Synthesis, structure, and catalytic performance of heterobimetallic coordination polymers with β-diketone containing imidazole group

Accepted Manuscript Synthesis, Structure, and Catalytic Performance of Heterobimetallic Coordination Polymers with β-diketone containing imidazole group Yan Huang, Ping Yang PII: DOI: Reference:

S0277-5387(18)30686-7 https://doi.org/10.1016/j.poly.2018.10.050 POLY 13524

To appear in:

Polyhedron

Received Date: Revised Date: Accepted Date:

5 August 2018 9 October 2018 17 October 2018

Please cite this article as: Y. Huang, P. Yang, Synthesis, Structure, and Catalytic Performance of Heterobimetallic Coordination Polymers with β-diketone containing imidazole group, Polyhedron (2018), doi: https://doi.org/ 10.1016/j.poly.2018.10.050

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Graphical abstract Complex [ZnFe(L)3Cl](NO3)·3(MeOH)·3(DMF) can catalyze the ring opening of epoxides with aromatic amines to produce β-amino alcohols at room temperature.

1

Abstract Four

heterobimetallic

Zn[Al(L)3]2(NO3)2

coordination (2),

polymers

[Cd[Al(L)3]2(NO3)2

Zn[Fe(L)3]2(NO3)2

(3),

(1), and

[ZnFe(L)3Cl](NO3)·3(MeOH)·3(DMF) (4) have been synthesized. The structural analyses of coordination polymers 1-4 showed that they were trigonal space group, among which, coordination polymer 4 was P3 chiral space group. The circular dichroism spectra also confirmed that coordination polymer 4 had chirality. Zn(II) ion in coordination polymer 4 was tetracoordinated, unsaturated, can act as Lewis acid catalyst. Therefore, coordination polymer 4 can catalyze the ring opening of epoxides with aromatic amines to produce β-amino alcohols at room temperature. The catalytic reaction was regioselective, easy to operate, and had good catalyst recovery and repeatability.

Keywords: Catalysis; Heterometallic coordination polymer; β-diketone; imidazole

2

Synthesis, Structure, and Catalytic Performance of Heterobimetallic Coordination Polymers with β-diketone containing imidazole group Yan Huang a, Ping Yang b, * a

Department of Xinsha, Guangzhou entry exit inspection and Quarantine Bureau, Guangzhou 510623, China; b

School of Environment, Jinan University, Guangzhou 511443, China

1. Introduction Increasing the functionalization of heterometallic coordination polymers has attracted the attention of many researchers. The most studied heterometallic coordination polymers are 3d-4f heterometallic coordination polymers, which are often used in magnetic applications [1, 2] and transition metal complexes for sensitizing rare earth luminescence [3, 4]. The latter can red shift the excitation wavelength to the visible region and can also be used as white light material when the emission is complementary [5, 6]. The p-d and d-d heterometallic coordination polymers have similar coordination properties, which make it difficult to build coordination compounds, and thus, they need careful selection of corresponding strategies [7]. In general, some ligands with atoms that have different coordination ability can be selected, and a small molecular complex is first formed. Then, the uncoordinated atom is further coordinated and assembled with another metal ion to obtain a desired heterometallic coordination polymer. For example, pyridine 2,4-dicarboxylic acid [8,

*

Corresponding author: Ping Yang, School of Environment, Jinan University, Guangzhou, 511443, China. E-mail: [email protected] 3

9] and pyrazine 2-carboxylic acid [10-14] can be coordinated with different metal ions to form heterometallic coordination polymers. N-containing β-diketone ligands are also a good class of ligands for building heterometallic coordination polymers. For example, 1-(4-pyridyl)-1,3-butanedione (4-PBD) can be coordinated with tetrahedral Be to form a polyline metalloligand, and it can then be further assembled into a one-dimensional chain with tetrahedral Cd [15]. The sketch of the ligand is shown in Scheme 1. 4-PBD can also generate tripodal metalloligand with six-coordinated Al, and then it can be assembled with tetrahedral Zn to form trigonal bipyramidal cages or assembled with quadrilateral Pd to form cap-octahedral cages [16]. 1,3-Bis(4-pyridyl)-1,3-propanedione (4-BPPD) can generate a six exo-oriented donor metalloligand with hexacoordinated Fe. A two-dimensional layer can be formed when four donors participate in coordination via tetrahedral coordination of Ag. A binodal 5,4-connected 2-fold interpenetrated three-dimensional network is formed when five donors are coordinated, and a trinodal 6,3,4-connected three-dimensional network is formed when six donors are coordinated [17]. 3-(4-Pyridyl)-2,4-pentanedione (4-PPD) reacts with tetracoordinate Be/Cu to form a linear metalloligand, forming a planar triangular metalloligand with Fe/Al, and then it reacts with N-philic Co, Cu, Ag, Zn, Cd, and Hg to form a one- or two-dimensional structure [15, 18-22]. In recent years the application of coordination polymers has shifted to catalysis because the coordinately unsaturated metal sites can act as Lewis acid catalysts for nucleophilic substitution reactions, such as ring opening of epoxide with amine [23,

