DOI: 10.1002/chem.201405800

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Reversible Transformation between Cubane and Stairstep Cu4I4 Clusters Using Heat or Solvent Vapor Seonghwa Cho, Youngeun Jeon, Sangjin Lee, Jineun Kim,* and Tae Ho Kim*[a] cations in the selective separation of gas mixtures. Therefore, we were motivated to study the reversible structural transformations in CPs based on CuI and N/S donor ligands by using gas–solid reactions. Herein, we report the structures, photoluminescence, and thermal properties of three CuI CPs. The reversible transformations of the crystal structures were controlled by conditions such as methanol vapor (MeOH(g)), acetonitrile vapor (MeCN(g)), and heat. A mixed N/S-donor ligand, 2-(tert-butylthio)-N-(pyridin-3-yl)acetamide (L), was synthesized by the reaction of 2-(tert-butylthio)acetic acid and 3-aminopyridine in chloroform, using a method similar to that reported in the literature.[12] Slow evaporation yielded good-quality crystals for single-crystal Xray diffraction (SCXRD; Scheme S1 in the Supporting Information; the crystal data for L are listed in Table S1, and an ORTEP view is shown in Figure S1). Three CuI CPs, [Cu4I4L2(MeCN)2]n (1), [Cu4I4L2]n (2), and {[Cu4I4L2]·MeOH}n (3) were prepared through the reaction of CuI and L in a 2:1 molar ratio in acetonitrile, acetonitrile/ethyl acetate (1:1), and acetonitrile/methanol (1:1), respectively (Scheme 1 and synthesis details in the Supporting Information). Good single crystals for SCXRD were obtained by slow evaporation. CPs 1–3 were characterized by elemental analysis, thermogravimetric analysis (TGA), differential thermal analysis (DTA), photoluminescence spectroscopy, powder XRD, and SEM (see details in the Supporting Information). A 1D loop-chain structure in CP 1 (Figure 1a, left) was confirmed by SCXRD studies (Tables S1 and S2 in the Supporting Information). CP 1 crystallizes in the triclinic P-1 space group with a crystallographically imposed inversion center. Each square compartment of the loop is composed of two stair-step Cu4I4 clusters, two acetonitrile molecules, and two Ls. All copper atoms in the Cu4I4 clusters have distorted tetrahedral geometries. The inner copper ions (Cu2) in the cluster are coordinated by three iodide ions and a pyridyl-N atom. The outer copper atoms (Cu1) are coordinated by two iodide ions, an S atom, and the N atom of an acetonitrile molecule, which gives CN stretching bands at 2299 and 2264 cm 1 (Figure S7, Supporting Information). The loop chains along the [220] direction are packed along the a-axis (Figure S3b, Supporting Information). In the crystal structure, weak intermolecular p–p interactions (3.695(17) ) between the pyridyl groups, as well as the C H···O hydrogen bonds (C13···O1, 3.268(4) , H13B···O1, 2.317 ), contribute to the stabilization of the packing (Figure 1a, right). CP 2 crystallizes in the monoclinic P21/n space group with a crystallographically imposed inversion center. 2D networks of CP 2 span the ac plane and are packed along the

Abstract: The controlled self-assembly of CuI and an asymmetric ligand with mixed N/S donors, 2-(tert-butylthio)-N-(pyridin-3-yl)acetamide (L), afforded three CuI coordination polymers (CPs), [Cu4I4L2(MeCN)2]n (1), [Cu4I4L2]n (2), and {[Cu4I4L2]·MeOH}n (3). X-ray analyses showed that CPs 1–3 are supramolecular isomers with 1, 2, and 3D structures, respectively. CP 1 adopts a stairstep Cu4I4 cluster, whereas CPs 2 and 3 are composed of cubane-like Cu4I4 clusters. Crystal-to-crystal transformations of 1 to 2 and 3 showed reversible transformations between different Cu4I4 clusters using heat or solvent (acetonitrile or methanol) vapor. CP 2 was reversibly transformed to 3 by the addition of methanol and heat. Therefore, the transformations between supramolecular isomers 1, 2, and 3 are completely reversible.

