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Synthesis, structures and properties of Cu and Cd complexes with 1,10-phenanthroline
Inorganic Chemistry Communications 13 (2010) 645–648
Contents lists available at ScienceDirect
Inorganic Chemistry Communications j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / i n o c h e
Synthesis, structures and properties of Cu and Cd complexes with 1,10-phenanthroline Jingya Sun ⁎, Xiangdi Tong, Huanzhi Xu College of Marine Sciences, Zhejiang Ocean University, Zhoushan 316000, PR China
a r t i c l e
i n f o
Article history: Received 8 January 2010 Accepted 2 March 2010 Available online 11 March 2010 Keywords: crystals structure weak interactions fluorescence 1, 10-phenanthroline
a b s t r a c t Three new Cu and Cd complexes, namely [Cu(phen)(isca)(EtOH)] (1) [Cu(phen)2(HCOOH)] (2) and [Cd (phen)Cl2](3) (phen = 1, 10-phenanthroline, isca = isophthalic acid) have been synthesized, which are characterized by elemental analysis, infrared spectrum and x-ray crystal diffraction. While strong hydrogen bonds play central roles in the formation of the 3D structure, the combined influence of the weak interactions such as C-H···O bonds, C-H···π and lone pair···π interactions are also evident in the structures. The preliminary investigation on the thermal and fluorescence property of the complexes are presented. Crown Copyright © 2010 Published by Elsevier B.V. All rights reserved.
Recently, interest has been focused on the design strategies and construction of the architectures with diversity topologies in supramolecular chemistry and crystal engineering [1]. Organic bridging ligands play an important role in the synthesis, and studies directed towards evaluating their influence on the formation of different network [2]. Self-assembly is the fundamental molecular recognition process adopted by nature to generate the elegant and intricate molecular machine, the formation of which is dependent upon an interplay of weak intermolecular interactions which are instrumental in the formation of weakly bound columns: offset π stacking plus C-H···π interactions [3]. Hydrogen bonding still remains the most reliable and widely used means of enforcing molecular recognition [4]. The selfassembly of molecular building blocks through molecular recognition has led the way in the development of a number of functional allorganic and hybrid inorganic-organic materials [5]. Besides these conventional strong hydrogen bonds, varieties of unconventional intermolecular interactions or contacts have also been found to be instrumental in determining the supramolecular structure of organic solids [6]. The supramolecular interactions with π aromatic clouds, such as C-H···π, cation···π and π···π stacking, have been demonstrated extensively both experimentally and theoretically [7–9]. In recent years, non-covalent interactions involving π-systems, such as C-H···π and anion-π interactions [10,11], which was primarily thought to be improbable due to the electron donating character of anions and the expected repulsive interactions with aromatic πsystems, have been extensively studied in the last decade. C-H···π interactions have been recognized by the scientific community as an
⁎ Corresponding author. E-mail address: [email protected] (J. Sun).
