Calixarene-Based {Ni14} Seesaws: Active Chloride Anions to be

Sep 29, 2016 - A discrete seesaw-like Ni14 cluster is assembled from two sandwich-like Ni4-(TC4A)2 SBUs and two shuttlecock-like Ni3-(TC4A) SBUs ...
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Calixarene-Based {Ni14} Seesaws: Active Chloride Anions to be Substituted by Isophthalic Acids Xinxin Hang,†,‡ Shentang Wang,†,‡ Tianyu Xue,*,† Xiaofei Zhu,† Haitao Han,†,‡ and Wuping Liao*,† †

State Key Laboratory of Rare Earth Resource Utilization, ERC for the Separation and Purification of REs and Thorium, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, P. R. China ‡ University of Chinese Academy of Sciences, Beijing 100049, P. R. China S Supporting Information *

ABSTRACT: A discrete seesaw-like Ni14 cluster is assembled from two sandwich-like Ni4-(TC4A)2 SBUs and two shuttlecock-like Ni3-(TC4A) SBUs (H4TC4A = p-tert-butylthiacalix[4]arene) with two imidazole-4,5-dicarboxylic acid (H3IDC) ligands. The substitution of active coordinated chloride anions with isophthalic acid derivatives leads to four new compounds with similar cluster structures.

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attempted the multidentate rigid ligand: imidazole-4,5dicarboxylic acid (H3IDC), which has versatile coordination modes and potential H-bonding interaction sites. We succeeded in obtaining a discrete seesaw-like {Ni14} cluster (CIAC-220), constructed by two sandwich-like Ni4-(TC4A)2 SBUs and two shuttlecock-like Ni3-TC4A SBUs which are held together by two IDC ligands. By carefully analyzing the structure of this cluster, we find that there are two active coordinated chloride anions which would be substituted by other anions or ligands. Here we chose isophthalic acids to test the possible substitution of chloride ions. Four isophthalic acids with different structures were successfully introduced into the cluster by binding the active coordination sites without destroying the cluster structure. Green lamellar crystals of CIAC-220 were obtained by the solvothermal reaction of NiCl2·6H2O, H4TC4A, and H3IDC in 1:1 (v:v) CH3OH/DMF mixed solvent (total 10 mL) with several drops of triethylamine at 130 °C for 72 h. Compound CIAC-220 crystallizes in the triclinic system with space group P1.̅ In an asymmetric unit, there are 14 crystallographically independent NiII atoms which are linked into a complete seesaw-like {Ni14} cluster (Figure 1). The {Ni14} cluster is constructed by two distinct kind of SBUs, the sandwich-like Ni4-(TC4A)2 SBU and the shuttlecock-like Ni3-TC4A SBU. Each asymmetric unit contains two sandwich-like Ni4-(TC4A)2 SBUs, two shuttlecock-like Ni3-TC4A SBUs, two IDC ligands, two bonded chloride ions and four coordinated solvent

igh-nuclearity coordination clusters are of great interest in physics and chemistry due to their aesthetical structures and important role in connecting the microscopic to macroscopic world and quantum to classic systems.1−7 Many groups around the world have sought to fabricate polynuclear clusters and achieved some inspiring accomplishments. For example, a number of giant homometallic clusters of 3d and 4f metal ions have been isolated, consisting of the metals Mn (Mn84, Mn32, Mn30),8−11 Fe (Fe168, Fe64),12,13 Co (Co36, Co32),14,15 Ni (Ni40, Ni34, Ni24),16−18 Cu (Cu44),19 and Er (Er60).20 In addition, several heterometallic 3d/3d and 3d/4f clusters have been reported, such as Mn28Cu17,21 Fe12Ln4,22 Ni32La20,23 Cu36Ln24,24 Gd36Ni12,25 and Ni54Gd54.26 Despite the large amount of work reported in this field so far, the rational design and synthesis of such materials is still a challenge. Calixarenes are versatile multidentate ligands for constructing polynulear compounds.27−30 A variety of calixarene- and resorcinarene-based coordination cages with well-defined shapes and sizes were obtained via metal-mediated selfassembly.29−34 Thiacalix[4]arenes (H4TC4A), a subset of calix[4]arenes, always react with metal ions to form a shuttlecock-like Mx-TC4A (commonly x = 1−4) secondary building unit (SBU). The Mx-TC4A SBUs are linked by auxiliary organic linkers to form large discrete molecular entities or extended network structures.28,31,35−41 In contrast to the previously mentioned metal−organic architectures which only contain shuttlecock-like Mx-TC4A SBUs, the assembly of discrete high-nuclearity architectures containing multiple SBUs was rarely reported. We reasoned that multifunctional organic ligands that contain appropriate coordination sites linked by a spacer with specific positional orientation would be favorable to construct a diversity of high-nuclearity clusters. We therefore © XXXX American Chemical Society