In recent years, studies of structural transformation mechanisms in the solid state have attracted attention among scientists.[1, 2] Crystal-to-crystal transformations primarily occur by stimulation with either heat or light, or by vapor-diffusion in the solid state.[3–5] Such transformation phenomena can be used for various applications, including chemical sensors, catalysts, and magnetic materials.[6–8] Copper(I) halides are capable of adopting a variety of coordination modes ranging from 0 D complexes to 3 D polymeric networks containing various cluster cores, such as rhomboid dimers, cubane or stairstep clusters, 1 D chains, and double-stranded stairs.[9] We have been interested in the development of photoluminescent CuI CPs based on CuI and N/S donor ligands.[10] Our studies have focused on the reversible or irreversible structural transformations and luminescence changes in these compounds as a function of temperature and solvent.[11] We have shown that conformational changes of the sulfur-containing ligands and the lability of the Cu S bond play an important role in these structural transformations.[11b] However, reversible crystal transformations of CuI CPs by solvent vapor have not yet been reported. Such transformations are important for their possible appli[a] S. Cho, Y. Jeon, S. Lee, Prof. J. Kim, Dr. T. H. Kim Department of Chemistry and Research Institute of Natural Science Gyeongsang National University 501 Jinju Daero, Jinju 660-701(Republic of Korea) E-mail: [email protected] [email protected] Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/chem.201405800. Chem. Eur. J. 2014, 20, 1 – 6

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Scheme 1. Preparation and crystal-to-crystal transformations of CPs 1–3.

Figure 1. Packing structures and intermolecular interactions of CPs: 1 (a), 2 (b), and 3 (c). The C H···O, N H···O, and O H···O hydrogen bonds and weak p···p interactions are shown as dashed lines.

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b-axis. In the crystal structure of CP 2, N H···O (N4···O1, 2.993(11) , H4N···O1, 2.151 , and N2···O2, 2.878(11) , H2N···O2, 2.004 ) hydrogen bonds contribute to the stabilization of the packing (Figure S4, Supporting Information). CP 3 crystallizes in the trigonal P3221 space group with a crystallographically imposed inversion center. Methanol molecules link two neighboring ligands by hydrogen bonds. In the crystal structure of CP 3, N H···O (N2···O2, 2.778(14) ), O H···O (O2···O1, 2.724(15) , H2O···O1, 2.266 ), and weak C H···O (C12···O1, 3.125(14) , H12B···O1, 2.596 ) hydrogen bonds contribute to the stabilization of the packing (Figure 1c). CPs 2 and 3 feature 2 D and 3 D networks generated by linking cubane Cu4I4 cluster cores with Ls. The two Ls in the asymmetric unit of CP 2 have two different conformations; the Ls are located on the same side of the cubane Cu4I4 cluster, as shown in Figure S2, Supporting Information, and one L crosses over the other. Each pyridyl group binds different cubane Cu4I4 clusters in the next column, resulting in a 2 D network structure (Figure 1b, left). Conversely, the asymmetric unit of CP 3 has only one conformation of L. The four Ls in a cubane Cu4I4 cluster generated by the symmetry operation bind four different cubane Cu4I4 clusters, forming the 3 D network structure (Figure 1c). Two of the copper ions in 2 and 3 exist in distorted tetrahedral environments with three iodide ions and one sulfur atom in their coordination shells, whereas the other two copper ions coordinate three iodide ions and a pyridyl-N atom in their coordination shells. The Cu–Cu (2.5988(18)– 2.8273(5) ), Cu I (2.5834(3)– 2.7240(10) ), Cu S (2.3293(19)– 2.3304(7) ), Cu N (2.030(6)– 2.041(3) , pyridyl-N) bond

