flexible H4L ligand and divers Ndonor ligands. Between the proximal Ni(II) ions, the variable-temperature (2−300 K) magnetic susceptibilities of 6 display overall weak antiferromagnetic coupling. In the complexes-catalyzed homo-coupling reaction of iodobenzene, 3, 5, 6 and 7 have been verified to be effectual catalysts for the synthesis of the biaryl compounds.

INTRODUCTION


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The biaryl motif is a pivotal building block on account of its universal presence in plentiful biologically significant pharmaceuticals, natural products, materials and agrochemicals.1-3 By means of their outstanding chemical and physical properties, the biaryl moiety can also be widely applied as a meritorious monomeric building block for conductive polymers,4-5 chiral recognition reagents for chromatography6 and a core structure of liquid crystals.7 The development of effective preparation methods for the production of the biaryl has catched the growing attention of investigator. Homo- and cross-coupling reactions are most frequently adopted techniques for the formation of carbon–carbon bond, especially for producing biaryl structures and their heteroaromatic analogues.8 Speaking historically, Ullmann reaction of aromatic halides was the first resultful method to prepare symmetrical biaryls when the metal copper was served as catalysts.9-10 However, these reactions demand the expenditure of equimolar amounts of copper and severe reaction conditions (over 200 °C).11 To develop the milder reaction conditions, multifarious catalysts was introduced to the Ullmann reaction subsequently. In the palladium- or nickel-catalyzed homo-coupling reaction, a reducing agent is indispensable,12 such as carbonic oxide gas,13 hydroquinone(HQ)14 or hydrogen gas.15 Nevertheless, this kinds of metal catalysts accompanying with the reducing agents are not only expensive but venenous. Moreover, the use of Grignard reagent make this reaction moisture-sensitive and not be controlled with ease in oxidative homo-coupling reaction of aryl-metal reagents.16 Meanwhile, the use of the transition metal halides also will make this reaction not green.16 Thus, new businesslike and eco-friendly catalysts for the homocoupling reaction are still required. Of late years, MOFs (metal−organic frameworks) have already appeared on the stage of catalytic field by right of its advantages. Of the plentiful reasonable methods to the project of MOFs, the course of choosing well-designed organic ligands as building blocks has been demonstrated to be an effective strategy with metal ions/clusters as nodes. The coordination chemistry of the ether-linked flexible tetracarboxylic acids ligand 5,5'-(hexane-1,6-diyl)-bis(oxy)diisophthalic acid (H4L) has scarcely been inspected. The interaction between the flexibility and rigidity of the organic constituent may have


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diverse connotations on the shaped lattice.17-21 Thus, H4L is expected to be a puissant precursor in the creation of miscellaneous high-dimensional structures/topologies. First, the ligand H4L can be deprotonated to the homologous carboxylate species (H3L−, H2L2−, H1L3−, and L4−), admiting its various coordination fashions to the inorganic connectors.17-21 Second, the (-CH2-)6 spacers with the flexible nature between the two oxyisophthalic acid fragments will render the carboxyl groups to link to metal ions in disparate directions, furnishing more likelihoods for the architecture of skeletons with versatile topologies and functional properties.22-31 Third, the existence of two methoxy groups will also enhance the flexibility of (-CH2-)6 long chain. Forth, the cooperation of four rotating carboxyl groups and eight freely twisting atoms would afford a directional control at three-dimensional (3D) extensions.32-36 On the other hand, the fully deprotonated modalities of H4L ligand present more negative charge (−4 valence). It is a good approach to adopt neutral N-heterocyclic spacers as secondary coligand to pillar the tetracarboxylate-metal networks and forward structural diversity in establishing multidimensional MOFs. Enlightened by the foregoing discussion, by drawing a series of N-donor coligands (Scheme S1) into the Ni(II)/L4− synthesis system, seven Ni(II) coordination complexes, owning more complicated structures

and

intriguing

topologies,

formulated

as

{[Ni(L)0.5(bpa)(H2O)]·2H2O}n

(1),

{[Ni2(L)(dpp)2(H2O)]·4H2O}n (2), {[Ni(L)0.5(pbmb)(H2O)]·H2O}n (3), {[Ni2(L)(bmp)2(H2O)]·7H2O}n (4), {[Ni(L)0.5(pbib)1.5]·2H2O}n (5), {[Ni2(L)(pbib)1.5]·3H2O}n (6) and [Ni(L)0.5(beb)2(H2O)]n (7) have been achieved to conduct the experiments on the preparation of the biaryl compounds. The structures and topological analyses of 1–7, in conjunction with a systemic research about the influence of different N-donor coligands on the ultima skeletons, will be stated. The thermal stabilities, solvent resistance property and photophysical properties of 1–7 have been inquiried in detail. Moreover, the magnetic susceptibility measurement of 6 has also been performed.

EXPERIMENTAL SRCTION ACS Paragon Plus Environment

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Materials and Physical Measurements. All of the solvents and reagents were commercially practicable. H4L was synthesized in accordance with a revised procedure from reported literature.37 Ligand pbmb, bmp, pbib and beb were manufactured in the light of the literature.38 A Bruker-ALPHA spectrophotometer, which employs KBr pellets, is adopted to record the FT-IR spectra of complexes within 400–4000 cm-1 scale. Thermogravimetric analyses were implemented adopting a Netzsch STA 449C thermal analyzer by a heating speed of 10 ºC min-1 in the air stream. A FLASH EA 1112 analyzer is selected and used for performing the elemental analyses of complexes. XRD patterns of complexes were accomplished on a PANalytical X’Pert PRO diffractometer making use of Cu Kα1 radiation. Diffuse reflectivity spectra of the solid samples were gathered by virtue of a Cary 500 spectrophotometer, which is equipped with a 110 nm diameter integrating sphere. The whole testing is from 200 nm to 800 nm utilizing barium sulfate as a standard. Synthesis Synthesis of {[Ni(L)0.5(bpa)(H2O)]·2H2O}n (1): Weighing 0.2 mmol Ni(OAc)2·4H2O (0.0496 g), 0.1 mmol L (0.0446 g), 0.1 mmol bpa (0.0184 g) and 0.4 mmol NaOH (0.0160 g) into a 25 mL container, then 8 mL distilled H2O was dumped in the mixture. After sealed, the mixture was heated at 130 °C for three days. After gradually cooling, turquoise strip-shaped crystals of 1 were acquired with a yield of 56 % (based on Ni). Anal. Calcd for C23H27NiN2O8 (%): C, 53.31; H, 5.25; N, 5.40. Found: C, 53.29; H, 5.26; N, 5.39. IR (KBr, cm–1): 3425(w), 3331(w), 3135(m), 2936(vw), 2864(vw), 1615(m), 1536(m), 1458(vw), 1399(vs), 1264(vm), 1213(vw), 1124(m), 1049(w), 831(w), 782(s), 725(s), 549(w), 471(s).