Received: July 20, 2016 Revised: September 23, 2016

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DOI: 10.1021/acs.cgd.6b01072 Cryst. Growth Des. XXXX, XXX, XXX−XXX

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Figure 1. Scheme for the construction of teeter-totter-like {Ni14} cluster by sandwich-like Ni4-(TC4A)2 SBUs and shuttlecock-like Ni3TC4A SBUs with two IDC molecules. Coordinated solvent molecules and H atoms are omitted for clarity.

molecules (DMF and H2O). In a Ni4-(TC4A)2 entity, two TC4A molecules stagger from each other in tail-to-tail arrangement and bond a same tetranuclear Ni4 square to form a sandwich-like SBU. Among eight NiII sites for the Ni4(TC4A)2 SBUs, the sites Ni1, Ni3 and Ni11, Ni13 are sixcoordinated by two phenoxy O atom, one sulfur atom from one TC4A molecule and two other phenoxy O atoms, another sulfur atom from the other TC4A ligand. Ni2 and Ni12 sites are bonded by two phenoxy O atoms and one sulfur from a TC4A and two other phenoxy O atoms from the other TC4A in a fivecoordination mode (Figure S1a). Ni4 and Ni14 sites are sixcoordinated by two phenoxy O atoms and one sulfur from a TC4A, one phenoxy O atom from the other TC4A, and two carboxyl O atom of an IDC ligand. The Ni−Ni distances along the edges of the Ni4 square are in the range of 3.00−3.63 Å and Ni−Ni−Ni angles are of 61.9−125.9°. In a Ni3-TC4A entity, the TC4A molecule adopting a cone conformation bonds a trinuclear Ni3 triangle through its four phenolic oxygen atoms and three sulfur atoms to form a shuttlecock-like SBU. Six crystallographically independent NiII sites for the Ni3-TC4A units are all six-coordinated by two phenoxy O atoms, one sulfur atom from the TC4A, one μ3-Cl atom, and one O and one N atom from the IDC ligand or two water molecules or one water and one DMF (Figure S1b). The Ni−Ni distances for the Ni3 triangles are in the range of 3.26−4.17 Å and Ni− Ni−Ni angles are of 50.0−77.9°. Two sandwich-like Ni4(TC4A)2 SBUs occupied the side positions, while two shuttlecock-like Ni3-TC4A SBUs are located on the middle acting as the holders, all of which are linked by two IDC ligands into a teeter-totter-like entity. To the best of our knowledge, CIAC-220 represents the first example of discrete metal− calixarene unit that contains both sandwich-like Ni4-(TC4A)2 SBUs and shuttlecock-like Ni3-TC4A SBUs. When carefully exploring the structure of this {Ni14} cluster, one can find that there is an obvious space above the chloride anions which act as the tridentate nodes with the distance of 5.0 Å. It is common that the coordinated halogen anions in the coordination compounds can be substituted if the target ligand has proper size and coordination mode. Due to the relatively longer distance between the chloride ions and enough space between two Ni4-(TC4A)2 SBUs, these two chloride anions would be substituted by some ligands such as isophthalic acid which has a distance between the carboxyl carbon atoms of nearly 5.0 Å and possible tridentate coordiantion mode of the carboxyl groups. As shown in Figure 2a, by introducing isophthalic acid into the reaction system, similar {Ni14}