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Communication loss behavior: coordinated acetonitrile molecules in CP 1 were removed in the range of 100– 120 8C and solvated methanol molecules in CP 3 were removed in the range of 120–150 8C. Conversely, CP 2 was stable to about 190 8C. The loss of L in CPs 1–3 by decomposition occurred at temperatures ranging from 190 to 400 8C. Two peaks at 118 and 140 8C in the DTA curves of 1 and 3, respectively, were important indicators of the crystal transformations of 1 and 3 to 2. These peaks were accompanied by significant losses in weight owing to the removal of the solvent molecules, as observed in Figure 2. Photographs of CPs 1–3 before heating without (a) and with (b) UV irradiation, and with UV irradiation the TGA curves. after heating (c). Photoluminescence spectra of polycrystalline CPs 1–3 before (d) and after (e) heating (lex = 350 nm). Figure 2 shows photographs of CPs 1–3 without and with UV irradiation, as well as their PL spectra before and after crystal transformation by heating at lengths in CPs 1–3 and Cu N (1.981(3) , acetonitrile–N) bond 130 8C. Before heating, CPs 1–3 were white powders and length in CP 1 are within the range of known values.[9–11] showed blue, orange, and yellow/green emissions, respectively, The photoluminescence spectra of CPs 1–3 in the solid state under UV irradiation. The emission color of CP 2 was the same at room temperature were investigated, and the emission before and after heating, whereas after heating the emission spectra are shown in Figure 2d. CPs 1–3 exhibited strong phocolors of CPs 1 and 3 were the same as that of CP 2, which intoluminescence with emission maxima at approximately 460, dicated that CPs 1 and 3 were transformed into CP 2. These 590, and 530 nm, respectively, upon excitation at 350 nm. The changes in emission color were consistent with the emission emissions from CPs 1–3 might be assigned to metal-to-ligand spectra before and after heating at 130 8C (Figure 2d and e, recharge-transfer (MLCT) and cluster center (CC) excited states, spectively). In addition, these transformations were confirmed with some mixing of the halide-to-ligand charge-transfer by the PXRD patterns (Figure S12 in the Supporting Informa(XLCT) and iodide-to-copper charge-transfer (XMCT) charaction). ters.[13] The photoluminescence properties of stair-step comFigure 3 shows photographs of the samples under UV irradiplex 1 are similar to those of a pinwheel-shaped Cu7I7 cluster ation, as well as their PXRD patterns, which demonstrates cryscomplex with an N/S donor ligand, which shows a partial stairtal transformations using solvent vapor from 2 to 3 via 1 and, step Cu4I4 structure.[10b] The emission maximum of 2 is similar to those of cubane Cu4I4 cluster complexes reported in the literature.[14] The emission maximum of 3 was expected, in the absence of methanol, to be similar to that of 2. Thus, the observed blueshift in the emission maximum of 3 in comparison with that of 2 was attributed to electron donation to the ligands from methanol molecules in the framework of CP 3. To investigate the thermal stabilities of CPs 1–3, TGA and DTA were carried out at a rate of 10 8C min 1 in a N2 atmosphere Figure 3. Photographs of CP 2 (a), CP 2 transformed by MeCN(g) (b), and MeOH(g) (c) under UV irradiation. Calcu(Figure S8, Supporting Informalated and experimental PXRD patterns of CP 2 (d), calculated and experimental PXRD patterns of CP 1 and CP 2 tion). The TGA curves for CPs transformed by MeCN(g), respectively (e), and calculated and experimental PXRD patterns of CP 3 and CP 1 trans1 and 3 exhibited similar weight- formed by MeOH(g), respectively (f). Chem. Eur. J. 2014, 20, 1 – 6

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conversely, from 3 to 2 via 1. Unfortunately, the crystal transformation between 2 and 3 did not occur with MeOH(g). However, the crystal transformation from 2 to 3 took place in MeOH(l). The interaction energy between the Ls and MeOH(g) may not be strong enough to achieve the conformation of L required for the transformation, whereas the solvation by MeOH(l) may cause movement of the Ls and provide enough energy for the transformation. The reverse transformation occurred by heating, as mentioned previously. During the crystal transformation from 2 to 1, cubane Cu4I4 clusters must be opened to form stair-step Cu4I4 clusters; this process is likely caused by coordination of acetonitrile molecules to the cubane Cu4I4 cluster. Acetonitrile coordination and cubane Cu4I4 cluster opening generates structural strain, which causes the rearrangement from the 2D network of 2 to the 1D loop chain structure of 1. In the crystal transformation from 1 to 3, stair-step Cu4I4 clusters must be closed to form cubane Cu4I4 clusters; this process is probably caused by the formation of hydrogen bonds between methanol molecules and Ls and between neighboring methanol molecules. These hydrogenbonding interactions generate structural strain, which causes rearrangement from the 1 D loop chain structure of 1 to the 3 D network structure of 3, as well as the rearrangement from stairstep Cu4I4 clusters to cubane Cu4I4 clusters. Surprisingly, this reversible transformation between stair-step and cubane Cu4I4 clusters has never been previously reported. Crystal transformations using solvent vapor from 2 to 1, 1 to 3, and 3 to 1 were completed after about 15, 90, and 20 min, as shown in Videos S1–S3 (Supporting Information), respectively. The relatively fast crystal transformations from 2 and 3 to 1 might occur because the easy and direct formation of bonds between the copper ions in the cubane Cu4I4 clusters and the N atoms of the acetonitrile molecules results in great strain. Conversely, the crystal transformation from 1 to 3 might occur more slowly owing to the relatively weak strain caused by hydrogen bond formation between ligands and methanol molecules. In summary, we have synthesized three supramolecular isomeric CuI CPs that showed reversible crystal transformations using solvent vapor or application of heat. Novel transformations of Cu4I4 between stairstep and cubane clusters were observed. We have demonstrated for the first time that the frameworks of the CPs were not maintained, but rearranged between 1D chain, 2D, and 3D networks during the reversible crystal transformations using solvent vapor. Remarkably, our results indicated that the cleavage of coordination bonds during these transformations could even occur in CPs at room temperature when great strain is present owing to the strong hydrogen-bonding interactions between the guest molecules and the CP framework. Such strong intermolecular interactions also affect the photoluminescence (PL) spectra and structural transformations of the CPs. Further studies on the reversible crystal transformations of CuI CPs with various Ls are in progress, as the changes in the physical properties that accompany the crystal transformations are important in detecting and separating volatile gases.