Synthesis of {[Ni2(L)(dpp)2(H2O)]·4H2O}n (2): The production process of 2 was analogous to that of 1 except that 0.2 mmol dpp (0.0396g) was used taking the palce of bpa. The green irregular blockshaped crystals of 2 were acquired in a yield of 40 % (based on Ni). Anal. Calcd for C48H56Ni2N4O15 (%): C, 55.09; H, 5.39; N, 5.35. Found: C, 55.06; H, 5.41; N, 5.33. IR (KBr, cm–1): 3428(m), 3129(s), 1617(m), 1547(w), 1413(vs), 1264(w), 1225(w), 1125(w), 1072(w), 1046(w), 914(w), 885(vw), 820(s), 782(vw), 738(vw), 723(vw), 560(w). ACS Paragon Plus Environment

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Synthesis of {[Ni(L)0.5(pbmb)(H2O)]·H2O}n (3): The synthetic process was analogous to 1 except that bpa was substituted by 0.2 mmol pbmb (0.0608 g). The pale yellow-green crystals were gained in a yield of 80 % (based on Ni). Anal. Calcd for C30H33NiN4O7 (%): C, 58.08; H, 5.36; N, 9.03. Found: C, 58.09; H, 5.39; N, 9.01. IR (KBr, cm–1): 3538(w), 3456(m), 3411(m), 3130(m), 2946(vw), 2854(vw), 1665(w), 1614(w), 1558(m), 1541(m), 1459(m), 1396(vs), 1316(w), 1289(w), 1264(w), 1230(w), 1162(w), 1139(w), 1034(m), 991(w), 909(w), 798(w), 730(m), 664(w), 560(w), 512(w), 434(w). Synthesis of {[Ni2(L)(bmp)2(H2O)]·7H2O}n (4): Weighing 0.2 mmol Ni(OAc)2·4H2O (0.0496 g), 0.1 mmol L (0.0446 g), 0.1 mmol bmp (0.0332 g), 0.4 mmol NaOH (0.0160 g) into a 25 mL container, then 4 mL distilled H2O was poured into the mixture. After sealed, the suspension was heated at 160 °C for three days. Cooling the mixture, yellow-green crystals of 4 were achieved in a yield of 34 % (based on Ni). Anal. Calcd for C64H82Ni2N8O18 (%): C, 56.15; H, 6.03; N, 8.18. Found: C, 56.13; H, 6.02; N, 8.21. IR (KBr, cm–1): 3428(m), 3131(m), 2940(w), 2863(w), 1614(w), 1547(s), 1512(vw), 1459(s), 1401(vs), 1290(vw), 1263(w), 1159(w), 1124(w), 1036(w), 928(w), 884(w), 781(s), 743(s), 674(vw), 560(vw), 436(vw). Synthesis of {[Ni(L)0.5(pbib)1.5]·2H2O}n (5): The experimental procedure is akin to that of 1, except that 0.2 mmol pbib (0.0476 g) was used displacing bpa. After cooling the solution, green irregularblock-shaped crystals were separated out (yield, 65 % based on Ni). Anal. Calcd for C32H34NiN6O7 (%): C, 57.07; H, 5.08; N, 12.48. Found: C, 57.09; H, 5.07; N, 12.50. IR (KBr, cm–1): 3429(m), 3137(m), 2937(w), 2869(w), 1627(s), 1587(w), 1547(w), 1519(w), 1457(w), 1444(w), 1375(vs), 1319(w), 1263(m), 1232(w), 1107(w), 1089(w), 1031(m), 938(w), 909(w), 889(w), 834(w), 781(s), 728(s), 659(w), 618(w), 560(w), 461(w). Synthesis of {[Ni2(L)(pbib)1.5]·3H2O}n (6): Weighing 0.2 mmol Ni(OAc)2·4H2O (0.0496 g), 0.1 mmol L (0.0446 g), 0.1 mmol pbib (0.0238 g), and 0.4 mmol NaOH (0.0160 g) into a 25 mL container, then a mixed solution of 8 mL EtOH/H2O (v:v = 1:3) was added in the mixture. After heating at 160 °C for three days in a closed vessed and cooling it, green irregular-shaped crystals were segregated from 6 ACS Paragon Plus Environment

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mother solution (yield, 62 % based on Ni). Anal. Calcd for C43H45Ni2N6O13 (%): C, 53.17; H, 4.67; N, 8.65. Found: C, 53.16; H, 4.69; N, 8.64. IR (KBr, cm–1): 3430(m), 3137(m), 2930(w), 2870(w), 1628(m), 1588(w), 1518(w), 1455(w), 1320(w), 1263(w), 1232(w), 1116(w), 1089(w), 1031(w), 937(w), 834(w), 781(s), 727(s), 659(w), 617(w), 560(w), 462(w). Synthesis of [Ni(L)0.5(beb)2(H2O)]n (7): The experiment is parallel to that of 1 except that 0.2 mmol beb (0.0788 g) was used in place of bpa. After cooling the final mixture, green strip-shaped crystals of 7 were achieved in a yield of 67 % (based on Ni). Anal. Calcd for C37H37NiN4O6 (%): C, 64.18; H, 5.38; N, 8.09. Found: C, 64.17; H, 5.39; N, 8.10. IR (KBr, cm–1): 3431(m), 3128(m), 2979(w), 2939(w), 1614(m), 1546(s), 1515(w), 1455(s), 1401(s), 1316(w), 1287(w), 1256(w), 1214(w), 1160(w), 1120(w), 1069(w), 1048(w), 1015(w), 973(w), 894(w), 849(s), 806(w), 781(s), 753(s), 736(s), 716(w), 615(w), 560(w), 488(w), 450(w), 407(w). Crystal Data Collection and Refinement. The collections of crystallographic data of the 1–7 were fulfilled at indoor temperature adopting a Rigaku Saturn 724 CCD diffractomer, which was equipped with Mo-Kα radiation (λ = 0.71073 Å). Utilizing multi-scan program, absorption corrections of these data were enforced. In the light of Lorentz and polarization effects, these data were corrected. The structures of 1–7 were handled by firsthand methods, and then refined by means of F2 with a full-matrix least-squares technique.39 All the non-hydrogen atoms were anisotropically refined. While the hydrogen atoms of H4L, which were assigned at perfect positions, were isotropically refined. For complex 1–7 and complex 6 under specific conditions, the results of their X-ray analyses are summed up in Table S1 (in the Supporting Information). Bond lengths and bond angles under selection of 1–7 and 6 under specific conditions are included in Table S2. For 1−7: CCDC reference numbers 1052514–1052520. For 6-H2O: CCDC reference numbers 1052521. Solvent Resistance Experiment. The experiment was researched by suspending the samples in boiling frequently-used solvents for forty-eight hours. In this process, the samples were supervised