Figure 2. (a) Illustration of the ligand substitution of the {Ni14} cluster through the labile coordination sites. (b) Crystal structures of the {Ni14} cluster familiy. The functionalized ligands are highlighted in green color. (c) Distance between the centers of the Ni3 cores in CIAC-220 and CIAC-221, respectively. (d) Dihedral angles through the two Ni3 cores in CIAC-220 and CIAC-221, respectively. Coordinated solvent molecules and H atoms in the structures are omitted for clarity.

architectures were successfully obtained, indicating that the coordinated chloride ion sites are rather active and can be readily applied to ligand exchange. Ligand exchange leads to higher symmetry of the crystal structures, that is, the space group was changed from P1̅ for CIAC-220 to P21/n for CIAC-221, which might be due to the fact that there is a rigid support (benzene ring) between two B

DOI: 10.1021/acs.cgd.6b01072 Cryst. Growth Des. XXXX, XXX, XXX−XXX

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structures. This work provides a new perspective toward the design and synthesis of high-nuclearity clusters. Our efforts to obtain the elegant calixarene-based molecular clusters are ongoing.

carboxyl groups of isophthalic acid while two chloride anions are separated in CIAC-220. As shown in Figure S3, a carboxyl group substitutes a chloride anion and binds three nickel atoms simultaneously by one carboxyl oxygen atom binding two nickel atoms and another oxygen atom binding another nickel atom. The isophthalic acid molecule acts as another bridge to hold up two Ni3-TC4A SBUs. It is found that the Ni3-TC4A SBUs are wrenched a little outside, that is, the distance between the centers of two Ni3 cores is enlongated from 7.3 to7.6 Å and the dihedral angle between two planes through the Ni3 cores is changed from 92.4° to 104.0° (Figure 2c,d). Furthermore, the packing of the clusters exhibits a profound change (Figure S4− S5). To investigate the effect of functional groups of isophthalic acid on the stability of substituted structures, we chose three derivatives such as 1,3,5-benzenetricarboxylic acid, 5-(5fluoropyridin-3-yl)isophthalic acid, and 5-(pyrimidin-5-yl) isophthalic acid to process the substitution. It was found that functional groups did not influence the formation of the {Ni14} cluster. However, in the substituted structures, the plane through pyridine ring (or pyrimidine ring) deviates heavily from that through the phenyl ring of isophthalic acid derivatives due to possible steric hindrance. Magnetic susceptibility measurements were carried out on fresh samples of CIAC-220 in an applied field of 1 kOe over the temperature range of 2−300 K as shown in Figure 3. The

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ASSOCIATED CONTENT

* Supporting Information S

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.cgd.6b01072. Full details for experimental procedures, single-crystal structure determination, TGA/DSC, FT-IR (PDF) Accession Codes

CCDC 1493167−1493171 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected]. *E-mail: [email protected]. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by National Natural Science Foundation of China (Nos. 21571172, 21521092, and 51222404).

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REFERENCES

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Figure 3. Plots of χMT and 1/χM vs T for CIAC-220 in a 1000 Oe field.

χMT value decreases gradually from 13.98 cm3 mol−1 K at 300 K to 1.72 cm3 mol−1 K at 2 K. For each NiII center, the experimental χMT value at room temperature is 1.00 cm3 mol−1 K, which is consistent with the typical spin-only value of the uncoupled NiII ion.42 The reciprocal molar susceptibility in 100−300 K follows the Curie−Weiss law of 1/χM = (T − θ)/C with C = 16.19 cm3 mol−1 K and θ = −45.83 K. The negative Weiss constant (θ) value suggests the presence of strong antiferromagnetic coupling interaction between NiII ions. In summary, we have successfully constructed a discrete Ni14 seesaw by linking the shuttlecock-like Ni3-TC4A SBUs and sandwich-like Ni4-(TC4A)2 SBUs with imidazole-4,5-dicarboxylic acid. The deliberate choice of the multidentate rigid ligand is crucial to designing and synthesizing such a cluster. Due to the activity of the coordinated chloride anions and enough space above, the chloride anions can be substituted by isophthalic acid and its derivatives. The functional groups of isophthalic acid do not affect the formation of similar C

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DOI: 10.1021/acs.cgd.6b01072 Cryst. Growth Des. XXXX, XXX, XXX−XXX