important type of supramolecular interaction. Likewise, experimental proofs for non-covalent interactions, and more generally for lone pair···π interactions, are presented in the literature [12–15]. In this context, we have succeeded in obtaining three new complexes [Cu(phen) (isca) (EtOH)] (1) [Cu(phen)2(HCOOH)] (2) and [Cd (phen)Cl2] (3) base on phen ligand [16]. Strong hydrogen bonds and π···π interactions play important roles in the formation of the 3D structure. Single-crystal X-ray diffraction measurement reveals that the crystal of the complex 1 conform to the space group P2(1)/n (Table S1). A molecular structure showing the arrangement about the Cu (II) metal center is shown in Fig. 1a. The Cu (II) ion lies on the inversion center so that the asymmetry unit comprises one-half of the formula unit. In the crystal structure of 1, there is one Cu (II) atom, one isophthalic acid ligand and one lattice EtOH molecules in each independent crystallographic unit. Each Cu (II) atom in 1 is primarily coordinated by four oxygen atoms from two isophthalic acid ligand (Cu-O(1) 1.96 Å; Cu-O (3) 1.92 Å) and two nitrogen atoms from the phen ligand (Cu-N(1) 2.002 Å; Cu-N(2) 2.001 Å) to furnish a distorted octahedral coordination geometry. Each pair of adjacent Cu (II) atoms is bridged by an isophthalic acid ligand to form a chain running along the c direction. These chains are decorated with phen ligands alternatedly at two sides (Fig. 3a). The isca phenyl rings at each side of the chain are arranged in a parallel fashion with an inter-ring distance of 7.88 Å. Indeed, each pair of homochiral polymeric chains intertwine into a unique double-stranded helix of C2 symmetry through π···π stacking interactions between the phen ligands (face-to-face distances of 3.736 Å) (Fig. 2a). The interfacial distance of 3.736 Å indicates a strong aromatic π···π stacking interaction. [17,18] These layers are further extended into two-dimensional (2D) networks through C-H···π interaction between phen and isca phenyl rings from adjacent layers [with C(17)-H(17)···Cg = 3.535 Å, Cg is the centroid of the ring defined by the atoms C2 to C7, the angle C (17)-H(17)···Cg is 153.48°] (Fig. 2b). Similar zipperlike interactions
1387-7003/$ – see front matter. Crown Copyright © 2010 Published by Elsevier B.V. All rights reserved. doi:10.1016/j.inoche.2010.03.009
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J. Sun et al. / Inorganic Chemistry Communications 13 (2010) 645–648
Fig. 1. The metal coordination environment in 1, 2 and 3. All the hydrogen atoms were omitted for clarity.
Fig. 2. Showing the face-to-face π···π stacking of complex 1 (a); The C-H···π interactions between the phen and isca in complex 1 (b).
have been reported previously in some three-dimensional coordination architectures constructed by two-dimensional layers [17]. Complex 2 conform to the space group C2/c space group (Table S1). A molecular structure showing the arrangement about the Cu (II) metal center is shown in Fig. 1b. The Cu atom is six coordinated and adopts distorted octahedral coordination geometry by coordinating to four nitrogen atoms from the phen ligands and two oxygen atoms from the carboxyl group of the methane acid ligand, with N1 in the axial position and O1 and N2 in the equatorial plane (Cu-O(1) 2.002 Å; Cu-N(1) 1.989 Å; Cu-N(2) 2.111 Å). These complexes are extended through π···π stacking between the phen forming a 2D network. There are 1D channels along b-axis,
and the perchlorate anions are filled into the 1D channels through strong hydrogen bonds and π···π stacking interaction (with central to central distance of 3.587 Å) as showing in Fig. S1. It is noteworthy that the perchlorate anion is not coordinated to the 3D framework due to its weak coordination ability. Analysis of the crystal packing of the title compound reveals the existence of anion-π interactions between the host and the anions (Fig. 4). The O2···centroid A distance is 3.38 Å and angle O1-ring centroid-aromatic plane amounts to 68.4°. The perchlorate oxygen atom O3 is also in contact with the phen plane (O2···centroid B distance is 3.862 Å and the angle 50.35°). Complex 3 conform to the space group C2/c (Table S1). The coordination environment of the central atom is shown in Fig. 1c. The structure expands along b axis through the bridging μ2-Cl ligand into a
Fig. 3. The π···π stacking interactions in complex 1 and 3 shown in spacefilling model.
Fig. 4. Crystal packing of complex 2 illustrating the anion···π contacts.
J. Sun et al. / Inorganic Chemistry Communications 13 (2010) 645–648
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In conclusion, we have prepared and characterized three complexes [Cu(phen)(isca)(EtOH)] (1) [Cu(phen)2(HCOOH)] (2) and [Cd (phen)Cl2](3) and determined its crystal structure. Hydrogen bonding and cation···π interactions are found to form the packing structure. Also, the complex display strong fluorescence property and good thermal stability. Acknowledgements The authors thank the Project Supported by Scientific Research Fund of Zhejiang Provincial Education Department (y200908138). Appendix A. Supplementary data CCDC 759131 - 759133 contains the supplementary crystallographic data for complex 1, 2 and 3. Thess data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www. ccdc.cam.ac.uk/ data_request/cif. Supplementary data associated with this article can be found, in the online version, at doi:10.1016/j. inoche.2010.03.009. References Fig. 5. Two chains were formed by π…π stacking interactions in complex 3.