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All chemicals and solvents used in the syntheses were of reagent grade and were used without further purification. The 1H and 13 C NMR spectra were recorded on a Bruker Advance-300 (300 MHz) NMR spectrometer. FTIR spectra were measured under vacuum with a Bruker DE/Vertex 80 V FTIR spectrometer. Elemental analyses were carried out on a Perkin–Elmer model 2400 analyzer. TGA and DTA were performed under nitrogen at a scan rate of 10 8C min 1 using a TA SDT Q600 thermogravimetric analyzer. ESImass spectra were obtained on a Thermo Scientific LCQ spectrometer. Solid-state luminescence spectra were acquired with a HITACHI F-7000 spectrophotometer; the pulsed excitation source was generated using 350 nm light from a Xenon lamp. For fieldemission SEM (FE-SEM), a small amount of compound was placed on a glass plate; after Pt coating, the specimen was examined with a JEOL JSM-6701F SEM. The PXRD patterns were obtained with a Bruker AXS D8 DISCOVER diffractometer by using CuKa (1.54056 ) radiation. The powder diffraction frames were collected at 258 intervals in the 2q range of 0–508 for 30 s at a detector distance of 15 cm. The two frames were integrated from 5 to 508 and merged. SCXRD data for L and 1–3 were collected with a Bruker SMART APEX II ULTRA diffractometer. The cell parameters for the compounds were obtained from a least-squares refinement of the spots (from 36 collected frames). Data collection, data reduction, and semiempirical absorption corrections were carried out using APEX2.[15] All of the calculations for the structure determination were carried out using SHELXTL.[16] In all cases, all non-hydrogen atoms were refined anisotropically. All hydrogen atoms were placed in calculated positions and refined isotropically riding on their respective parent atoms. Relevant crystal data collection parameters, refinement data for the crystal structures, and the selected bond lengths and angles of L and 1–3 are summarized in Tables S1–S3 (Supporting Information). CCDC-1001936–1001938 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.

Acknowledgements This research was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science, and Technology (grants: 2014R1A1A4A01009105 and 2012R1A1B3003337). Keywords: cluster transformation · coordination polymers · crystal transformation · photoluminescence · supramolecular chemistry [1] a) J. J. Vittal, Coord. Chem. Rev. 2007, 251, 1781 – 1795; b) J. S. Costa, S. Rodriguez-Jimenez, G. A. Craig, B. Barth, C. M. Beavers, S. J. Teat, G. Aromi, J. Am. Chem. Soc. 2014, 136, 3869 – 3874; c) D. Liu, M. Li, D. Li, Chem. Commun. 2009, 6943 – 6945; d) G. Mnguez Espallargas, M. Hippler, A. J. Florence, P. Fernandes, J. van de Streek, M. Brunelli, W. I. F. David, K. Shankland, L. Brammer, J. Am. Chem. Soc. 2007, 129, 15606 – 15614; e) S. Libri, M. Mahler, G. M. Espallargas, D. C. N. G. Singh, J. Soleimannejad, H. Adams, M. D. Burgard, N. P. Rath, M. Brunelli, L. Brammer, Angew. Chem. Int. Ed. 2008, 47, 1693 – 1697; Angew. Chem. 2008, 120, 1717 – 1721. [2] a) T. Seki, K. Sakurada, H. Ito, Angew. Chem. Int. Ed. 2013, 52, 12828 – 12832; Angew. Chem. 2013, 125, 13062 – 13066; b) Z. Duan, Y. Zhang, B. Zhang, D. Zhu, J. Am. Chem. Soc. 2009, 131, 6934 – 6935; c) J. Mart-

