- Email: [email protected]
Hydrothermal synthesis, crystal structure and properties of a thermally stable dysprosium porphyrin with a three-dimensional porous open framework
Inorganic Chemistry Communications 49 (2014) 16–18
Contents lists available at ScienceDirect
Inorganic Chemistry Communications journal homepage: www.elsevier.com/locate/inoche
Hydrothermal synthesis, crystal structure and properties of a thermally stable dysprosium porphyrin with a three-dimensional porous open framework Wen-Tong Chen a,b,⁎, Qiu-Yan Luo a, Ya-Ping Xu a, Yan-Kang Dai a, Shan-Lin Huang a, Pei-Yu Guo a a b
Institute of Applied Chemistry, School of Chemistry and Chemical Engineering, Jiangxi Province Key Laboratory of Coordination Chemistry, Jinggangshan University, Ji'an, Jiangxi 343009, China State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, China
a r t i c l e
i n f o
Article history: Received 26 June 2014 Received in revised form 4 September 2014 Accepted 9 September 2014 Available online 10 September 2014 Keywords: Dysprosium Hydrothermal Open framework Porphyrin Thermally stable
a b s t r a c t A thermally stable dysprosium porphyrin with a three-dimensional (3D) porous open framework, [Dy(H2TPPS)]n∙ nH3O∙2nH 2O (1) (H 2TPPS = tetra(4-sulfonatophenyl)porphyrin), has been synthesized via hydrothermal reactions and structurally analyzed by an X-ray single-crystal diffraction method. The 24-membered macrocyclic ring of H2TPPS is exactly coplanar and the center is free from metal. The dysprosium ion is coordinated by eight Osulfonic atoms from eight H2TPPS moieties, forming a distorted square antiprism geometry. Complex 1 shows a void space of 210 Å3, occupying 9.06% of the unit-cell volume. The 3D porous open framework of 1 is thermally stable up to 380 °C. Complex 1 exhibits a red fluorescence emission with a quantum yield and lifetime of 2.7% and 136 μs, respectively. CV result reveals one reductive peak at − 0.33 V and one quasi-reversible wave with E1/2 = − 0.81 V. © 2014 Elsevier B.V. All rights reserved.
Porphyrin complexes have recently become one of the most attractive chemical systems, because they can display important applications in the areas of chemical sensors, catalysis, opto-electronics, molecular sieves, adsorption, pigments, medicine, solar cells and so on [1–5]. During the process of synthesizing novel porphyrin complexes, many free-based porphyrins have been applied, for instance, tetrakis(4(carboxymethyleneoxy)phenyl)porphyrin (TCMOPP), meso-tetra(4pyridyl)porphyrin (TPyP), tetrakis(4-carboxyphenyl)porphyrin (TCPP) and tetrakis(3,5-dicarboxyphenyl)porphyrin (TDCPP) [6–11]. In contrast, to our knowledge, tetra(4-sulfonatophenyl)porphyrin (H2TPPS) has been rarely used to prepare new porphyrin complexes [12,13]. As a matter of fact, H2TPPS is a useful ligand to prepare new porphyrin complexes due to its rigid, large and square planar symmetrical geometry. H2TPPS can afford a lot of coordination sites such as the center of the 24-membered macrocyclic ring and twelve oxygen atoms of four sulfonic groups. Lanthanide ions are also interesting owing to their variety of coordination numbers, fluorescent properties and magnetic properties. As a result, lanthanide complexes have been widely investigated both theoretically and practically and, up to date, a great deal of lanthanide complexes has thus far been reported [14–16]. In recent years, we mainly focus on the synthesis and characterization of lanthanide porphyrin complexes which probably possess novel structures and properties. In ⁎ Corresponding author at: Institute of Applied Chemistry, School of Chemistry and Chemical Engineering, Jiangxi Province Key Laboratory of Coordination Chemistry, Jinggangshan University, Ji'an, Jiangxi 343009, China. E-mail address: [email protected] (W.-T. Chen).
http://dx.doi.org/10.1016/j.inoche.2014.09.012 1387-7003/© 2014 Elsevier B.V. All rights reserved.