chain. In the presence of the large lateral aromatic ligand phen, the chain can be directed by stronge π···π stacking interactions into zipper-like double-stranded chain (Fig. 3b and Fig. 5) with central to central distance of 3.687 Å. The solid-state emission spectra of the complex 1 are investigated at room temperature. The emission spectrum of the title complex is given in Fig. 6. The fluorescent spectrum study shows that the title complex exhibits a broad and strong emission band with a maximum wavelength of 420 nm upon photoexcitation at 330 nm compare with pure phen ligand (emission wavelength of 377 nm) [19]. This observation indicates that the luminescence of the complex is a molecular property, attributeable to a π-π* transition of the ligand. Therefore, the emission property of the complex may be attributed to the intraligand (phen) emission from the free ligand [20–23]. The x-ray powder diffraction show that the experimental PXRD patterns of the complexes in excellent agreement with the patterns simulated from the single crystal date (Fig. S2). However, the peak of complex 3 were disappeared after the sample heating at 230 °C for 3 h, which indicate that the crystal form has been changed or the structure were collapsed. But the change of complex 1 and 2 are not obvious.
Fig. 6. Fluorescent emission spectrum of 1 at the solid state.
[1] J.C. Jones, Chem. Soc. Rev. 27 (1998) 289. [2] S.L. James, Chem. Soc. Rev. 32 (2003) 276. [3] (a) S.L.R. MacGillivray, J.L. Atwood, Nature 389 (1997) 469; (b) K. Biradha, M.J. Zaworotko, J. Am. Chem. Soc. 120 (1998) 6431; (c) L.J. Childs, N.W. Alcock, M. Hannon, Angew. Chem. Int. Ed. 40 (2001) 1079. [4] (a) Y. Zhang, Z. Yang, F. Yuan, H. Gu, P. Gao, B. Xu, J. Am. Chem. Soc. 126 (2004) 15028; (b) D. Braga, F. Grepioni, G.R. Desiraju, Chem. Rev. 98 (1998) 1375; (c) K.T. Honman, A.M. Pivovar, J.A. Swift, M.D. Ward, Acc. Chem. Res. 34 (2001) 107; (d) V. Percec, M. Glodde, T.K. Bera, Y. Miura, I. Shiyanovskaya, K.D. Singer, V.S.K. Balagurusamy, P.A. Heiney, I. Schnell, A. Rapp, H.-W. Spiess, S.D. Hudsonk, H. Duank, Nature 419 (2002) 384; (e) A. Corna, F. Rey, J. Rius, M.J. Sabater, S. Valencla, Nature 431 (2004) 287; (f) G.A. Jeffrey, An Introduction to Hydrogen Bonding, Oxford University Press, Oxford, 1997. [5] (a) D. Braga, L. Brammer, N.R. Champness, Cryst. Eng. Comm. 7 (2005) 1; (b) C.J. Kepert, Chem. Commun. (2006) 695. [6] (a) S. Blais, J.A. Ripmeester, L.R. MacGillivray, Cryst. Growth Des. 6 (2006) 2427; (b) C.J. Kepert, Chem. Commun. (2006) 695. [7] (a) J.C. Ma, D.A. Dougherty, Chem. Rev. 97 (1997) 1303; (b) E.A. Meyer, R.K. Castellano, F. Diederich, Angew. Chem. Int. Ed 42 (2003) 1210; (c) M. Egli, S. Sarkhel, Acc. Chem. Res. 40 (2007) 197. [8] (a) M. Mascal, A. Armstrong, M.D. Bartberger, J. Am. Chem. Soc. 124 (2002) 6274; (b) I. Alkorta, I. Rozas, J. Elguero, J. Org. Chem. 62 (1997) 4687; (c) C. Garau, D. Quiñonero, A. Frontera, P. Ballester, A. Costa, P.M. Deyà, New J. Chem. 27 (2003) 