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[3]

[4]

[5]

[6]

[7]

Rujas, N. Islam, D. Hashizume, F. Izumi, M. Fujita, M. Kawano, J. Am. Chem. Soc. 2011, 133, 5853 – 5860; d) S. C. Hau, P. S. Cheng, T. C. Mak, J. Am. Chem. Soc. 2012, 134, 2922 – 2925; e) M. Kondo, M. Murata, H. Nishihara, E. Nishibori, S. Aoyagi, M. Yoshida, Y. Kinoshita, M. Sakata, Angew. Chem. Int. Ed. 2006, 45, 5461 – 5464; Angew. Chem. 2006, 118, 5587 – 5590. a) J. Sun, F. Dai, W. Yuan, W. Bi, X. Zhao, W. Sun, D. Sun, Angew. Chem. Int. Ed. 2011, 50, 7061 – 7064; Angew. Chem. 2011, 123, 7199 – 7202; b) G. Mahmoudi, A. Morsali, Cryst. Growth Des. 2008, 8, 391 – 394; c) H. Sadeghzadeh, A. Morsali, Inorg. Chem. 2009, 48, 10871 – 10873; d) X.-N. Cheng, W.-X. Zhang, X.-M. Chen, J. Am. Chem. Soc. 2007, 129, 15738 – 15739. a) G. K. Kole, T. Kojima, M. Kawano, J. J. Vittal, Angew. Chem. Int. Ed. 2014, 53, 2143 – 2146; Angew. Chem. 2014, 126, 2175 – 2178; b) D. B. Varshney, X. Gao, T. Frisˇcˇic´, L. R. MacGillivray, Angew. Chem. Int. Ed. 2006, 45, 646 – 650; Angew. Chem. 2006, 118, 662 – 666; c) P. B. Chatterjee, A. Audhya, S. Bhattacharya, S. M. T. Abtab, K. Bhattacharya, M. Chaudhury, J. Am. Chem. Soc. 2010, 132, 15842 – 15845. a) K. Uehara, T. Taketsugu, K. Yonehara, N. Mizuno, Inorg. Chem. 2013, 52, 1133 – 1140; b) S. H. Lim, M. M. Olmstead, A. L. Balch, Chem. Sci. 2013, 4, 311 – 318; c) A. Kobayashi, K. Komatsu, H. Ohara, W. Kamada, Y. Chishina, K. Tsuge, H. C. Chang, M. Kato, Inorg. Chem. 2013, 52, 13188 – 13198; d) S. Supriya, S. K. Das, J. Am. Chem. Soc. 2007, 129, 3464 – 3465; e) B. Li, R.-J. Wei, J. Tao, R.-B. Huang, L.-S. Zheng, Z. Zheng, J. Am. Chem. Soc. 2010, 132, 1558 – 1566; f) J.-J. Wu, Y.-X. Ye, Y.-Y. Qiu, Z.-P. Qiao, M.-L. Cao, B.-H. Ye, Inorg. Chem. 2013, 52, 6450 – 6456; g) S. M. Mobin, A. K. Srivastava, P. Mathur, G. K. Lahiri, Inorg. Chem. 2009, 48, 4652 – 4654. a) G.-R. Park, H.-J. Yang, T.-H. Kim, J.-E. Kim, Inorg. Chem. 2011, 50, 961 – 968; b) R. J. Wei, J. Tao, R. B. Huang, L. S. Zheng, Inorg. Chem. 2011, 50, 8553 – 8564; c) T. H. Kim, S. Lee, Y. Jeon, Y. W. Shin, J. Kim, Inorg. Chem. Commun. 2013, 33, 114 – 117; d) A. D. Naik, K. Robeyns, C. F. Meunier, A. F. Leonard, A. Rotaru, B. Tinant, Y. Filinchuk, B. L. Su, Y. Garcia, Inorg. Chem. 2014, 53, 1263 – 1265. a) J. Huang, L. He, J. Zhang, L. Chen, C.-Y. Su, J. Mol. Catal. A 2010, 317, 97 – 103; b) D. N. Dybtsev, A. L. Nuzhdin, H. Chun, K. P. Bryliakov, E. P. Talsi, V. P. Fedin, K. Kim, Angew. Chem. Int. Ed. 2006, 45, 916 – 920;

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www.chemeurj.org

These are not the final page numbers! ÞÞ

[8] [9]