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under a optical microscope. Then, the samples were embathed with water and dried spontaneously. The X-ray diffraction was engaged to fulfill the measurement of the unit-cell parameters. Magnetic Experiment. Under the applied field of 1 kOe, the magnetic susceptibilities (χMT-T and χM−1-T) were carried out on a SQUID MPMS XL-7 instrument in the temperature region of 2−300 K. With the help of Pascal’s constants, we also execute the diamagnetic corrections for the magnetic data of 6.40 A general procedure of the preparation of the biaryl compounds with catalysts 1–7.16 Iodobenzene (0.5 mmol), catalyst (0.05 mmol, complexes 1–7) and magnesium ribbon (0.6 mmol) were mixed together and refluxed in anhydrous tetrahydrofuran (2 mL) under dry air. After 6 h, the cool reacting solution was filtrated and the dilute hydrochloric acid (0.5 N, 10 mL) was added into filtrate. Then extracted with acetic ether, the united organic layers was washed with water, then dried by anhydrous sodium sulfate, filtered, concentrated in vacuo. The raw product was purified by column chromatography on silica gel with hexane. Column chromatography was implemented with 200–300 mesh silica gel. 1H NMR spectra were taken notes on 400 MHz instrument. (In the supporting information)

RESULTS AND DISCUSSION Crystal Structure of {[Ni(L)0.5(bpa)(H2O)]·2H2O}n (1): The asymmetric unit of 1 comprises one crystallographically independent Ni(II) ion, one bpa ligand, half a L anion, one coordinated water molecule as well as two lattice water molecules (Figure S1a). Ni1 ion is six coordinated with coordination geometry of octahedron, which is fulfilled by two oxygen atoms (O1 and O2) originating from one µ1-η1:η1-chelate carboxylate, one oxygen atom (O5A) supplied by one monodentate carboxylate, and one nitrogen atom (N1) of bpa ligand forming the equatorial plane, and one oxygen atom (O3) of coordinated water molecule as well as one nitrogen atom (N2B) of bpa ligand that is situated in the axial positions with an O3−Ni1−N2B bond angle of 172.80(1) °. The Ni–O bond ACS Paragon Plus Environment

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distances vary from 2.047(3) to 2.255(3) Å, while the Ni1–N1/N2B bond lengths are 2.052(3)/2.081(3) Å, severally. There exist five torsion angles of 168.5(1) °, -147.6(1) °, -60.5(2) °, -51.6(2) ° and -58.9(2) ° along the C chain and ether bond in the H4L. The completely deprotonated H4L in 1 exhibit one coordination mode: (κ1)-(κ2)-(κ1)-(κ2)-µ4 (Mode I), as shown in Scheme S2. In this mode, two carboxylate groups take chelating bidentate coordination modes, and the other two carboxylate groups show the monodentate fashions. On the basis of the connection mode, each Ni(II) ion is joined by L4− anions into a 2D net with left- and right-handed helical chains, which are arranged alternately running along bc plane (Figure 1a). Both of them have a pitch of 17.606(4) Å, which is in perfect accordance with the length of b-axis. The 1D infinite zigzag chain (Ni(II)/bpa chain) along the crystallographic c-axis is manufactured by the anticonformational bpa spacers with a C−C−C−C torsion angle of 179.39 ° and Ni(II) ions carrying a Ni···Ni distance of 13.3391 Å (Figure S1b). The Ni(II)/L4− nets are pillared by 1D chains of Ni(II)/bpa via the Ni−N connections to produce a 3D framework with large channels (16.49 Å × 18.63 Å) along the c axis (Figure 1b). To stabilize the overall framework and minimize the big hollow cavities in 1, the large chamber facilitates other two independent equivalent networks to interpenetrate, triggering the creation of a 3-fold interpenetrated skeleton (Figure 1c). Topologically, the Ni1 cation can be clarified as a 4-connected node, that is connected to four equivalent nodes by means of two bpa ligands and two L4− anions. Each L4− anion links with four Ni(II) atoms, so the L4− can be identified as a 4-connected node. Moreover, the bpa is simplified as linear linkers. Accordingly, the whole structure of 1 is related to a (4,4)-connected bbf net with a vertex symbol of (64·82)(66) (Figure 1c). Crystal Structure of {[Ni2(L)(dpp)2(H2O)]·4H2O}n (2): The two unique nickel cations including Ni1 and Ni2 (entire site occupancy, severally) are all situated in distorted octahedral coordination geometries (Figure S2a). Ni1 ion is ligated by O1, O2, O3B, O4B atoms from two distinct µ1-η1:η1-chelate carboxylates (Ni1−O distances: 2.002(1)−2.281(2) Å) and N1, N2A atoms from two separate dpp 9 ACS Paragon Plus Environment


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ligands (Ni1−N1 = 2.034(2), Ni1−N2A = 2.027(2) Å). The O2, O3B, O4B and N2A atoms comprise the equatorial plane, and the O1 and N1 atoms occupy axial positions. The bond angles around Ni1 range from 61.11(5) to 159.92(5) °. Ni2 ion is equatorially surrounded by O7, O8 atoms from one µ1-η1:η1chelate carboxylate (Ni2−O7 = 2.097(2), Ni2−O8 = 2.152(2) Å), one oxygen (O9C) from one monodentate carboxylate (Ni2−O9C= 2.049(1) Å), and N3 atom from dpp ligand (Ni2−N3 = 2.056(2) Å). The two axial sites on the metal are occupied by one N atom (N4D) from one dpp ligand (Ni2−N4D = 2.085(2) Å) and one terminal water oxygen atom (O11) (Ni2−O11 = 2.128(2) Å). The bond angles around Ni2 range from 61.52(6) to 179.29(7) °. Two different kinds of dpp ligands (namely, dpp-I and dpp-II) exist in 2, both of them exhibits TT (T = trans) conformation in the case of the counter orientations of the -CH2- groups. The dpp-I coordinates to Ni1(II) centers to generate a 1D left-handed helical chain with a pitch of 16.951(3) Å, while Ni2(II) centers are joined by dpp-II to engender a 1D right-handed helical chain that own the same pitch (Figure 2a). Passing its four carboxylate groups, each L4− acts as a µ4-bridge to connect four Ni(II) ions and the coordination mode of (κ2)-(κ1)-(κ2)-(κ2)-µ4 (Mode II of Scheme S2) for L4− is found in complex 2. The linkage of L4− anions and Ni(II) cations provide a 2D Ni-L backbone along the bc plane (Figure 2b). Due to the flexibility of L ligands, there exists left- and right-handed helical chains in the 2D Ni-L backbone of 2. Their screw axes are also all parallel with the b axis, in addition, the pitch is also 16.951(3) Å. These 2D Ni-L networks are connected together by sharing the Ni(II) atoms with 1D Ni(II)-dpp chains to furnish a 3D metal−organic framework containing the cavities (Figure 2c). Three such nets are interwoven into a 3-fold interpenetrated 3D structure (Figure 2d). Through the above description, we can see that Ni1 atom and Ni2 atom can be perceived as a 4connected node, respectively, which link to two L4− ligands and two dpp ligands, severally. Each L4− can be also reduced to a four-connected node, which connects two Ni1 atoms and two Ni2 atoms, and the dpp ligand can be considered to be a linear linker. Ultimately, the 3D networks of 2 can be depicted as a (4,4,4)-connected bbf network with a Schäfli symbol of (66)2(64·82) (Figure 2d). ACS Paragon Plus Environment

