3D Inorganic Cuprous Iodide Open-Framework Templated by In Situ N

Ai-Huan Sun , Jie Pan , Song-De Han , Xu-Yan Xue , Qi Wei , Jin-Hua Li , and ... Guang-Ning Liu , Ruo-Yu Zhao , Hong Xu , Zi-Han Wang , Qi-Sheng Liu ,...
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3D Inorganic Cuprous Iodide Open-Framework Templated by In Situ N‑Methylated 2,4,6-Tri(4-pyridyl)-1,3,5-triazine Ai-Huan Sun, Song-De Han, Jie Pan, Jin-Hua Li, Guo-Ming Wang,* and Zong-Hua Wang College of Chemistry and Chemical Engineering, Collaborative Innovation Center of Marine Biomass Fiber Materials and Textiles, Qingdao University, Shandong 266071, China S Supporting Information *

ABSTRACT: A novel 3D inorganic cuprous iodide framework templated by in situ N-methylated 2,4,6-tri(4-pyridyl)-1,3,5triazine (TPT) was solvothermally prepared and structurally characterized. The title compound bearing chiral cuprous iodide chains as building units is the first 3D extended framework with the TPT-derivatives as template. The UV−vis diffuse-reflectance measurement reveals that 1 possesses semiconductor behavior with band gaps of 1.35 eV. The photoluminescent property of 1 has also been studied. shape, and flexibility of the organic amines may affect the process of assembly.17−20 Hitherto, the organic amines have been exploited in the fabrication of copper iodide-based frameworks, in which those organic species may participate in the resulting structures in three different forms. The first exist as protonated cations, acting as charge balancer and/or interacting with the CuI frameworks by electrostatic/supramolecular interactions,21−24 while the second participates in the formation of frameworks via direct covalent coordination with the Cu(I) ions.25−29 Assembling the typical copper(I) iodide clusters with DABCO (1,4-diazabicyclo[2.2.2]octane) can produce a series of cluster organic frameworks (COFs) with intriguing structures and photoluminescence.30−33 Typical examples include supramolecular isomerism in [Cu4I4(dabco)2],30 zeolite-like COF with new 66 topology,31 and MTN-type COF with giant cages.33 The third is coordinated to the metal ions to form isolated complexes as SDAs to direct the assembly.34−36 Undoubtedly, the decoration or mediation of the organic groups significantly enriches the framework constituent compared with the inorganic architecture based on the connection of copper(I) and iodide. As a rigid and neutral polypyridine ligand with C3 symmetry, the TPT molecule has been well utilized to construct extended

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etal halides evoke much interest from researchers due to their abundant structural chemistry and potential applications in the domains of photoluminescence, semiconductors, and phase transition materials.1−6 The assembly of distinct metal ions and halide anions (especially Cl−, Br−, I−) in the presence of various structure-directing agents (SDAs) (or templates) have generated numerous targeted structures with desirable properties, which is well epitomized by the metal halide with perovskite structures,7−10 haloantimonates(III), and halobismuthates(III) driven by various organic amines.11−16 Among the various reported metal halides, the copper(I) iodide family features rich structural characteristics and chemical or physical properties.17−20 The flexible coordination numbers of Cu(I) (from 2 to 4) and iodides (from terminal to μ2- and up to μ8-bridging) could in situ generate a series of CuxIy building units (rhomboid dimer Cu2I2, cubane tetramer Cu4I4, Cu6I6 hexamer, etc.), which provides freedom of fabricating a cuprous iodide structure.19 However, most of the reported cases are low-dimensional, which may be ascribable to the relatively low coordination number of the Cu(I) ion. Studies have demonstrated that the introduction of organoammonium into the cuprous iodide systems greatly diversify the structural chemistry and corresponding properties because of the intrinsic nature of the hybrid constituents.19 Thus, the meticulous choice of proper organoammonium plays an important part in the synthesis of the targeted structure, especially the high-dimensional framework, because the size, © XXXX American Chemical Society

Received: February 27, 2017 Revised: May 15, 2017 Published: June 5, 2017 A

DOI: 10.1021/acs.cgd.7b00296 Cryst. Growth Des. XXXX, XXX, XXX−XXX

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Figure 1. (a) Drawing showing the Cu10I18 cluster of 1. (b) Structure of 3D inorganic network along [100] direction. (c) Space-filling plot of the right-handed and right-handed helical CuI chains. (d) Topological view of the 3D 4-connected qzd net.

The cavities are occupied by Me3TPT groups to compensate the negative charge of the framework. It is worth mentioning that there are two types of helical chains with opposite configuration in compound 1. Along the [100] direction, unique right-handed helical chains are constructed from the infinite connection of {Cu(11)−I(1)− Cu(1)−I(6)−Cu(5)−I(10)−Cu(7)−I(14)−Cu(9)−I(18)− Cu(12)−I(2)−Cu(2)−I(5)−Cu(4)−I(9)−Cu(6)−I1(2)− Cu(10)−I(16)−Cu(11)−I(1)−Cu(1)−I(3)−Cu(12)−I(18)− Cu(9)−I(17)} (Figure 1c). Simultaneously, other unique lefthanded helical chains of {Cu(11)−I(17)−Cu(9)−I(18)− Cu(12)−I(3)−Cu(1)−I(1)} are generated by the μ2- and μ3I− bridged to Cu(I) atoms along the [001] direction. To further understand the present 3D structure, topological analysis is performed on compound 1. Each Cu10I18 SBU connects four metal atoms; hence, it can be considered a 4-connected node. Moreover, Cu(11) and Cu(12) atoms can be regarded as linkers. As a result, the whole 3D framework exhibits a 4connected qzd net with the point symbol of {75.9} (Figure 1d). Although the TPT has been well used in the generation of hybrid molecular materials, it is usually directly covalently coordinated to the metal ions by the N-coordination site. There are only a few discrete cases with the H3TPT as counterions. Moreover, no case for the TPT-templated 3D framework is reported up to now. Compound 1 represents the first 3D architecture driven by the TPT-derivate template. A overview of the literature indicated there are few inorganic 3D copper(I) halide architectures. Compound 1 is also the first 3D inorganic copper(I) iodide architecture with the organoammonium as SDA. Notably, the starting reactant TPT in situ converted to (Me)3TPT via N-methylation of TPT and MeOH. Such in situ alkylation has also been observed in other metal halide systems. The successful preparation of 1 not only enriches the existing family of TPT-based molecular materials, but also offers a rare 3D extended framework structure templated by Me3TPT. This work highlights the potential of TPT as a novel template (or SDA) in the preparation of high-dimensional copper(I) halide materials and provides the opportunity to generate a novel framework structure directed by the TPT-derivative ligand.