this work, we report the preparation, crystal structure and properties of a lanthanide porphyrin complex, [Dy(H2TPPS)]n∙ nH3O∙2nH2O (1) (H2TPPS = tetra(4-sulfonatophenyl)porphyrin), which is synthesized via hydrothermal reactions. Complex 1 features a 3D porous open framework which is thermally stable as high as 380 °C. Compound 1 was obtained from the reaction of DyCl3·6H2O and H2TPPS by hydrothermal reaction [17]. A single-crystal X-ray diffraction study [18] revealed that complex 1 crystallizes in the tetragonal system with a space group P4/mcc and the asymmetric unit contains one Dy(III) atom, one sulfur atom, two oxygen atoms, one nitrogen atom, nine carbon atoms and two crystal water molecules, as shown in Fig. S1. The 24membered macrocyclic ring of H2TPPS is totally coplanar and the center is uncoordinated with metal. With respect to the plane of the 24membered macrocyclic ring, the twist angle of the four aryl rings is 90°. The neighboring porphyrin macrocyclic planes are parallel and the closest distance between them is 4.9916(4) Å. The Dy(III) is eight coordinated with a slightly distorted square anti-prism coordination geometry defined by eight oxygen atoms from eight sulfonic ligands. The bond distance of Dy(III)–O in complex 1 is 2.351(2) Å which is in the normal range and comparable with those documented in the literature [19–22]. Every two Dy(III) atoms are interconnected by four sulfonic ligands to give a one-dimensional (1D) chain running along the c-axis (Fig. S2). The Dy(III)·Dy(III) distance is 4.9043(4) Å. Each H2TPPS moiety coordinates to eight Dy(III) atoms and each Dy(III) atom links to eight H2TPPS molecules, yielding a condensed 3D porous open framework with the crystal water molecules residing in the voids, as shown in Fig. 1. It should be pointed out that complex 1 exhibits a void space of 210 Å3, occupying 9.06% of the unit-cell volume. The void space in 1
W.-T. Chen et al. / Inorganic Chemistry Communications 49 (2014) 16–18
17
Fig. 2. Nanosecond transient spectra performed in ethanol solutions.
Fig. 1. A packing diagram of the 3D porous open framework viewed down along the c-axis.
is smaller than other MOFs with porphyrin ligands found in the references [23–25]. For the sake of discovering the thermal stability of the open framework of complex 1, we carried out the TG and DTA measurements under flowing air atmosphere. 15 mg powdery sample of 1 was loaded into an alumina pan and heated with a ramp rate of 10 °C/min. Fig. S3 shows the results of the TG and DTA experiments. The TG curve of complex 1 discovers that its 3D porous open framework is thermally stable up to as high as 380 °C. From the beginning temperature to 100 °C in the TG diagram, a weight loss of 4.65% can be found, which is probably ascribed to the escape of the crystal water molecules in the voids (calcd. 4.79%). From 100 °C to 380 °C is a thermostable zone. The 3D porous open framework of complex 1 collapses at 380 °C with one endothermic peak centered at 464 °C, as shown in the DTA diagram. In general, dysprosium-containing complexes can exhibit good fluorescence property. Moreover, porphyrins can also display fluorescence in solution state, but porphyrins cannot show fluorescence in solid state due to the well-known concentration quenching effect. Based on these considerations, we measured the fluorescence spectra of complex 1 in ethanol solutions at room temperature. As shown in Fig. S4, when it was excited by the wavelength of 656 nm, complex 1 exhibits four excitation bands residing at 405, 431, 522 and 550 nm, respectively; contrariwise, upon the excitation of 550 nm, complex 1 shows a maximum fluorescent emission band at 656 nm in the red region. This fluorescent emission band at 656 nm is clearly ascribed to the characteristic band of the porphyrin moiety. Therefore, the characteristic bands of dysprosium cannot be found in the fluorescence spectra of complex 1. The reason for the lack of the characteristic emission bands of the dysprosium is probably that the H2TPPS is not a good ‘antenna’ for transferring the adsorbed light energy to the dysprosium ions. Adopting the time-correlated single photon counting method, we obtained the fluorescence lifetime of complex 1 in ethanol solutions with the use of 421 nm excitation light, because the light in such a wavelength can be effectively absorbed by porphyrins. The nanosecond transient spectra of complex 1 carried out in ethanol solutions are displayed in Fig. 2. The nanosecond transient spectra are fitted as a single exponential, in order to obtain the time-resolved fluorescent decay time. We finally found that the fluorescent lifetime of complex 1 is 136 μs in ethanol solutions. We also tested the emission quantum yield of complex 1 in ethanol solutions and the emission quantum yield is determined to be 2.7%.