4

24]. β-Amino alcohols, which are synthesized through aminolysis of epoxides with corresponding amines, have a wide range of applications in medicine, non-natural amino acids, and chiral auxiliary asymmetric synthesis [25-28]. High reaction temperatures and excess nucleophiles are often required in the absence of a catalyst, and these result in lower yields, poor reaction regioselectivity, and stereoselectivity [29, 30]. To solve these problems, a wide variety of catalysts have been developed [31-33]. Coordination polymers has high crystallinity and uniform pores to make they can catalyze reactions with selectivity based on substrate size and shape. Moreover, the catalytic active sites of coordination polymers can be tuned via their metal nodes or organic ligands through pre-synthetic or post-synthetic approaches. In view of the advantages of coordination polymer catalysts, therefore, it is necessary to expand more research. In the structural regulation synthesis of our previous studies [34, 35], it was found that 1-(4-(1H-imidazol-yl)phenyl)butane-1,3-dione (HL) preferred a trans-configuration and that the coordination angle was larger, which facilitated building high dimensional structures. Moreover, HL contains N and O coordination atoms and can be coordinated with metal ions that have different properties, and thus, it has the potential to be used in constructing heterobimetallic coordination polymers. In this paper, the ligand was chosen to react with O-philic Fe/Al ions and N-philic Zn/Cd ions to generate the heterobimetallic coordination polymers and the catalytic activity of these compounds toward ring opening reactions of epoxides with aromatic amines was studied.

5

Scheme 1 Sketches of the ligands 4-PBD, 4-BPPD, 4-PPD and HL. 2. Experimental Section 2.1 Materials and Methods All chemicals used were analytical reagent and were not pretreated before use. Elemental analysis (C, H, N) was measured using a Elementar Vario EL elemental analyzer. IR spectra was performed on a Bruker TENSOR 27 (4000-400 cm–1) infrared spectrometer using KBr pellets. NMR spectra were recorded on a Varian Mercury-Plus 300 MHz NMR spectrometer, and all chemical shifts were based on TMS as a reference. Electron spray ionization mass spectrometry (ESI-MS) was recorded on a SHIMADZU LCMS-2010A mass spectrometer to obtain the molecular ion peak of compound, and methanol was selected as the carrier solvent. Thermal analysis was carried out on Netzsch TG 209 F3 Tarsus thermogravimetric analyzer

6

(nitrogen atmosphere). The reference compound was Al2O3, and the heating rate was 10 °C/min. The powder X-ray diffraction (PXRD) was measured on a Bruker D8 advanced diffractometer with Cu Kα radiation (λ = 0.15409 nm) at a scanning rate of 4°/min with 2θ ranging from 5 to 35°. PXRD patterns simulated with a single crystal data were generated using the software Mercury 1.4.2. Circular dichroism (CD) spectra were collected on a JASCO J-810 CD spectrometer. UV-Vis spectra were recorded on a CARY-300 spectrometer (VARIAN). GC-MS studies were performed with a Shimadzu instrument (QP 2010) with an RTX-5SIL-MS column. The ligand 1-(4-(1H-imidazol-yl)phenyl)butane-1,3-dione (HL) was synthesized according to our previous articles [34, 35]. 2.2 Synthesis of coordination polymer 1 H2O/EtOH (2 mL, 1/1) was carefully layered on a solution of Al(NO3)3·9H2O (0.02 mmol) and Cd(NO3)2·2H2O (0.03 mmol) in water (1 mL), and then a solution of HL (0.06 mmol) in ethanol (1 mL) was further layered on the buffer solution. After standing for a week, colorless crystals of Cd[Al(L)3]2(NO3)2 (1) were obtained (11 mg, yield 65% based on Al). C78H66N14O18Al2Cd: calcd. C 56.65; H 4.02; N 11.86%; found: C 56.04; H 4.10; N 11.73%. IR (KBr pellet, cm−1): 3432 w, 3119 w, 1605 m, 1561 m, 1537 m, 1510 s, 1452 m, 1405 m, 1383 s, 1305 m, 1259 w, 1190 w, 1122 w, 1059 w, 1016 w, 962 w, 854 m, 780 w, 655 w, 620 w, 472 w. 2.3 Synthesis of coordination polymer 2 The precursor Al(L)3 was readily prepared according to mix Al(NO3)3·9H2O and HL in H2O/EtOH (1/1). Then, DMF (1 mL) was carefully layered on a solution of Al(L)3