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Crystal Structure of {[Ni(L)0.5(pbmb)(H2O)]·H2O}n (3): Delineated in Figure S3a, the Ni center is bonded to three oxygen atoms belonging to two separated L4− ligands, one oxygen atom (O6) from one coordinated water molecule, as well as N1 atom and N3 atom from two pbmb ligands to generate a distorted octahedral coordination geometry. The distances of Ni1–N1/N3 are 2.115(3)/2.062(3) Å, while the Ni1–O bond lengths range from 2.031(2) to 2.166(2) Å. In 3, the pbmb adopts asymmetrical trans-conformation with two disparate Ndonor···N−Csp3···Csp3 torsion angle of 89.204 º and 103.643 º. Ni1 and symmetry-related Ni1B (1-x, 2-y, 1-z) are concatenated by two pbmb ligands forming a [Ni(pbmb)]2 unit with a 16-membered metallorings (Figure 3a). The bridged Ni···Ni distance along µ-pbmb is 9.932 Å. The L4− anions connects four Ni(II) cations in a (κ2)(κ1)-(κ2)-(κ1)-µ4 coordination mode (Mode III of Scheme S2). In this mode, four carboxylic groups behave as µ1-η1:η1, µ1-η1:η0, µ1-η1:η1 and µ1-η1:η0 modes in a clockwise direction, separately. On account of this coordination mode, the L4− anion works as a bridging ligand to bind the Ni(II) ions building a 1D ladder chains along the c direction (Figure 3b). The Ni(II) ions of two contiguous 1D Ni(II)/L4− chains were connected by the trans-conformational pbmb effecting the 2D sheet of 3 parallel to the ac crystal face (Figure 3c). Based on the above, each L4− links four Ni(II) atoms, and so, the L4− can be deemed as a 4-connected node. As for each Ni(II) atom, it links two L4− and one [Ni(pbmb)]2 unit, hence, the Ni(II) atom is reckoned as a 3-connector. Allowing for the simplification principle, the structure of 3 is a (3,4)connected 3,4L13 topology, and the point symbol is (4·62)(42·62·82) (Figure 3d). Crystal Structure of {[Ni2(L)(bmp)2(H2O)]·7H2O}n (4): As illustrated in Figure S4a, the Ni1 ion is located in an octahedral coordination environment, that is anchored by one oxygen (O1) from one monodentate carboxylate (Ni1−O1 = 2.114(2) Å), two oxygens (O3, O4) from one µ1-η1:η1-chelate carboxylate (Ni1−O3 = 2.114(2), Ni1−O4 = 2.121(3) Å), one O5 atom of coordinated water molecule (Ni1−O5 = 2.068(2) Å) and N1, N5 atoms from two bmp ligands (Ni1−N1 = 2.056(3), Ni1−N5 = 2.136(3) Å). The axial positions are padded with O1 and N5 with an O1−Ni1−N5 bond angle of 11 ACS Paragon Plus Environment


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172.59(1) °. Ni2 also takes on a distorted octahedral coordination geometry, nevertheless, which is coordinated by four carboxylic oxygen atoms (O6C, O7C, O8 and O9) from two unlike L ligands (Ni2−O6C = 2.061(2), Ni2−O7C = 2.243(2), Ni2−O8 = 2.104(2), Ni2−O9 = 2.144(2) Å) and two nitrogen atoms (N4A, N8B) from two bmp ligands (Ni2−N4A = 2.044(3), Ni2−N8B = 2.048(3) Å). The bond angles around Ni2 ions fall in the range of 60.87(9)−168.96(9) º. There are two independent bmp ligands in 4. The first type (bmp-I) adopts asymmetric cisconformation, and two diverse Ndonor···N−Csp3···Csp3 torsion angles is 95.176 º and 115.858 º, singly. The

second

type

(bmp-II)

adopts

asymmetric

trans-conformation,

and

two

distinct

Ndonor···N−Csp3···Csp3 torsion angles is 73.812 º and 86.517 º, severally. Ni1(II) and Ni2(II) atoms are alternately joined by the two bmp to give a 36-membered macrocyclic rings with Ni1···Ni2 separation of 11.441(3) Å across the bridging bmp-I and 12.030(4) Å across the bridging bmp-II, singly (Figure 4a). The L ligand possesses one coordination mode (Mode IV of Scheme S2): (κ2)-(κ2)-(κ1)-(κ2)-µ4 to coordinate with four Ni2+ cations through four carboxyl oxygen atoms. The three carboxyl groups of them all adopt chelating bidentate coordination modes, the forth one in a monodentate coordination pattern. The Ni(II) atoms are concatenated by L4− anions to yield a 1D parallelogram channel with the dimensions of approximately 9.2 × 10.4 Å2 (including van der Walls radii of the atoms) (Figure 4b). The expansion of 4 into a 3D net is also implemented by linking 36-membered metallorings through 1D parallelogram channels (Figure 4c). Topology analysis of 4 is executed. we can consider each L4− anion as a 4-connecting node, that is jointed to four isovalent nodes through two Ni1 cations and two Ni2 cations. The Ni1 and Ni2 cations can be also considered as 4-connected nodes, severally, which are connected to four equivingcoholnt nodes through two L4− anions and two bmp ligands, singly. Moreover, the bmp-I and bmp-II are reduced to linear linkers, separately. Eventually, the entire structure of 4 can be supposed to be a (4,4,4)connected mog Moganite net, and the vertex symbol is (4·64·8)2(42·62·82) (Figure 4d).


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Crystal Structure of {[Ni(L)0.5(pbib)1.5]·2H2O}n (5): As painted in Figure S5a, the Ni(II) atom sits in a twisty octahedral coordination geometry with NiO2N3 coordination environment, that is defined by N1, N3 and N5 atoms from three pbib ligands and O1, O2 and O3A atoms from two different L4− ligands. The variation range of Ni−O bond separations is from 2.048(2) to 2.266(2) Å, while that of Ni−N bond lengths is from 2.063(2) to 2.105(2) Å. There are three classes of standalone pbib, and all of them present symmetrical trans-conformation. Ndonor···N−Csp3···Csp3 torsion angles of pbib-I, pbib-II and pbib-III are 50.921 º, 68.585 º and 81.220 º, separately. The three types of pbib behave as bidentate mode to connect with two proximal Ni(II) ions alternately to provide a 2D net along the a-axis (Figure 5a). The Ni···Ni distances across the pbib-I, pbib-II and pbib-III bridges are 13.384 (pbib-I), 13.785 (pbib-II) and 14.083 (pbib-III) Å, seperately. The L ligand in 5 takes on one coordination mode (Mode V of Scheme S2: (κ1)-(κ2)-(κ1)-(κ2)-µ4) to coordinate with Ni2+ cations via six carboxyl oxygens, and four carboxyl groups of them adopt µ1-η1:η0, µ2-η1:η1, µ1-η1:η0 and µ2-η1:η1 coordination modes, severally. The neighboring Ni(II) atoms are jointed by the L ligand leading to the formation of a 1D ladder chain along the a direction (Figure 5b). The Ni/pbib 2D layers and the Ni/L4− 1D chain are held together by sharing the Ni(II) atoms, resulting in a 3D architecture (Figure 5c). Topologically, each Ni(II) ion is encircled by three pbib ligand and two L4− ligands, and each L4− is linked with three Ni(II) ions. If the Ni(II) ion is perceived as a 5-connector, the L4− can be predigested as 4-connected nodes and pbib is taken for linkers, the 3D skelecton of 5 can be classified as a (4,5)connected new topology and the point symbol is (4·69)(42·66·82) (Figure 5d). Crystal Structure of {[Ni2(L)(pbib)1.5]·3H2O}n (6): 6 presents an elegant (4,7)-connected 3D network. Figure S6a illuminates the coordination surroundings of the Ni(II) ions. The Ni1(II) ion and Ni2(II) ion both adopt distorted octahedral coordination environments in nature. The Ni1(II) ion is bound with O1, O4, O5B, O6B and O9A, which derives from four L4− anions as well as one nitrogen atom (N1) coming from one separate pbib. The Ni1−O bond separations vary from 2.015(3) to 2.145(2) 13 ACS Paragon Plus Environment