As pointed out by Kadish and his colleagues, some important factors that mainly decide the redox potentials of porphyrins are the solvents, porphyrin themselves and the supporting electrolytes, and so forth. Leaning upon the kinds of porphyrins, these redox potentials could be possibly different even up to 1.0 V [26]. We carried out the cyclic voltammetry (CV) experiments of complex 1 with an ethanol solution sample (containing 0.1 mol·L− 1 TBAPF6) in argon atmosphere under room temperature. As shown in Fig. 3, a slow sweep CV of complex 1 reveals one reductive peak at − 0.33 V and one quasi-reversible wave with E1/2 = − 0.81 V (the reductive and oxidative peaks are − 0.90 V and − 0.71 V, respectively). In conclusion, using hydrothermal reactions, we have prepared and structurally analyzed a dysprosium porphyrin [Dy(H2TPPS)]n·nH3O·2nH2O (H2TPPS = tetra(4-sulfonatophenyl) porphyrin). The title complex is characterized by a robust 3D porous open framework with a void space of 210 Å3 . The 3D porous open framework of 1 is thermally stable up to 380 °C. Complex 1 displays a fluorescence emission band in the red region. The quantum yield and lifetime are determined to be 2.7% and 136 μs, respectively. CV measurements discover one quasi-reversible wave with E1/2 = − 0.81 V and one reductive peak at − 0.33 V.
Acknowledgments We thank the financial support of the NSF of China (21361013), the NSF of Jiangxi Province (20132BAB203010), the science and technology project of Jiangxi Provincial Department of Education (GJJ14554) and the open foundation (No. 20130014) of the State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences.
Fig. 3. CV diagram of 1 under argon atmosphere.
18
W.-T. Chen et al. / Inorganic Chemistry Communications 49 (2014) 16–18
Appendix A. Supplementary material Supplementary data to this article can be found online at http://dx. doi.org/10.1016/j.inoche.2014.09.012. These data include MOL file and InChiKey of the most important compounds described in this article.
[18]
References [1] J.A. Faiz, V. Heitz, J.P. Sauvage, Chem. Soc. Rev. 2 (2009) 422. [2] C. Bucher, C.H. Devillers, J.C. Moutet, G. Royal, E. Saint-Aman, Coord. Chem. Rev. 253 (2009) 21. [3] C. Di Natale, D. Monti, R. Paolesse, Mater. Today 13 (2010) 46. [4] K. Maeda, K.B. Henbest, F. Cintolesi, I. Kuprov, C.T. Rodgers, P.A. Liddell, D. Gust, C.R. Timmel, P.J. Hore, Nature 453 (2008) 387. [5] W. Tu, J. Lei, G. Jian, Z. Hu, H. Ju, Chem. Eur. J. 16 (2010) 4120. [6] C. Zou, C.D. Wu, Dalton Trans. 41 (2012) 3879. [7] A. Fateeva, P.A. Chater, C.P. Ireland, A.A. Tahir, Y.Z. Khimyak, P.V. Wiper, J.R. Darwent, M.J. Rosseinsky, Angew. Chem. Int. Ed. 51 (2012) 7440. [8] S. Matsunaga, N. Endo, W. Mori, Eur. J. Inorg. Chem. (2011) 4550. [9] C. Zou, M.H. Xie, G.Q. Kong, C.D. Wu, CrystEngComm 14 (2012) 4850. [10] W. Morris, B. Volosskiy, S. Demir, F. Gándara, P.L. McGrier, H. Furukawa, D. Cascio, J.F. Stoddart, O.M. Yaghi, Inorg. Chem. 51 (2012) 6443. [11] N.C. Smythe, D.P. Butler, C.E. Moore, W.R. McGowan, A.L. Rheingold, L.G. Beauvais, Dalton Trans. 