7

(0.03 mmol) in dichloromethane (2 mL), and then a solution of Zn(NO 3)2·6H2O (0.09 mmol) in methanol (1 mL) was further layered on the buffer solution. After standing for a week, colorless crystals of Zn[Al(L)3]2(NO3)2 (2) were obtained (8 mg, yield 33% based on Al). C78H66N14O18Al2Zn: calcd. C 58.31; H 4.14; N 12.20%; found: C 57.90; H 4.31; N 11.97%. IR (KBr pellet, cm−1): 3430 w, 3115 w, 1601 m, 1563 m, 1535 m, 1509 s, 1453 m, 1404 m, 1386 s, 1304 m, 1269 w, 1189 w, 1130 w, 1058 w, 1014 w, 962 w, 854 m, 780 w, 656 w, 620 w, 475 w. 2.4 Synthesis of coordination polymer 3 A solution of HL (0.1 mmol) in DMF (2 mL) was added to a solution of Fe(ClO4)2·6H2O (0.03 mmol) in methanol (1 mL) and shaken well. Then, a solution of Zn(NO3)2·6H2O (0.05 mmol) in methanol (1 mL) was added. After standing for a week, red crystals of Zn[Fe(L)3]2(NO3)2 (3) were obtained (11 mg, yield 43% based on Fe). C78H66N14O18Fe2Zn: calcd. C 56.28; H 4.00; N 11.78%; found: C 55.93; H 4.16; N 11.56%. IR (KBr pellet, cm−1): 3427 w, 3115 w, 1601 m, 1563 m, 1535 m, 1509 s, 1448 m, 1403 m, 1384 s, 1310 m, 1253 w, 1189 w, 1122 w, 1059 w, 1016 w, 962 w, 851 m, 781 w, 660 w, 627 w, 471 w. 2.5 Synthesis of coordination polymer 4 A solution of HL (0.1 mmol) in DMF (2 mL) was added to a solution of FeCl3·6H2O (0.03 mmol) in methanol (1 mL) and shaken well. Then, a solution of Zn(NO 3)2·6H2O (0.05 mmol) in methanol (1 mL) was added. After standing for a week, red crystals of [ZnFe(L)3Cl](NO3)·3(MeOH)·3(DMF) (4) were obtained (24 mg, yield 65% based on Fe). Elemental analysis for (C51H66N10O15ZnClFe): Anal. Calcd. C, 51.70; H, 5.58; N,

8

11.83; found: C, 51.74; H, 5.55; N, 11.81. IR (KBr pellet, cm−1): 3439 w, 3114 w, 1672 cm, 1602 m, 1561 m, 1532 m, 1516 s, 1456 m, 1403 m, 1387 s, 1303 m, 1254 w, 1198 w, 1126 w, 1058 w, 1013 w, 968 w, 857 m, 780 w, 658 w. To confirm the effect of the Cl ion on the structure, A solution of HL (0.1 mmol) in DMF (2 mL) was added to a solution of Al(NO3)3·9H2O (0.03 mmol) in methanol (1 mL) and shaken well. Then, a solution of ZnCl2 (0.05 mmol) in methanol (1 mL) was added. After standing for a week, colorless crystals were obtained (cell parameters were similar to those of 4). 2.6 Catalytic test Generally, the central metal of coordination polymers with coordinatively unsaturated sites has the possibility to have the catalytic activity [23, 36]. However, the central metal of coordination polymers 1-3 are all saturated with hexacoordinates, so coordination polymers 1-3 were not tested in catalysis. An equimolar mixture of epoxides (5 mmol, epichlorohydrin, 1,2-epoxyethylbenzene, and cyclohexene oxide) and aniline (5 mmol) was stirred at room temperature and solvent-free conditions in the presence of 0.5% catalyst (coordination polymer 4). The reaction was monitored using a TLC method. After reaction 6 h, 2 mL of ethyl acetate was added to dilute the solution, and the solid catalyst was removed via filtering. The crude product was purified by column chromatography on silica gel using hexane / ethyl acetate mixture (5:1) as the eluent. The products were identified and quantified by ESI-MS, NMR, and GC-MS techniques. The recovered catalyst was washed with diethyl ether, dried, and reused without further purification or regeneration. The control group was treated