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Å, while the Ni1−N1 bond length is 2.060(3) Å. Different from Ni1, the Ni2(II) ion is surrounded by four carboxyl oxygen atoms (O1, O2, O3 and O8A) originating from three L4− anions and N3, N5 atoms from two pbib. The length range of Ni2−O bonds is from 2.028(3) to 2.288(2) Å, nevertheless, the lengths of Ni2−N3 and Ni2−N5 bonds are 2.104(3) Å and 2.052(3) Å, separately. In this structure, the L4− ligand acts as a seven-connector to link seven Ni atoms with the (κ1-κ1)-(κ2κ1-µ2)-(κ1-κ1)-(κ2)-µ7 coordination mode (Mode VI of Scheme S2), in which four carboxyl groups adopt syn-anti-µ2-η1:η1, µ2-η2:η1, syn-anti-µ2-η1:η1 and µ1-η1:η1 coordination modes, severally. Ni1 and Ni2 ions are joined together through two µ2-η2:η1 bridging carboxylate groups and one µ2-η2:η1 bridging carboxylate group to furnish a binuclear [Ni2(CO2)3] SBU. The intermetallic distance of Ni1···Ni2 is about 3.440 Å within the subunit. The binuclear [Ni2(CO2)3] units are expanded by the L4− ligands to form a 2D layer containing 1D chanels with the dimensions of roughly 8.7 × 9.9 Å2 (Figure 6a). Similar to 5, there are also three kinds of freestanding pbib, all of which also show symmetrical transconformation, while Ndonor···N−Csp3···Csp3 torsion angles of pbib-I, pbib-II and pbib-III are 56.823 º, 119.089 º and 138.234 º, singly. The two adjoining Ni2(II) ions are bridged by pbib-I and pbib-III to induce a 1D meso-helix chain (Figure 6b). The helical pitch is 10.063(2) Å, which is related to the length of b-axis. Moreover, the Ni2···Ni2 separations across the pbib bridges are 12.576 (pbib-I) and 15.461 (pbib-III) Å, seperately. Meantime, the pbib-II links the Ni1(II) ions with a Ni1···Ni1 separation of 14.883 Å acrossing in the middle of the aboved 1D channels. The complicated 3D framework of 6 was constructed through the combination of the 1D meso-helix chains Ni2(II)-(pbib-I)-(pbib-III) and the Ni(II)-L4− 2D nets (Figure 6c). Based on the concept of topology, the binuclear SBU can be deemed to be a seven-connected node, linking with three pbib ligands and four L4− anions. The L4− ligand links four binuclear SBUs. Thus, the L4− ligand is considered as a 4-connected node. The final 3D skeleton exhibits a binodal (4,7)-connected new topology, and the Schäfli symbol is (45·5) (47·53·611) (Figure 6d).


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Crystal Structure of [Ni(L)0.5(beb)2(H2O)]n (7): 7 is a 2D bilayer network. As demonstrated in Figure S7a, the octahedral coordination around Ni1 is supplied by three carboxylate oxygens (O1, O2 and O5A) from two different L4− moieties (Ni1−O1 = 2.151(2); Ni1−O2 = 2.104(2); Ni1−O5A = 2.067(2) Å) and O3 atom from coordinated water Ni1−O3 = 2.068(2) Å) generating the square base, and the axial coordination is endowed by N1 and N3 atoms from two beb ligands (Ni1−N1 = 2.101(3); Ni1−N3 = 2.125(3) Å). The L4− anions connects four Ni(II) cations, where two carboxylate groups take µ1-η1:η1 coordination modes, the other two carboxylate groups adopt µ1-η1:η0 fashions (Mode VII of Scheme S2). By this way, the Ni(II) atoms are jointed by the L4− anions to generate a 1D ladder-like chain propagating along ab plane (Figure 7a). There are one independent beb ligand in 7. The beb adopts asymmetric transconformation, and two disparate Ndonor···N−Csp3···Csp3 torsion angles are 80.554 º and 109.185 º, severally. The Ni1(II) ions are bridged by this type of beb to product a 1D zigzag chain stretchting along the c-axis (Ni···Ni distance: 14.241 Å) (Figure 7b). The Ni(II)/L4− 1D ladder-like chain and 1D Ni(II)/beb chain connect each other through sharing the common Ni(II) ions to result in the formation of a 2D bilayer net (Figure 7c). Topologically, the Ni(II) can be perceived as a 4-connected node since it links two L4− ligands and two beb ligands, at the same time, the L4− ligand can be seen as a 4-connector by connecting four Ni(II) atoms. Thus, the resulting structure of 7 is accounted as a (4,4)-connected net with its Point (Schäfli) symbol of (42·64)(4·64·8), that is fingered as 4,4L28 topology (Figure 7d). Effects of the Coordination modes of the L4− anion on complexes 1–7. On the strength of the upper structure descriptions, we find that the L4− anion can adopt various of coordination modes, linking to four (complexes 1–5, 7) or seven (complex 6) metal ions. In 1–5 and 7, each L4− anion all connects four Ni(II) ions corresponding to Mode I–V and VII, severally (Scheme S2). Different from 1–5 and 7, each L4− anion in 6 links with seven Ni(II) ions corresponding to Mode ACS Paragon Plus Environment