211; (d) J.W. Steed, R.K. Juneja, J.L. Atood, Angew. Chem. Int. Ed. 33 (1994) 2456. [9] R.S. Yaroslav, S.V. Lindeman, S.V. Rosokha, J.K. Kochi, Angew. Chem. Int. Ed. 43 (2004) 4650. [10] D. Kim, P. Tarakeshwar, S.K. Kwang, J. Phys. Chem. A. 108 (2004) 1250. [11] I. Alkorta, I. Rozas, J. Elguero, J. Am. Chem. Soc. 124 (2002) 8593. [12] O.B. Berryman, F. Hof, M.J. Hynes, D.W. Johnson, Chem. Commun. (2006) 506. [13] S. Demeshko, S. Dechert, F. Meyer, J. Am. Chem. Soc. 126 (2004) 4508. [14] P. deHoog, P. Gamez, I. Mutikainen, U. Turpeinen, J. Reedijk, Angew. Chem. Int. Ed. 43 (2004) 5815. [15] (a) J.E. Gautrot, P. Hodge, D. Cupertinob, M. Helliwella, New J. Chem. 30 (2006) 1801; (b) T.J. Mooibroek, S.J. Teat, C. Massera, P. Gamez, J. Reedijk, Cryst. Growth Des. 6 (2006) 1569. [16] Synthesis of [Cu(phen)(isca)(EtOH)] (1). To a solution of phen (0.180 g, 1mmol) in EtOH (10mL) was slowly added to a solution of CuCl2 (0.132 g, 1mmol) in deionized water (10 mL). The mixture was stirred for 10 min at room temperature and then placed in a 25 mL Teflon-lined autoclave and heated at 80°C for 120 h. The autoclave was cooled over a period of 5 h at 10 °Ch-1, and the product was collected by filtration, then dried at ambient temperature to give 1 as blue crystals. Yield: (75%, based on Cu). Anal. Calcd for C22H18CuN2O5 (%): C, 58.21; H, 4.00; N, 6.17. Found: C, 58.96; H, 4.15; N, 6.56. IR data (KBr pellets, cm-1): 2950w (v CH3), 3350s (v H-O), 1690, 1556m (v C = N), 1363, 1160, 1080, 852, 760, 563.Synthesis of [Cu (phen)2(HCOOH)] (2) To a solution of phen (0.180 g, 1mmol) in DMF (10mL) was slowly added to a solution of Cu(ClO4)2 (0.261 g, 1mmol) in deionized water (10 mL). A blue solution was formed after the resulting mixture was stirred at room temperature for 30 min. Slow evaporation of the solvent at room temperature led to the formation of blue block crystals of 2. Yield: (78%, based on Cu). Anal. Calcd for C25H17N4O6CuCl (%): C, 52.82; H, 3.01; N, 9.86. Found: C,
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52.08; H, 3.07; N, 9.63. IR data (KBr pellets, cm-1): 1731s (v C = O), 1565m (v C = N), 1520, 1307s, 1100s (v Cl=O), 849, 772, 726, 627, 427.Synthesis of [Cd (phen)Cl2](3) To a solution of phen (0.180 g, 1 mmol) in DMF (10 mL) was slowly added to a solution of CdCl2 (0.183 g, 1mmol) in deionized water (10 mL). A colorless solution was formed after the resulting mixture was stirred at room temperature for 30 min. Slow evaporation of the solvent at room temperature led to the formation of colorless block crystals of 3. Yield: (68%, based on Cd). Anal. Calcd for C12H8N2CdCl2 (%): C, 39.65; H, 2.22; N, 7.71. Found: C, 39.08; H, 2.07; N, 7.63. IR data (KBr pellets, cm-1): 1565m (v C = N), 1520, 1305s, 849s. [17] M.-L. Tong, H.-J. Chen, X.-M. Chen, Inorg. Chem. 39 (2000) 2235; S.-L. Zheng, M.-L. Tong, R.-W. Fu, X.-M. Chen, S.W. Ng, Inorg. Chem. 40 (2001) 3562;
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Contents lists available at ScienceDirect
Inorganic Chemistry Communications j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / i n o c h e