9

with no catalyst. 2.7 X-ray crystallography Data for the coordination polymers of 1-4 were collected on a Bruker Smart Apex CCD area detector and a Rigaku R-AXIS SPIDER IP (Mo Kα, λ = 0.071073 nm or Cu Kα, λ = 0.154178 nm), and the SADABS program were used for absorption correction. The crystal structure was obtained using the direct method and refined using the SHELXTL package on a full-matrix least-squares structure based on F2. Except for the extremely severely disordered atoms, other non-hydrogen atoms were refined anisotropically. The geometric hydrogenation method was used to add hydrogen atoms on the organic group, and the differential Fourier synthesis method was employed to add hydrogen atoms to the solvent water. Parts of Solvents and counter anions cannot be refined because of weak diffraction, and SQUEEZE was used for the overall quality of the data. Further details of the X-ray structural analyses for coordination polymers 1-4 are given in Table 1 and Table 2. The selected bond lengths for 1-4 are listed in Table A.1.

3. Results and discussion 3.1 Crystal structure As seen in Table 1, coordination polymers 1-3 were trigonal space group (R−3 or R−3c) and had similar structures (see Supporting Information). The structure of coordination polymer 1 is taken as an example for discussion. The independent unit contained one Al(III) ion, one Cd(II) ion, and one HL ligand molecule. Solvents and

10

counter anions cannot be refined because of weak diffraction, and SQUEEZE was used for the overall quality of the data [37]. The Al(III) ion was on the three-fold rotational axis and was chelated by six oxygen atoms of the β-diketone group of three ligands (Fig. 1), and the three imidazole groups pointed to the same end, forming a tripodal metalloligand (Fig. 2a). The Cd(II) ion was on a six-fold rotational axis, surrounded by six imidazole N atoms of six ligands, and can be seen as six junctions. Each ligand was trans-bridged with one Al(III) ion and one Cd(II) ion, which can be seen as connecting lines and simplified the structure to a two dimensional kgd topology (Fig. 2b).

Fig. 1 ORTEP drawing of coordination polymer 1 with thermal ellipsoids 30% probability. This is a partial view of the compound. Symmetry code: A 1–y, x–y, z. B 1–x+y, 1–x, z. C y, –x+y, –z. D –x+y, –x, z. E x–y, x, –z. F –x, –y, –z. G –y, x–y, z.

The kgd topology can be considered as a stack of Cd3Al4(L)9 unit by edge sharing. Each Cd3Al4(L)9 unit can be considered as a parallelepiped lacking a vertex (Fig. 2a), with included angles of 73.5° and 106.5° and a side length of 12.55 Å. The layers can 11

attract each other through weak C(1)–H(1)•••O(2) hydrogen bonds (3.527(5) Å, 106.4(3)°) to form ABC••• type stacks (Fig. 2c and Fig. 2d). A regular quadrilateral channel (12.55 × 12.55 Å) was formed in the layer with a void ratio of 50.6%. Compared to 4-PBD, the metalloligand formed by HL with the first metal (Al/Fe) were also three-pronged, and the angles were similar (71.45°~86.46°). However, since the second metal was an octahedral six-junction rather than a V-shaped two-junction or planar four-junction, and thus, the structure dimension increased [16].

Fig. 2 (a) schematic drawing, (b) kgd topology, (c) hydrogen bonds, and (d) stacking diagram of coordination polymer 1.