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VI (Scheme S2). The structural diversities of 1–7 can be vested in the divergent coordination modes of carboxylate groups and the discrimination of distortion degree of flexible chain in the H4L molecule. For 1, 3, 5 and 7, the carboxylate group of L4− all bind with the central metals via a (κ1)-(κ2)-(κ1)-(κ2)µ4 fashion. Different from each other, this kind of coordination fashion in 1 causes the appearance of a 2D Ni-L4− net with helical chains; that in 3 brings about the generation of a 1D Ni-L4− ladder chain with 19.494 Å Ni···Ni distance across 38-membered rings composing of two L4− and two Ni(II) ions; that in 5 afford a 1D Ni-L4− ladder chain with 14.492 Å Ni···Ni distance across 38-membered rings comprising of two L4− and two Ni(II) ions; that in 7 induces the appearance of 1D Ni-L4− ladder chain with 13.632 Å Ni···Ni distance across 38-membered rings making up of two L4− and two Ni(II) ions. For 2 and 4, the carboxylate group of L4− both coordinate with the central metals via a (κ2)-(κ2)-(κ1)-(κ2)-µ4 fashion. This type of coordination fashion in 2 gives rise to the presence of a 2D Ni-L backbone accompanying with helical chains; while that in 4 results in a 1D parallelogram channel. For 6, the carboxylate group of L4− anion links with seven Ni(II) ions through the (κ1-κ1)-(κ2-κ1-µ2)-(κ1-κ1)-(κ2)-µ7 coordination mode forming a 2D layer containing 1D chanels. Effects of the N-donor ligands on the frameworks of complexes 1–7. The N-donors wield a profound influence on the eventual structures of the complexes. The anticonformational bpa spacers in 1 bridge Ni(II) ions to come into being a 1D infinite zigzag chain. The Ni(II)/bpa chain serves as pillars, linking the neighbouring Ni(II)/L4− nets into a 3-fold interpenetrated 3D framework with a vertex symbol of (64·82)(66). For 2, two different kinds of dpp ligands I and II act as bidentate ligands coordinating to Ni (II) ions, singly. The dpp-I bridges Ni1(II) centers to offer a 1D left-handed helical chain, while dpp-II bridges Ni2(II) centers to furnish a 1D right-handed helical chain. The 2D Ni-L networks in 2 are tied together by sharing the Ni(II) centers with 1D Ni(II)-dpp chains to yield a 3-fold interpenetrated 3D skeleton, and the Schäfli symbol is (66)2(64·82). The pbmb adopting asymmetrical trans-conformation in 3 link Ni1 atom as well as symmetry-related Ni1B (1-x, 2-y, 1-z) atom affording a [Ni(pbmb)]2 unit following a 16-membered metallorings. The Ni(II) ions of two 16 ACS Paragon Plus Environment

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adjoining 1D Ni(II)/L4− chains were connected toghther by the trans-conformational pbmb supplying a 2D sheet with point symbol of (4·62)(42·62·82). For 4, Ni1(II) and Ni2(II) atoms are alternately bridged by the two classes of bmp (bmp-I and bmp-II) to lead to a 36-membered macrocyclic rings, which combine with 1D Ni-L parallelogram channels to result in a 3D network with a vertex symbol of (4·64·8)2(42·62·82). For 5, the three types of pbib (pbib-I, pbib-II and pbib-III) behave as bidentate mode to joint two contiguous Ni(II) ions alternately to afford a 2D net. The Ni/pbib 2D layers are connected by Ni/L4− 1D chain inducing a 3D architecture with point symbol of (4·69)(42·66·82). In 6, there are also three kinds of independent pbib (pbib-I, pbib-II and pbib-III). The two adjoining Ni2(II) ions are bridged by pbib-I and pbib-III to produce a 1D meso-helix chain. At the same time, the pbib-II links the Ni1(II) ions acrossing in the middle of 1D channels that are included in the Ni-L 2D layer. The combination of the 1D meso-helix chains Ni2(II)-(pbib-I)-(pbib-III) and the Ni(II)-L4− 2D nets constructs a complicated 3D framework with the Schäfli symbol of (45·5)(47·53·611). In 7, transconformational beb ligand coordinates with Ni1(II) atoms into 1D chain. The combination of the 1D Ni(II)/beb chain and 1D Ni(II)/L4− chain leads to a 2D bilayer net. Analyses of Thermal Stability. To assess the stability of the architectures 1–7, thermogravimetric analyses were executed in the temperature range of 30−800 °C under air atmosphere (Figure S9) (Supporting Information). For 1, the mass loss of 9.70% happening between 39 and 137 °C could be affiliated to the release of one coordinated water molecule and two guest water molecules (calcd 10.42%). The weight loss from 312 to 484 °C corresponds to the losses of bpa and L4−, leading to the NiO residue of 16.49% (calcd, 14.41%). The TG curve of 2 exhibits the mass loss of 6.40% from 38 to 144 °C, which is probably because of the release of four guest water molecules (calcd 6.88%). The weight loss occurring between 374 and 446 °C could be assigned to the decomposition of the organic ligands and one coordinated water, accompanying with the NiO residue of 16.25% (calcd, 14.27%). Complex 3 lost the weight of 5.9% ranging from 119 to 218 °C, that can be attributed to the departure of one coordinated water molecule (calc. 5.8%). The ACS Paragon Plus Environment

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removal of organic components took place at 326 °C, finally, giving NiO residue of 12.78% (calcd, 12.04%) at 515 °C. Complex 4 presents that the weight loss of 8.99% from 36 to 163 °C is interrelated to the loss of seven lattice water molecules (calcd, 9.21%). The entire skeleton of 4 starts to decompose from 346 to 492 °C, that is parallel to the decomposition of one coordinated water and bmp as well as L4−, and the NiO residue of 11.01% (calcd, 10.91%) is observed. The TGA curve of 5 displays the weight loss process of 5.49% from 74 to 137 °C, that corresponds to the decomposition of two isolated water molecules (calcd, 5.35%). The second step weight loss occurs in the range of 374−506 °C, corresponding to the decomposition of pbib and L4−. A residue of NiO (obsd, 12.10%, calcd, 11.09%) is discovered. For 6, the TGA manifests a weight loss of 5.83% from 39 to 158 °C that involved the release of three lattice water molecules (calcd, 5.56%), afterwards, a plateau region is sighted. Eventually, the overall skeleton of 6 gets down to decompose from 363 °C, and the NiO residue of 16.81% (calcd, 15.38%) is observed at 491 °C. The TG curve of 7 reveals the mass loss of 2.30% ranging from 172 to 222 °C, that potentially ascribes to the departure of one coordinated water molecule (calc. 2.60%). The skeleton of 7 began to disassemble at 332 °C, then the NiO residue of 10.87% (calcd, 10.79%) is detected at 571 °C. Magnetic Properties Measurements. For the magnetisms of these samples, we mainly study the magnetic coupling interactions between metal ions. The structure of 6 includes the binuclear [Ni2(CO2)3] SBU, and the intermetallic distance of Ni1···Ni2 is about 3.440 Å within the bimetallic subunit. Judging from this, the magnetic coupling interactions between metal ions are strong in 6. Therefore, we only investigate the magnetic susceptibility of powdered sample 6 in the range of 2−300 K under a 1 KOe applied magnetic field, and discuss the magnetic coupling interactions between Ni(II) ions. Its magnetic behaviors are demonstrated in Figure S10. At 300 K, the χMT values of 6 are 2.57 cm3 K mol−1, that is somewhat larger than the spin-only value (2.00 cm3 K mol−1, g = 2.0 and S = 1) anticipated for high-spin [Ni(II)]2 ions. This disparity might be induced by the spin-orbit coupling characteristic of nickel(II) complexes with an 3A2g ACS Paragon Plus Environment