[10]

[11]

[12] [13] [14]

[15] [16]

Angew. Chem. 2006, 118, 930 – 934; c) Z. Huang, P. S. White, M. Brookhart, Nature 2010, 465, 598 – 601. a) M. Nihei, L. Han, H. Oshio, J. Am. Chem. Soc. 2007, 129, 5312 – 5313; b) W. Fujita, K. Awaga, J. Am. Chem. Soc. 1997, 119, 4563 – 4564. a) K. M. Henline, C. Wang, R. D. Pike, J. C. Ahern, B. Sousa, H. H. Patterson, A. T. Kerr, C. L. Cahill, Cryst. Growth Des. 2014, 14, 1449 – 1458; b) M. Knorr, F. Guyon, A. Khatyr, C. Strohmann, M. Allain, S. M. Aly, A. Lapprand, D. Fortin, P. D. Harvey, Inorg. Chem. 2012, 51, 9917 – 9934; c) A. Bonnot, C. Strohmann, M. Knorr, P. D. Harvey, J. Cluster Sci. 2014, 25, 261 – 275; d) Y. Zhang, T. Wu, R. Liu, T. Dou, X. Bu, P. Feng, Cryst. Growth Des. 2010, 10, 2047 – 2049; e) J. Y. Lee, S. Y. Lee, W. Sim, K.-M. Park, J. Kim, S. S. Lee, J. Am. Chem. Soc. 2008, 130, 6902 – 6903; f) P. C. Ford, E. Cariati, J. Bourassa, Chem. Rev. 1999, 99, 3625 – 3648; g) X.-Q. Wang, J.-K. Cheng, Y.-H. Wen, J. Zhang, Z.-J. Li, Y.-G. Yao, Inorg. Chem. Commun. 2005, 8, 897 – 899; h) J. Vallejos, I. Brito, A. Cardenas, M. Bolte, J. Llanos, M. Lopez-Rodriguez, Inorg. Chem. Commun. 2012, 24, 59 – 62. a) Y. Jeon, S. Cheon, S. Cho, K. Y. Lee, T. H. Kim, J. Kim, Cryst. Growth Des. 2014, 14, 2105 – 2109; b) S. Cheon, T. H. Kim, Y. Jeon, J. Kim, K.-M. Park, CrystEngComm 2013, 15, 451. a) T. H. Kim, Y. W. Shin, J. H. Jung, J. S. Kim, J. Kim, Angew. Chem. Int. Ed. 2008, 47, 685 – 688; Angew. Chem. 2008, 120, 697 – 700; b) T. H. Kim, H. Yang, G. Park, K. Y. Lee, J. Kim, Chem. Asian J. 2010, 5, 252 – 255. T. H. Kim, Y. W. Shin, S. S. Lee, J. Kim, Inorg. Chem. Commun. 2007, 10, 11 – 14. H. Araki, K. Tsuge, Y. Sasaki, S. Ishizaka, N. Kitamura, Inorg. Chem. 2005, 44, 9667 – 9675. a) S. Hu, M. L. Tong, Dalton Trans. 2005, 1165 – 1167; b) X. Chai, S. Zhang, Y. Chen, Y. Sun, H. Zhang, X. Xu, Inorg. Chem. Commun. 2010, 13, 240 – 243; c) S. Yuan, S.-S. Liu, D. Sun, CrystEngComm 2014, 16, 1927. Bruker, APEX2 Version 2009.1 – 0, Data Collection and ProcessingSoftware, Bruker AXS Inc., Madison, Wisconsin, 2008. Bruker, SHELXTL-PC Version 6.22, Program for Solution and Refinement of Crystal Structures, Bruker AXS Inc., Madison, Wisconsin, 2001.

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Cluster transformations: Three supramolecular isomeric CuI coordination polymers showed reversible crystal transformations using solvent vapor or the application of heat (see scheme). Surprisingly, transformations between stairstep and cubane Cu4I4 clusters were observed during the crystal transformations.

S. Cho, Y. Jeon, S. Lee, J. Kim,* T. H. Kim* && – && Reversible Transformation between Cubane and Stairstep Cu4I4 Clusters Using Heat or Solvent Vapor

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Reversible transformation between cubane and stairstep Cu4I4 clusters using heat or solvent vapor.

The controlled self-assembly of CuI and an asymmetric ligand with mixed N/S donors, 2-(tert-butylthio)-N-(pyridin-3-yl)acetamide (L), afforded three C...
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