framework materials and isolated cages with fascinating properties.37−39 However, in most of the reported TPTcontaining molecular materials, the TPT is coordinated to the metal ions via the N-donors. Only in a few isolated examples is the TPT protonated.40 To the best of our knowledge, there is no case reported for high-dimensional frameworks with (protonated) TPT as SDAs. Herein, we report the first 3D inorganic cuprous iodide open-framework templated by in situ N-methylated TPT ((Me)3TPT), [(Me)3TPT]2[Cu12I18] (1). Compound 1 was obtained from the solvothermal reaction of CuI, TPT, and HI (45% solution) at 120 °C for 4 days. Interestingly, the initial material TPT converted into (Me)3TPT via in situ N-methylation of TPT and MeOH, which locate and act as SDA to direct the formation of the resulting 3D inorganic skeleton. Single-crystal X-ray diffraction analysis reveals that 1 crystallizes in trigonal space group P32. The asymmetric unit consists of 12 copper(I) atoms, 18 iodine atoms, and 2 (Me)3TPT cationic moieties. Of the 12 Cu atoms, Cu(1) to Cu(4) atoms, together with Cu(7) to Cu(10) atoms, are coordinated by four I− ions with distorted tetrahedral geometries. For Cu(5), Cu(6), Cu(11), and Cu(12) atoms, they are all three-coordinated by I− ions, giving similar distorted {CuI3} triangle geometries. The Cu−I distances are located in the range 2.510−2.910 Å, and I−Cu−I bond angles are in the scope of 95.97° and 136.90°. Interestingly, the Cu(1) to Cu(10) atoms are linked together by I− ions and direct Cu−Cu bonds, displaying a fascinating Cu10I18 secondary building units (SBUs) as shown in Figure 1a. The Cu···Cu distances span from 2.438 to 2.967 Å, being a little shorter than the sum of van der Waals radii of Cu(I) (2.8 Å) and implying a strong metal− metal cuprophilic interaction in the cluster. As depicted in Figure 1b, each decanuclear Cu10I18 cluster links its quivalent neighbors via sharing the Cu(11) atom to produce a 1D Cu10 cluster-based chain extending along the a axis and b axis. Furthermore, the inorganic chains in 1 propagate in two noncoplanar directions that are assembled by the Cu(12) atom, resulting in an intriguing 3D network. Along the a axis, the staggered chains create a key-shaped 27membered window sized at 25.382 × 24.077 Å2 (Figure S1). B

DOI: 10.1021/acs.cgd.7b00296 Cryst. Growth Des. XXXX, XXX, XXX−XXX

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Figure 2. (a) Optical diffuse reflectance spectrum for 1. (b) Solid-state emission spectra of compound 1 at room temperature.

Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

As illustrated in Figure S2, no obvious weight loss was observed before 250 °C for compound 1. Upon further heating, it undergoes a weight loss of 19.26% between 250 and 470 °C, which is caused by the decomposition of organic amines (calcd 19.00%). The solid-state optical diffuse reflection spectrum of the title compound was measured at room temperature. According to the Kubelka−Munk function where α/S = (1 − R)2/2R, optical diffuse reflectance studies reveal that the band gap of 1 is approximately 1.35 eV (Figure 2a), showing that 1 is a potential semiconductor material. Considering the luminescent properties of d10 ions, the photoluminescence of compound 1 was studied at room temperature in the solid state. The peak at 520 nm was due to the triplet clustercentered (3CC) transitions, while the peak at 430 nm was ascribed to the triplet metal to ligand charge transfer transitions.31−33 In summary, a novel 3D inorganic cuprous iodide openframework has been synthesized by employing in situ Nmethylated Me3TPT as structure directing agent. It exhibits an unprecedented 3D architecture with two types of helical chains. The most important feature of 1 is its 27-membered window along the bc plane. It is worth mentioning that compound 1 is the first 3D inorganic copper(I) iodide structure with the TPTderivate as SDA up to now. This work has demonstrated that the design and construction of novel high-dimensional openframework materials through the use of TPT is possible. Further investigation of halogeno-cuprate materials is in progress.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Song-De Han: 0000-0001-6335-8083 Guo-Ming Wang: 0000-0003-0156-904X Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS We acknowledge the grants from the Natural Science Foundation of China (21571111, 21601101) and Taishan Scholar Program (ts201511027).

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* Supporting Information S

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.cgd.7b00296. Experimental section, supplementary structural figures and tables, PXRD, TGA, luminescence, and IR curves (PDF) Accession Codes

CCDC 1534077 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 data_ [email protected], or by contacting The Cambridge C

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DOI: 10.1021/acs.cgd.7b00296 Cryst. Growth Des. XXXX, XXX, XXX−XXX