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ground state leading to an increasing g factor.41-44 With the temperature descends, the value of χmT decreases sequentially to 0.64 cm3 K mol-1 at 2 K, manifesting regnant antiferromagnetic interactions between the Ni(II) ions linked by carboxylate bridges within the dinuclear cluster. The plot of χm-1 versus T for 6 adheres to the Curie–Weiss law of 1/χM = (T − θ)/C in the temperature range of 2–300 K, with the Curie constant C = 2.59 cm3 K mol-1 and the Weiss constant θ = –2.51K. Carefully looking into the structure of 6, the magnetic exchange pathways between dimeric Ni(II) ions for 6 have been found, which comprises two syn–anti carboxyl bridge (Ni-OCO-Ni) and one µ2Ocarboxyl bridge with the exchange angle Ni-Ocarboxyl-Ni of 111.129 º between Ni1 and Ni2. To quantitatively evaluate the magnetic interactions in 6, the magnetic data were analyzed by way of the presentation for a dinuclear Ni(II) system (S1 = S2 = 1) evolved from the isotropic spin Hamiltonian H = -2JΣS1S2 with the effect of synergy of zero-field splitting not considered and the interaction between adjacent dinuclear units taken into account.45-49

χd =

χm =

2 Ng 2 β 2 exp(2 J / kT ) + 5 exp(6 J / kT ) [ ] kT 1 + 3exp(2 J / kT ) + 5exp(6 J / kT )

χd 1 − χ d (2 zJ '/ Ng 2 β 2 )

The prime fitting parameters are J = –1.02 cm-1, zJ′ = –0.01 cm-1, g = 2.27, and R = 2.31 ×10-4. These results sustain the manipulation of a weak intradimer antiferromagnetic interaction as well as very weak inter-dimer interaction in 6. Photophysical Properties and Optical Band Gaps. Several coordination architectures have been certified to be towardly semiconductors in the former literature.50 Illuminated by these files, we inspected the conductivity potentials of complexes 1–7. As depicted in Figure 8, diffuse-reflectance UV-vis spectrum of the H4L displays two doughty absorption bands (λmax = 257 nm, 4.82 eV; λmax = 328 nm, 3.78 eV) in the range of 200–400 nm, that are assigned to


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the typical π→π* transitions.51-54 Besides, the UV-vis absorption spectra of these N-donor coligands manifest stronger absorption bands and the maxima is less than 300 nm (4.13 eV), such as 205, 245 and 283 nm for bpa, 202 and 245 nm for dpp, 208 and 255 nm for pbmb, 205 and 251 nm for bmp, 240 and 257 nm for pbib, and 211 and 294 nm for beb in the scale of 200–400 nm. In the light of the relevant literatures,55-59 the absorption bands of all the free N-donor ligands are attributable to the π→π* transitions of the aromatic rings, severally. As pictured Figure 9, 1–7 show the analogous absorption bands with maxima more than 600 nm (2.06 eV), which can be principally ascribed to the d-d transition of Ni(II) ion. According to method in the literatures,60-64 we obtain the plot of Kubelka−Munk function F versus energy E and assess the band gaps (Eg) of 1–7 (Figure S11). The Eg values are 1.23 eV for 1, 1.13 eV for 2, 1.09 eV for 3, 1.17 eV for 4, 1.20 eV for 5, 1.25 eV for 6 and 1.19 eV for 7, singly. The smaller Eg values are in favour of the electron transition, which may be beneficial to catalysis. The Catalytic Capacity. The homo-coupling reaction of aryl halides represent vigoroso synthetic methods for symmetrical biaryls and play momentous roles on fine chemical and pharmaceutical industries.65-70 To date, the complexes as heterogeneous catalysts has almost not been reported in the Ullmann reaction. Herein, we study the complexes-catalyzed homo-coupling of iodobenzene under the condition of existence of metallic magnesium. Compared with orthodox catalysts for this reaction, the introduction of the metalcomplexes catalysts will bring some advantages, such as the lower amount of catalyst, mild reaction conditions, non-poisonous, environmental friendliness. Because 1 and 2 are both 3-fold interpenetrated networks, which are of no advantage to this reaction. While the crystal yield of 4 is a little low. Accordingly, complexes 1, 2 and 4 will not be the candidate of suitable catalysts. To research the catalytic activity of complexes, we need verify their stable existence in common solvent. Hence, the analyses of solvent resistance property are carried out in the first place. The chemical resistance of complexes 3, 5, 6 and 7 was interrogated via suspending these samples in boiling N,N’-dimethyl formamide, acetonitrile, tetrahydrofuran, ethanol, methanol and water for about 48 h by 20 ACS Paragon Plus Environment

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following representative industrial chemical processes. In the interval, the crystal samples were spied under a microscope in cycles. For 3, it could keep its original shape not only in the water, but also in acetonitrile. 5 is superior to 3 for it could preserve its original shape in N,N’-dimethyl formamide, acetonitrile and water. While 6 could save its original shape in ethanol, acetonitrile and water. What’s particularly attractive is that 7 conveyes preeminent chemical resistance to those solvents mentioned above except for boiling methanol. X-ray diffraction indicated that their unit-cell parameters well-nigh did not change (Table S3). Perceptibly, their primal frameworks were integrated and unbroken. It is strange that this four complexes all could not store in boiling methanol. The outstanding chemical resistance of 7 in refluxing water as well as ecumenical organic solvents is passably assigned to the existence of two-dimensional bilayer, which could be in favour of the stability of the skeletons. Finally, we survey the catalytic activity of the complexes 3, 5, 6 and 7 in detail and find that they are effective catalysts for the homo-coupling of iodobenzene. The catalytic results of 3, 5, 6 and 7 are listed in Table 1. They give a conversion of 49 %, 51 %, 44 % and 48 % for biphenyl compounds, severally. This situation show that 3, 5, 6 and 7 have catalytic activities for the synthesis of the symmetric biphenyl compounds. In 3, although the Ni(II) ions are six-coordinated, the associated water molecule, which is fine leaving groups, is likely to depart during catalytic process. As a result, the remaining unsaturated nickel sites (five-coordinated) are exposed to reaction substrate, which will be beneficial to this reaction. Besides, the atoms in the L4− anion are nearly in the same plane for 3. This causes that the 2D structure of 3 owns numerous large open channel (dimensions of 16.393×11.571 Å and 15.198×11.582 Å). The big open channels can promote the transport of organic substrates and products (biphenyl), taking advantage of the touch of the substrates and the catalytic active sites. Unfortunately, the Ni(II) ions are both six-coordinated and the coordinated waters are absent in 5 and 6. The good news is that, the existence of the 1D channel will be conducive to the transmission of the reaction substrates in 5 (dimension of 9.999×9.275 Å) and 6 (dimension of 21.377×13.840 Å), further facilitate catalytic reaction. As for 7, the six-coordinated Ni(II) ion contains one associated water molecule, which will be