Synthesis, structures and properties of Cu and Cd complexes with 1,10-phenanthroline Jingya Sun ⁎, Xiangdi Tong, Huanzhi Xu College of Marine Sciences, Zhejiang Ocean University, Zhoushan 316000, PR China
a r t i c l e
i n f o
Article history: Received 8 January 2010 Accepted 2 March 2010 Available online 11 March 2010 Keywords: crystals structure weak interactions fluorescence 1, 10-phenanthroline
a b s t r a c t Three new Cu and Cd complexes, namely [Cu(phen)(isca)(EtOH)] (1) [Cu(phen)2(HCOOH)] (2) and [Cd (phen)Cl2](3) (phen = 1, 10-phenanthroline, isca = isophthalic acid) have been synthesized, which are characterized by elemental analysis, infrared spectrum and x-ray crystal diffraction. While strong hydrogen bonds play central roles in the formation of the 3D structure, the combined influence of the weak interactions such as C-H···O bonds, C-H···π and lone pair···π interactions are also evident in the structures. The preliminary investigation on the thermal and fluorescence property of the complexes are presented. Crown Copyright © 2010 Published by Elsevier B.V. All rights reserved.
Recently, interest has been focused on the design strategies and construction of the architectures with diversity topologies in supramolecular chemistry and crystal engineering [1]. Organic bridging ligands play an important role in the synthesis, and studies directed towards evaluating their influence on the formation of different network [2]. Self-assembly is the fundamental molecular recognition process adopted by nature to generate the elegant and intricate molecular machine, the formation of which is dependent upon an interplay of weak intermolecular interactions which are instrumental in the formation of weakly bound columns: offset π stacking plus C-H···π interactions [3]. Hydrogen bonding still remains the most reliable and widely used means of enforcing molecular recognition [4]. The selfassembly of molecular building blocks through molecular recognition has led the way in the development of a number of functional allorganic and hybrid inorganic-organic materials [5]. Besides these conventional strong hydrogen bonds, varieties of unconventional intermolecular interactions or contacts have also been found to be instrumental in determining the supramolecular structure of organic solids [6]. The supramolecular interactions with π aromatic clouds, such as C-H···π, cation···π and π···π stacking, have been demonstrated extensively both experimentally and theoretically [7–9]. In recent years, non-covalent interactions involving π-systems, such as C-H···π and anion-π interactions [10,11], which was primarily thought to be improbable due to the electron donating character of anions and the expected repulsive interactions with aromatic πsystems, have been extensively studied in the last decade. C-H···π interactions have been recognized by the scientific community as an
⁎ Corresponding author. E-mail address: [email protected] (J. Sun).