12

As seen in Table 2, coordination polymer 4 was a trigonal system and P3 chiral space group. The independent contained one Fe(III) ion, one Zn(II) ion, one HL ligand molecule, one methanol molecule, one DMF molecule, and two counter anions. The Fe(III) ions on the three-fold rotational axis were coordinated by six oxygens of the β-diketone group of three ligands (Fig. 3). The Fe(III) ions was a chiral center. The three imidazole groups pointed to the same end, forming a tripodal metalloligand (angle 82.4°). Due to the different size and geometry of anions in the reaction, the coordination sphere of zinc ion and network structures of coordination polymer 4 are different from those of coordination polymer 1 [38-40]. The Zn(II) ion on the three-fold rotational axis was surrounded by three imidazole N atoms of three ligands and one chloride ion and can be seen as three junctions. Each ligand bridged one Fe(III) ion and one Zn(II) ion in trans bridges, and this can be seen as connecting lines and simplified the structure to a two dimensional hcb topology (Fig. 4a).

Fig. 3 ORTEP drawing of coordination polymer 4 with thermal ellipsoids 30% probability. Symmetry code: A: 1 – y, x – y, z. B: 1 –x + y, 1 – x, z. C: –y, x – y, z. D: –x + y, –x, z. 13

Compared to coordination polymer 1, each Fe3Zn3(L)6 unit is equivalent to a parallelepiped that removes two vertices from the body diagonal, and can be regarded as a chair hexagon (Fig. 4a) with an included angle of 82.4° and a side length of 12.3 Å. The units were connected in a wave layer via a shared edge, and the layers overlapped and shaded into each other through weak C(9)–H(9)···Cl(1) hydrogen bonds (3.70(1) Å, 150.4(8)°) (Fig. 4b). A hexagonal channel with a diameter of about 8 Å was formed in the c direction with a void rate of 44.8%.

Fig. 4 (a) hcb topology and (b) hydrogen bonds and stacking diagram of coordination polymer 4.

14

3.2 Powder X-ray Diffraction As seen in Fig. A.1 and Fig. A.2, the powder X-ray diffraction pattern of coordination polymer 1 and 4 agreed well with the powder X-ray diffraction pattern simulated from the single crystal data, indicating that the products were a pure phase (see Supporting Information).

3.3 Solid state Circular Dichroism spectra of coordination polymer 4 As seen in Fig. 5, coordination polymer 4 had a broad UV absorption peak at 340 nm (ε = 1.15×105 L·mol−1·cm−1), 4-R (with right-hand configuration) had a positive CD absorption peak at 353 nm, and the CD spectrum of 4-L (with left-hand configuration) mirrored each other.

Fig. 5 UV-Vis spectra of coordination polymer 4, ethanol solution with a concentration of 1×10−5 mol/L; the CD spectra of coordination polymer 4 in the solid state at room temperature.

15

3.4 Ring opening of epoxides catalyzed by coordination polymer 4 As seen in Scheme 2, the tetracoordinated Zn(II) in coordination polymer 4 was surrounded by three imidazole groups and one chloride ion. The zinc ion is sp3 hybridization and unsaturated (the saturation state is sp3d2), and their empty 4d orbital could accept electron pairs. So coordination polymer 4 can be regarded as a Lewis acid catalyst, which accepts nucleophilic attack of the O atom in the epoxides, thus catalyzing amination [23].

Scheme 2 Possible mechanism of coordination polymer 4 for catalytic ring opening of epoxides with aromatic amine.

Because the lone pair of electrons in the arylamine participated in the aromatic ring π-conjugation and reduced its nucleophilicity, the reaction rate of the epoxides with aniline at room temperature was very low. In this context, a catalyst is often required to activate the epoxides to promote reaction. Coordination polymer 4 was employed to catalyze the reaction of aniline and cyclohexene oxide, 1,2-epoxyethylbenzene, and epichlorohydrin to investigate its catalytic performance. Under these conditions, a smooth reaction resulted that produced the corresponding β-amino alcohol in high yield (Table 3).