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a boon for the well-off occurrence of catalytic reaction. Based on these discussions, we speculate that the porosity, which is favourable factor for the catalytic reaction, may improve catalyst activity. Because our catalytic reaction is heterogeneous catalysis, the catalysts having a large enough surface area are necessary. Moreover, to attest the stability of samples after catalytic reaction, we take 3 for example. The superb match between the PXRD of the 3 retrieved from the catalytic reaction as well as that of the initial solid of 3 attests that 3 is strong in the catalytic condition (Figure S12). The SEM images of catalysts after catalytic reaction have also been unfolded in Figure S13. These samples exhibit a similar morphology consisiting of irregular particles with the wide particle size distribution, which is possibly the reasons leading to close catalytic effect. A conceivable mechanism is proposed in Scheme S3. Firstly, the Grignard reagent, which is produced by iodobenzene and magnesium, is activated by the catalyst (3, 5, 6 or 7) to provide I. Then, this species I reacted with iodobenzene to come into being a diaryl-substituted nickel complex intermediate II. Reductive elimination of the homocoupling product revitalized catalytically active species catalyst (3, 5, 6 or 7).

CONCLUSIONS In brief, seven Ni(II)/L4−/N-donor coligands coordination polymers with alluring frameworks have been triumphantly built under hydrothermal/solvothermal conditions. This work implys that the hire of mixed-ligands is a rational and feasible tactics to adjust and control the development of highdimensionality skeletons. The structural diversities of polymers 1–7 indicate that the conformation of the H4L ligand and additional N-donors play critical roles in the assembly of the final framework. Magnetic studies of 6 indicate that it may be potential magnetic material. Furthermore, in the complexes-catalyzed homo-coupling reaction of iodobenzene, 3, 5, 6 and 7 have been confirmed to be valid catalysts for the preparation of the biphenyl. Succedent studies will be concentrated on the catalytic performance of diversiform complexes fabricated by the flexible tetracarboxylic acid ligands and more N-donor ligands as well as other metal ions.


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Acknowledgment. This work was financially supported by the National Natural Science Foundation (Nos 21371155) and Research Found for the Doctoral Program of Higher Education of China (20124101110002).

Supporting Information Available: X-ray crystallographic data, selected bond lengths and bond angles, additional crystal figures, powder X-ray patterns, thermogravimetric curve, the χMT vs T plot and χM-1 vs T plot for 6, diffuse reflectance UV-VIS-NIR spectra for 1–7, 1H NMR spectra for Bibenzene. This information is available free of charge via the Internet at http://pubs.acs.org/.


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(a)

Page 24 of 38

(b)

(c)

Figure 1. (a) Schematic plot of the 2D Ni(II)/L4− net with helical chains. (b) Abridged general view of the 3D architecture fabricated by 2D Ni(II)/L4− layers and bpa pillars in 1. (c) Diagrammatic drawing of the 3-fold interpenetrated net for 1.


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(a)

(b)

L (c)

R (d)

Figure 2. (a) View of the Ni(II)/dpp helical chains. (b) View of the 2D Ni(II)/L4− net created by alternately helical chains. (c) Schematic view of the 3D framework built by the combination of 2D Ni-L networks and 1D Ni(II)-dpp chains. (d) Diagrammatic drawing of the 3-fold interpenetrated net for 2.


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(a)

(b)

(c)

(d)

Figure 3. (a) View of the 16-membered metallorings consisted of two Ni(II) atoms and two pbmb ligands. (b) The L4− anions bond with Ni(II) ions to generate a 1D ladder chain along the ab plane. (c) The 2D layer structure of 3 viewed along the b direction. (d) Schematic description of a (3,4)-connected 3,4L13 topology net with point symbol of (4·62)(42·62·82) for 3.


26

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(b)

(a)

(c)

(d)

Figure 4. (a) View of the 36-membered macrocyclic rings comprised of four Ni(II) atoms and four bmp ligands. (b) The 1D parallelogram channel constructed by Ni(II) atoms and L4− anions. (c) Schematic view of 3D structure of 4. (d) Schemetic view of the 3D topology network for 4.


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(a)

(b)

(c) (d)

Figure 5. (a) The three types of pbib link two adjacent Ni(II) ions into a 2D net. (b) Perspective view of 1D ladder chain composed of Ni(II) atoms and L4− anions. (c) View of the 3D network accomplished by 1D Ni(II)/L4− chain and 2D Ni(II)/pbib layer. (d) Schemetic diagram of the 3D topology net for 5.


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(a)

(c)

(b) (d)

Figure 6. (a) The 2D Ni(II)/L4− layer containing 1D chanels with the dimensions of roughly 8.7 × 9.9 Å2. (b) Two types of pbib (pbib-I and pbib-III) bridge two contiguous Ni(II) ions alternately to furnish a meso-helix chain. (c) Picture of the 3D coordination framework of 6. (d) Schemetic view of the 3D topology network for 6.


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(a)

(b) (c) (d)

Figure 7. (a) View of the 1D ladder chain made up of Ni(II) atoms and L4− anions. (b) The 1D infinite chain created by beb and Ni(II) atoms. (c) The 2D double layered structure of 7. (d) Schemetic diagram of the topology net with point symbol of (42·64)(4·64·8) for 7.


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Sample

Main absorption bands/nm

H 4L

257, 328

bpa

205, 245, 283

dpp

202, 245

pbmb

208, 255

bmp

205, 251

pbib

240, 257

beb

211, 294

Figure 8. UV-vis absorption spectra at room temperature and main absorption bands for the free organic ligands.

Sample

Main absorption bands/nm

1

240, 305, 386, 646

2

234, 303, 388, 635

3

239, 277, 297, 403, 683

4

237, 308, 391, 652

5

237, 303, 391, 657

6

240, 305, 391, 660

7

240, 311, 391, 657

Figure 9. UV-vis absorption spectra at room temperature and main absorption bands for complexes 1−7.


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Table 1. Complexes-catalyzed homo-coupling of Iodobenzene

Catalyst

Yield (%)

3

49

5

51

6

44

7

48


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For Table of Contents Use Only

Ni(II) Coordination Polymers Constructed from the Flexible Tetracarboxylic Acid and Different N-donor ligands: Structural Diversity and Catalytic Activity Lu Liu, a,b Chao Huang, a Xiaonan Xue, a Ming Li, a Hongwei Hou*, a Yaoting Fan a Seven Ni(II) coordination complexes with fascinating architectures and topological motifs have been prepared.

The

variable-temperature

magnetic

susceptibilities

of

6

display

overall

weak

antiferromagnetic coupling between the adjacent Ni(II) ions. In the complexes-catalyzed homo-coupling reaction of iodobenzene, 3, 5, 6 and 7 can serve as effective catalysts for the synthesis of the biaryl motifs.

Mg, catalyst(10%)

2

I

THF, reflux, 6h


38

Ni(II) Coordination Polymers Constructed from the Flexible

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