important type of supramolecular interaction. Likewise, experimental proofs for non-covalent interactions, and more generally for lone pair···π interactions, are presented in the literature [12–15]. In this context, we have succeeded in obtaining three new complexes [Cu(phen) (isca) (EtOH)] (1) [Cu(phen)2(HCOOH)] (2) and [Cd (phen)Cl2] (3) base on phen ligand [16]. Strong hydrogen bonds and π···π interactions play important roles in the formation of the 3D structure. Single-crystal X-ray diffraction measurement reveals that the crystal of the complex 1 conform to the space group P2(1)/n (Table S1). A molecular structure showing the arrangement about the Cu (II) metal center is shown in Fig. 1a. The Cu (II) ion lies on the inversion center so that the asymmetry unit comprises one-half of the formula unit. In the crystal structure of 1, there is one Cu (II) atom, one isophthalic acid ligand and one lattice EtOH molecules in each independent crystallographic unit. Each Cu (II) atom in 1 is primarily coordinated by four oxygen atoms from two isophthalic acid ligand (Cu-O(1) 1.96 Å; Cu-O (3) 1.92 Å) and two nitrogen atoms from the phen ligand (Cu-N(1) 2.002 Å; Cu-N(2) 2.001 Å) to furnish a distorted octahedral coordination geometry. Each pair of adjacent Cu (II) atoms is bridged by an isophthalic acid ligand to form a chain running along the c direction. These chains are decorated with phen ligands alternatedly at two sides (Fig. 3a). The isca phenyl rings at each side of the chain are arranged in a parallel fashion with an inter-ring distance of 7.88 Å. Indeed, each pair of homochiral polymeric chains intertwine into a unique double-stranded helix of C2 symmetry through π···π stacking interactions between the phen ligands (face-to-face distances of 3.736 Å) (Fig. 2a). The interfacial distance of 3.736 Å indicates a strong aromatic π···π stacking interaction. [17,18] These layers are further extended into two-dimensional (2D) networks through C-H···π interaction between phen and isca phenyl rings from adjacent layers [with C(17)-H(17)···Cg = 3.535 Å, Cg is the centroid of the ring defined by the atoms C2 to C7, the angle C (17)-H(17)···Cg is 153.48°] (Fig. 2b). Similar zipperlike interactions
1387-7003/$ – see front matter. Crown Copyright © 2010 Published by Elsevier B.V. All rights reserved. doi:10.1016/j.inoche.2010.03.009
646
J. Sun et al. / Inorganic Chemistry Communications 13 (2010) 645–648
Fig. 1. The metal coordination environment in 1, 2 and 3. All the hydrogen atoms were omitted for clarity.
Fig. 2. Showing the face-to-face π···π stacking of complex 1 (a); The C-H···π interactions between the phen and isca in complex 1 (b).
have been reported previously in some three-dimensional coordination architectures constructed by two-dimensional layers [17]. Complex 2 conform to the space group C2/c space group (Table S1). A molecular structure showing the arrangement about the Cu (II) metal center is shown in Fig. 1b. The Cu atom is six coordinated and adopts distorted octahedral coordination geometry by coordinating to four nitrogen atoms from the phen ligands and two oxygen atoms from the carboxyl group of the methane acid ligand, with N1 in the axial position and O1 and N2 in the equatorial plane (Cu-O(1) 2.002 Å; Cu-N(1) 1.989 Å; Cu-N(2) 2.111 Å). These complexes are extended through π···π stacking between the phen forming a 2D network. There are 1D channels along b-axis,
and the perchlorate anions are filled into the 1D channels through strong hydrogen bonds and π···π stacking interaction (with central to central distance of 3.587 Å) as showing in Fig. S1. It is noteworthy that the perchlorate anion is not coordinated to the 3D framework due to its weak coordination ability. Analysis of the crystal packing of the title compound reveals the existence of anion-π interactions between the host and the anions (Fig. 4). The O2···centroid A distance is 3.38 Å and angle O1-ring centroid-aromatic plane amounts to 68.4°. The perchlorate oxygen atom O3 is also in contact with the phen plane (O2···centroid B distance is 3.862 Å and the angle 50.35°). Complex 3 conform to the space group C2/c (Table S1). The coordination environment of the central atom is shown in Fig. 1c. The structure expands along b axis through the bridging μ2-Cl ligand into a
Fig. 3. The π···π stacking interactions in complex 1 and 3 shown in spacefilling model.
Fig. 4. Crystal packing of complex 2 illustrating the anion···π contacts.
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In conclusion, we have prepared and characterized three complexes [Cu(phen)(isca)(EtOH)] (1) [Cu(phen)2(HCOOH)] (2) and [Cd (phen)Cl2](3) and determined its crystal structure. Hydrogen bonding and cation···π interactions are found to form the packing structure. Also, the complex display strong fluorescence property and good thermal stability. Acknowledgements The authors thank the Project Supported by Scientific Research Fund of Zhejiang Provincial Education Department (y200908138). Appendix A. Supplementary data CCDC 759131 - 759133 contains the supplementary crystallographic data for complex 1, 2 and 3. Thess data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www. ccdc.cam.ac.uk/ data_request/cif. Supplementary data associated with this article can be found, in the online version, at doi:10.1016/j. inoche.2010.03.009. References Fig. 5. Two chains were formed by π…π stacking interactions in complex 3.