41 (2012) 7855. [12] J. Demel, P. Kubát, F. Millange, J. Marrot, I. Císařová, K. Lang, Inorg. Chem. 52 (2013) 2779. [13] W.T. Chen, Y. Yamada, G.N. Liu, A. Kubota, T. Ichikawa, Y. Kojima, G.C. Guo, S. Fukuzumi, Dalton Trans. 40 (2011) 12826. [14] Y. Cui, H. Xu, Y. Yue, Z. Guo, J. Yu, Z. Chen, J. Gao, Y. Yang, G. Qian, B. Chen, J. Am. Chem. Soc. 134 (2012) 3979. [15] E. Pershagen, J. Nordholm, K.E. Borbas, J. Am. Chem. Soc. 134 (2012) 9832. [16] D.T. Thielemann, A.T. Wagner, E. Rösch, D.K. Kölmel, J.G. Heck, B. Rudat, M. Neumaier, C. Feldmann, U. Schepers, S. Bräse, P.W. Roesky, J. Am. Chem. Soc. 135 (2013) 7454. [17] Synthesis of 1: It was prepared from a mixture of DyCl3·6H2O (0.1 mmol, 38 mg), H2TPPS (0.1 mmol, 94 mg), 10 mL distilled water in a 25 mL Teflon-lined autoclave
[19] [20] [21] [22] [23] [24] [25] [26]
under autogenous pressure at 473 K for ten days. After cooling to room temperature, purple block crystals were collected by filtration and washed with distilled water in 33% yield (based on dysprosium). m/z (MALDI-TOF-MS in CHCl3 (matrix: CHCA)) 1093.46 (Dy(H2TPPS) requires 1093.97) (Fig. S5). Crystal data: C 44 H 33 DyN 4 O 15 S 4 , M = 1148.48, tetragonal, P4/mcc (No. 124), a = 15.3763(6), c = 9.8086(9) Å, V = 2319.1(2) Å 3 , Z = 2, μ(Mo Kα) = 1. 865 mm − 1 , T = 123.15 K, R 1 = 0.0448, wR 2 = 0.1249. CCDC 994078. Anal. Calcd. for C44 H 33 DyN 4 O 15 S 4 : C, 46.01; H, 2.90; N, 4.88. Found: C, 46.12; H, 2. 87; N, 4.84. IR spectra (KBr, cm − 1 ): 3428(vs), 3104(m), 2364(w), 1700(w), 1636(m), 1399(w), 1247(vs), 1178(vs), 1125(vs), 1051(vs), 1003(vs), 970(w), 855(w), 806(m), 742(vs), 669(w) and 631(vs). The single crystal Xray diffraction data of 1 were acquired with the use of a Rigaku Mercury CCD X-ray diffractometer equipped with graphite-monochromatic MoKα (λ = 0. 71073 Å) radiation using a ω scan mode. The unit cell parameters were obtained from the full-matrix least-squares refinement. Semi-empirical absorption corrections and data reduction were applied by the CrystalClear software. The crystal structure was solved by the direct methods and refined by full-matrix leastsquares on F2 with the Siemens SHELXTL™ Version 5 package of crystallographic software. Hydrogen atoms were generated geometrically, refined isotropically and allowed to ride on the parent atoms. All non-hydrogen atoms were located with successive difference Fourier syntheses and refined anisotropically. H. Ke, L. Zhao, Y. Guo, J. Tang, Eur. J. Inorg. Chem. 27 (2011) 4153. S.L. Cai, S.R. Zheng, J. Fan, J.B. Tan, T.T. Xiao, W.G. Zhang, J. Solid State Chem. 184 (2011) 3172. X.L. Hao, M.F. Luo, X. Wang, X.J. Feng, Y.G. Li, Y.H. Wang, E.B. Wang, Inorg. Chem. Commun. 14 (2011) 1698. X.Y. Xiao, Y.Q. Wei, W.X. Zheng, K.C. Wu, Chin. J. Struct. Chem. 30 (2011) 1543. H.C. Kim, Y.S. Lee, S. Huh, S.J. Lee, Y. Kim, Dalton Trans. 43 (2014) 5680. X.L. Yang, M.H. Xie, C. Zou, Y. He, B. Chen, M. O'Keeffe, C.D. Wu, J. Am. Chem. Soc. 134 (2012) 10638. X.S. Wang, M. Chrzanowski, C. Kim, W.Y. Gao, L. Wojtas, Y.S. Chen, X.P. Zhang, S. Ma, Chem. Commun. 48 (2012) 7173. K.M. Kadish, E. Van Caemelbecke, F. D'Souza, M. Lin, D.J. Nurco, C.J. Medforth, T.P. Forsyth, B. Krattinger, K.M. Smith, S. Fukuzumi, I. Nakanishi, J.A. Shelnutt, Inorg. Chem. 38 (1999) 2188.