16

When coordination polymer 4 was used to catalyze the reaction of cyclohexene oxide with aniline, product 1 (2-(phenylamino)cyclohexan-1-ol) was obtained as a single product. Mass spectrometry: m/z = 192 (M+1). 1H NMR (CDCl3, 300 MHz): δ 1.18 (m, 1H); 1.34 (m, 3H); 1.76 (m, 2H); 2.11 (m, 2H); 3.16 (m, 1H); 3.43 (m, 1H); 6.85 (m, 3H); 7.21 (t, 2H). The mass spectrum and 1H NMR spectrum are shown in Fig. A.3. It was also found that higher yields (94%) can be obtained in the absence of solvent at room temperature. For comparison, the author also used coordination polymer 4 to catalyze the reaction of

1,2-epoxyethylbenzene

with

aniline

to

give

product

2

(1-phenyl-2-(phenylamino)ethan-1-ol) as a single product. Mass spectrometry: m/z = 214 (M+1). 1H NMR (DMSO-d6, 300 MHz): δ 3.59 (m, 2H); 4.32 (d, 1H); 4.95 (t, 1H, OH); 5.94 (d, 1H, NH); 6.47 (m, 3H); 6.95 (t, 2H); 7.17 (t, 1H); 7.27 (t, 2H); 7.34 (d, 2H). The mass spectrum and 1H NMR spectrum are shown in Fig. A.4. The aniline attacked the carbon without the phenyl substituent, which has low activity, instead of the common the carbon with the phenyl substituent [28]. It was also found that higher regioselective products can be obtained at room temperature under solvent-free conditions; yield: 88%. When catalyzing the reaction of epichlorohydrin with aniline, the aniline may attack either the carbon with the chloromethyl substituent or the carbon without the chloromethyl substituent or both, although the mass spectrometry and 1H NMR spectra of product 3 showed a pure compound (Fig. A.5). Mass spectrometry: m/z = 186 (M+1). 1H NMR (DMSO-d6, 300 MHz): δ 3.05 (m, 1H, –CH2–); 3.15 (m, 1H, –

17

CH2–); 3.61 (m, 1H, –CH2–); 3.67 (m, 1H, –CH2–); 3.83 (s, 1H, >CH–); 5.31 (s, 1H, OH); 5.52 (s, 1H, NH); 6.51 (t, 1H, benzene, J = 15 Hz, J’ = 6 Hz, J’’ = 9 Hz); 6.59 (d, 2H, benzene, J = 9 Hz); 7.04 (t, 2H, benzene, J = 15 Hz, J’ = 9 Hz, J’’ = 6 Hz). To determine which C reacted, the author recorded 13C nuclear magnetic spectroscopy of product 3 (Fig. A.6). 13C NMR (DMSO-d6, 300 MHz): δ 47.52, 48.82, 69.57, 112.79, 116.47, 129.52, 149.24. The results show that only the carbon without the chloromethyl

substituent

was

attacked

(product

3

is

1-chloro-3-(phenylamino)propan-2-ol), indicating that coordination polymer 4 has regioselective catalysis. In addition, the TLC study found a small amount of a second product,

which

was

characterized

(3,3'-(phenylazanediyl)bis(1-chloropropan-2-ol))

after

as

product

purification

via

4 column

chromatography (Fig. A.7). Mass spectrometry: m/z = 278 (M + 1). 1H NMR (CDCl3, 300 MHz): δ 3.24 (dd, 1H); 3.47 (dd, 1H); 3.62 (m, 5H); 3.88 (d, 1H); 4.16 (m, 2H); 6.70-6.86 (m, 3H); 7.23-7.29 (m, 2H). These results show that coordination polymer 4 can catalyze the ring opening of epoxides by primary amines and also catalyze secondary amines. To obtain product 3 as a single product, a slight excess of aniline is sufficient. This indicates that coordination polymer 4 has good regioselective catalysis for aromatic amine nucleophilic attack on the ring-opening reaction of alkylene oxide, and thus, it can be used as a standby catalyst for this reaction.

4. Conclusion In summary, we used the ligand HL to culture four heterobimetallic coordination

18

polymers that were classified in two categories via the slow evaporation and liquid phase

diffusion

at

room

temperature.