chain. In the presence of the large lateral aromatic ligand phen, the chain can be directed by stronge π···π stacking interactions into zipper-like double-stranded chain (Fig. 3b and Fig. 5) with central to central distance of 3.687 Å. The solid-state emission spectra of the complex 1 are investigated at room temperature. The emission spectrum of the title complex is given in Fig. 6. The fluorescent spectrum study shows that the title complex exhibits a broad and strong emission band with a maximum wavelength of 420 nm upon photoexcitation at 330 nm compare with pure phen ligand (emission wavelength of 377 nm) [19]. This observation indicates that the luminescence of the complex is a molecular property, attributeable to a π-π* transition of the ligand. Therefore, the emission property of the complex may be attributed to the intraligand (phen) emission from the free ligand [20–23]. The x-ray powder diffraction show that the experimental PXRD patterns of the complexes in excellent agreement with the patterns simulated from the single crystal date (Fig. S2). However, the peak of complex 3 were disappeared after the sample heating at 230 °C for 3 h, which indicate that the crystal form has been changed or the structure were collapsed. But the change of complex 1 and 2 are not obvious.
Fig. 6. Fluorescent emission spectrum of 1 at the solid state.
[1] J.C. Jones, Chem. Soc. Rev. 27 (1998) 289. [2] S.L. James, Chem. Soc. Rev. 32 (2003) 276. [3] (a) S.L.R. MacGillivray, J.L. Atwood, Nature 389 (1997) 469; (b) K. Biradha, M.J. Zaworotko, J. Am. Chem. Soc. 120 (1998) 6431; (c) L.J. Childs, N.W. Alcock, M. Hannon, Angew. Chem. Int. Ed. 40 (2001) 1079. [4] (a) Y. Zhang, Z. Yang, F. Yuan, H. Gu, P. Gao, B. Xu, J. Am. Chem. Soc. 126 (2004) 15028; (b) D. Braga, F. Grepioni, G.R. Desiraju, Chem. Rev. 98 (1998) 1375; (c) K.T. Honman, A.M. Pivovar, J.A. Swift, M.D. Ward, Acc. Chem. Res. 34 (2001) 107; (d) V. Percec, M. Glodde, T.K. Bera, Y. Miura, I. Shiyanovskaya, K.D. Singer, V.S.K. Balagurusamy, P.A. Heiney, I. Schnell, A. Rapp, H.-W. Spiess, S.D. Hudsonk, H. Duank, Nature 419 (2002) 384; (e) A. Corna, F. Rey, J. Rius, M.J. Sabater, S. Valencla, Nature 431 (2004) 287; (f) G.A. Jeffrey, An Introduction to Hydrogen Bonding, Oxford University Press, Oxford, 1997. [5] (a) D. Braga, L. Brammer, N.R. Champness, Cryst. Eng. Comm. 7 (2005) 1; (b) C.J. Kepert, Chem. Commun. (2006) 695. [6] (a) S. Blais, J.A. Ripmeester, L.R. MacGillivray, Cryst. Growth Des. 6 (2006) 2427; (b) C.J. Kepert, Chem. Commun. (2006) 695. [7] (a) J.C. Ma, D.A. Dougherty, Chem. Rev. 97 (1997) 1303; (b) E.A. Meyer, R.K. Castellano, F. Diederich, Angew. Chem. Int. Ed 42 (2003) 1210; (c) M. Egli, S. Sarkhel, Acc. Chem. Res. 40 (2007) 197. [8] (a) M. Mascal, A. Armstrong, M.D. Bartberger, J. Am. Chem. Soc. 124 (2002) 6274; (b) I. Alkorta, I. Rozas, J. Elguero, J. Org. Chem. 62 (1997) 4687; (c) C. Garau, D. Quiñonero, A. Frontera, P. Ballester, A. Costa, P.M. Deyà, New J. Chem. 