Coordination

polymers

1-3

were

two-dimensional kgd layers. As expected, the oxygen-binding Fe/Al ions in these coordination polymers coordinated with the β-diketones of the three ligands, and the nitrogen-philic Zn/Cd ions coordinated with the imidazoles of the six ligands. The Fe(III) ions in coordination polymer 4 still had three chelated β-diketones, but the Zn(II) ions became four-coordinate because of the introduction of chloride ions in FeCl3 in the raw material, and this resulted in a two-dimensional hcb layer structure. Thus, the anion had a certain effect on the structure configuration. Coordination polymers 1-4 each had a large void content and can each be used as a potential adsorbent storage material. The Zn(II) ion coordination in coordination polymer 4 was unsaturated and had Lewis acidity. Coordination polymers 4 can catalyze the ring opening of epoxides with aromatic amines to produce β-amino alcohols at room temperature. The catalytic reaction was regioselective, easy to operate, and had good catalyst recovery and repeatability. Appendix A. Supplementary data CCDC < 801392, 1849432, 1849442, 1849461, and 1849462 > contains the supplementary crystallographic data for < Coordination polymers 1-4 >. These data can

be

obtained

free

via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or

of from

charge the

Cambridge

Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail: [email protected].

19

Supplementary

data

to

this

article

can

be

found

online

at

https://doi.org/10.1016/j.poly.xxxx.xx.xxx.

Acknowledgements This work was supported by the National Natural Science Foundation of China [grant number 41701349] and Sun Yat-Sen University.

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Yaghoobnejad

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Table 1 Crystal data and structure refinement for coordination polymers 1-3 Coordination polymer

1

2

3

Empirical formula

C78H66N12O12Al2Cd

C78H66N12O12Al2Zn

C78H66N12O12Fe2Zn

Formula weight

1529.79

1482.76

1540.50

Temperature (K)

153(2)

153(2)

153(2)

Wavelength (Å)

0.71073

0.71073

0.71073

Crystal system

Rhombohedral

Rhombohedral

Rhombohedral

Space group

R–3

R–3

R–3c

a (Å)

15.0191(8)

16.1469(9)

13.3219(7)

b (Å)

15.0191(8)

16.1469(9)

13.3219(7)

c (Å)

45.789(3)

43.317(5)

89.148(8)

V (Å3)

8945.0(9)

9780.6(14)

13701.7(16)

Z

3

3

6

Dc (Mg/m3)

0.852

0.755

1.120

μ (mm-1)

0.242

0.242

0.631

F(000)

2364

2310

4776

Reflections collected

9195

11504

11773

Unique, Rint

3823, 0.0653

4204, 0.0978

3005, 0.0523

Data/restraints/parameters

3823 / 0 / 160

4204 / 18 / 173

3005 / 0 / 160

GOF on F2

1.082

1.036

0.994

R1 [I>2σ(I)]

0.0754

0.1010

0.0425

wR2 (all data)

0.2329

0.3027

0.1062

Δρmax / Δρmin (e·Å–3)

0.573 / –0.875

0.587 / –0.381

0.406 / –0.387

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Table 2 Crystal data and structure refinement for coordination polymer 4 Coordination polymer

4-R

4-L (SQUEEZE)

Empirical formula

C51H66N10O15ZnClFe

C39H33N6O6ZnClFe

Formula weight

1183.75

838.38

Temperature (K)

153(2)

153(2)

Wavelength (Å)

1.54178

0.71073

Crystal system

Trigonal

Trigonal

Space group

P3

P3

a (Å)

16.1741(3)

16.173(3)

b (Å)

16.1741(3)

16.173(3)

c (Å)

6.4604(2)

6.497(3)

V (Å3)

1463.63(6)

1471.7(8)

Z

1

1

Dc (Mg/m3)

1.411

0.946

μ (mm-1)

3.539

0.735

F(000)

649

430

Reflections collected

5185

4334

Unique, Rint

3136, 0.0289

1901, 0.0421

Data/restraints/parameters

3136 / 7 / 243

1901 / 1 / 164

GOF on F2

1.088

0.995

R1 [I>2σ(I)]

0.0859

0.0890

wR2 (all data)

0.2674

0.2398

Flack parameter

0.087(15)

0.08(5)

Δρmax / Δρmin (e·Å–3)

1.897 / –2.616

1.443 / –1.779

24

Table 3 Ring opening reactions of a few epoxides with aniline using catalyst coordination polymer 4 Entrya Epoxide Product Yield (%)b 1 94, 93c, 92d

2

88

3

75

a

Conditions: catalyst 0.5%; 6 h stirring, room temperature. bYield calculated from the GC-MS using internal standard. c,dIsolated yield after third and fifth run, respectively. As a control, reactions without any catalyst under identical conditions gave negligible products (yield < 5%).

25