27 (2003) 211; (d) J.W. Steed, R.K. Juneja, J.L. Atood, Angew. Chem. Int. Ed. 33 (1994) 2456. [9] R.S. Yaroslav, S.V. Lindeman, S.V. Rosokha, J.K. Kochi, Angew. Chem. Int. Ed. 43 (2004) 4650. [10] D. Kim, P. Tarakeshwar, S.K. Kwang, J. Phys. Chem. A. 108 (2004) 1250. [11] I. Alkorta, I. Rozas, J. Elguero, J. Am. Chem. Soc. 124 (2002) 8593. [12] O.B. Berryman, F. Hof, M.J. Hynes, D.W. Johnson, Chem. Commun. (2006) 506. [13] S. Demeshko, S. Dechert, F. Meyer, J. Am. Chem. Soc. 126 (2004) 4508. [14] P. deHoog, P. Gamez, I. Mutikainen, U. Turpeinen, J. Reedijk, Angew. Chem. Int. Ed. 43 (2004) 5815. [15] (a) J.E. Gautrot, P. Hodge, D. Cupertinob, M. Helliwella, New J. Chem. 30 (2006) 1801; (b) T.J. Mooibroek, S.J. Teat, C. Massera, P. Gamez, J. Reedijk, Cryst. Growth Des. 6 (2006) 1569. [16] Synthesis of [Cu(phen)(isca)(EtOH)] (1). To a solution of phen (0.180 g, 1mmol) in EtOH (10mL) was slowly added to a solution of CuCl2 (0.132 g, 1mmol) in deionized water (10 mL). The mixture was stirred for 10 min at room temperature and then placed in a 25 mL Teflon-lined autoclave and heated at 80°C for 120 h. The autoclave was cooled over a period of 5 h at 10 °Ch-1, and the product was collected by filtration, then dried at ambient temperature to give 1 as blue crystals. Yield: (75%, based on Cu). Anal. Calcd for C22H18CuN2O5 (%): C, 58.21; H, 4.00; N, 6.17. Found: C, 58.96; H, 4.15; N, 6.56. IR data (KBr pellets, cm-1): 2950w (v CH3), 3350s (v H-O), 1690, 1556m (v C = N), 1363, 1160, 1080, 852, 760, 563.Synthesis of [Cu (phen)2(HCOOH)] (2) To a solution of phen (0.180 g, 1mmol) in DMF (10mL) was slowly added to a solution of Cu(ClO4)2 (0.261 g, 1mmol) in deionized water (10 mL). A blue solution was formed after the resulting mixture was stirred at room temperature for 30 min. Slow evaporation of the solvent at room temperature led to the formation of blue block crystals of 2. Yield: (78%, based on Cu). Anal. Calcd for C25H17N4O6CuCl (%): C, 52.82; H, 3.01; N, 9.86. Found: C,
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52.08; H, 3.07; N, 9.63. IR data (KBr pellets, cm-1): 1731s (v C = O), 1565m (v C = N), 1520, 1307s, 1100s (v Cl=O), 849, 772, 726, 627, 427.Synthesis of [Cd (phen)Cl2](3) To a solution of phen (0.180 g, 1 mmol) in DMF (10 mL) was slowly added to a solution of CdCl2 (0.183 g, 1mmol) in deionized water (10 mL). A colorless solution was formed after the resulting mixture was stirred at room temperature for 30 min. Slow evaporation of the solvent at room temperature led to the formation of colorless block crystals of 3. Yield: (68%, based on Cd). Anal. Calcd for C12H8N2CdCl2 (%): C, 39.65; H, 2.22; N, 7.71. Found: C, 39.08; H, 2.07; N, 7.63. IR data (KBr pellets, cm-1): 1565m (v C = N), 1520, 1305s, 849s. [17] M.-L. Tong, H.-J. Chen, X.-M. Chen, Inorg. Chem. 39 (2000) 2235; S.-L. Zheng, M.-L. Tong, R.-W. Fu, X.-M. Chen, S.W. Ng, Inorg. Chem. 40 (2001) 3562;
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