Contents lists available at ScienceDirect
Inorganic Chemistry Communications journal homepage: www.elsevier.com/locate/inoche
Hydrothermal synthesis, crystal structure and properties of a thermally stable dysprosium porphyrin with a three-dimensional porous open framework Wen-Tong Chen a,b,⁎, Qiu-Yan Luo a, Ya-Ping Xu a, Yan-Kang Dai a, Shan-Lin Huang a, Pei-Yu Guo a a b
Institute of Applied Chemistry, School of Chemistry and Chemical Engineering, Jiangxi Province Key Laboratory of Coordination Chemistry, Jinggangshan University, Ji'an, Jiangxi 343009, China State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, China
a r t i c l e
i n f o
Article history: Received 26 June 2014 Received in revised form 4 September 2014 Accepted 9 September 2014 Available online 10 September 2014 Keywords: Dysprosium Hydrothermal Open framework Porphyrin Thermally stable
a b s t r a c t A thermally stable dysprosium porphyrin with a three-dimensional (3D) porous open framework, [Dy(H2TPPS)]n∙ nH3O∙2nH 2O (1) (H 2TPPS = tetra(4-sulfonatophenyl)porphyrin), has been synthesized via hydrothermal reactions and structurally analyzed by an X-ray single-crystal diffraction method. The 24-membered macrocyclic ring of H2TPPS is exactly coplanar and the center is free from metal. The dysprosium ion is coordinated by eight Osulfonic atoms from eight H2TPPS moieties, forming a distorted square antiprism geometry. Complex 1 shows a void space of 210 Å3, occupying 9.06% of the unit-cell volume. The 3D porous open framework of 1 is thermally stable up to 380 °C. Complex 1 exhibits a red fluorescence emission with a quantum yield and lifetime of 2.7% and 136 μs, respectively. CV result reveals one reductive peak at − 0.33 V and one quasi-reversible wave with E1/2 = − 0.81 V. © 2014 Elsevier B.V. All rights reserved.
Porphyrin complexes have recently become one of the most attractive chemical systems, because they can display important applications in the areas of chemical sensors, catalysis, opto-electronics, molecular sieves, adsorption, pigments, medicine, solar cells and so on [1–5]. During the process of synthesizing novel porphyrin complexes, many free-based porphyrins have been applied, for instance, tetrakis(4(carboxymethyleneoxy)phenyl)porphyrin (TCMOPP), meso-tetra(4pyridyl)porphyrin (TPyP), tetrakis(4-carboxyphenyl)porphyrin (TCPP) and tetrakis(3,5-dicarboxyphenyl)porphyrin (TDCPP) [6–11]. In contrast, to our knowledge, tetra(4-sulfonatophenyl)porphyrin (H2TPPS) has been rarely used to prepare new porphyrin complexes [12,13]. As a matter of fact, H2TPPS is a useful ligand to prepare new porphyrin complexes due to its rigid, large and square planar symmetrical geometry. H2TPPS can afford a lot of coordination sites such as the center of the 24-membered macrocyclic ring and twelve oxygen atoms of four sulfonic groups. Lanthanide ions are also interesting owing to their variety of coordination numbers, fluorescent properties and magnetic properties. As a result, lanthanide complexes have been widely investigated both theoretically and practically and, up to date, a great deal of lanthanide complexes has thus far been reported [14–16]. In recent years, we mainly focus on the synthesis and characterization of lanthanide porphyrin complexes which probably possess novel structures and properties. In ⁎ Corresponding author at: Institute of Applied Chemistry, School of Chemistry and Chemical Engineering, Jiangxi Province Key Laboratory of Coordination Chemistry, Jinggangshan University, Ji'an, Jiangxi 343009, China. E-mail address: [email protected] (W.-T. Chen).
http://dx.doi.org/10.1016/j.inoche.2014.09.012 1387-7003/© 2014 Elsevier B.V. All rights reserved.
this work, we report the preparation, crystal structure and properties of a lanthanide porphyrin complex, [Dy(H2TPPS)]n∙ nH3O∙2nH2O (1) (H2TPPS = tetra(4-sulfonatophenyl)porphyrin), which is synthesized via hydrothermal reactions. Complex 1 features a 3D porous open framework which is thermally stable as high as 380 °C. Compound 1 was obtained from the reaction of DyCl3·6H2O and H2TPPS by hydrothermal reaction [17]. A single-crystal X-ray diffraction study [18] revealed that complex 1 crystallizes in the tetragonal system with a space group P4/mcc and the asymmetric unit contains one Dy(III) atom, one sulfur atom, two oxygen atoms, one nitrogen atom, nine carbon atoms and two crystal water molecules, as shown in Fig. S1. The 24membered macrocyclic ring of H2TPPS is totally coplanar and the center is uncoordinated with metal. With respect to the plane of the 24membered macrocyclic ring, the twist angle of the four aryl rings is 90°. The neighboring porphyrin macrocyclic planes are parallel and the closest distance between them is 4.9916(4) Å. The Dy(III) is eight coordinated with a slightly distorted square anti-prism coordination geometry defined by eight oxygen atoms from eight sulfonic ligands. The bond distance of Dy(III)–O in complex 1 is 2.351(2) Å which is in the normal range and comparable with those documented in the literature [19–22]. Every two Dy(III) atoms are interconnected by four sulfonic ligands to give a one-dimensional (1D) chain running along the c-axis (Fig. S2). The Dy(III)·Dy(III) distance is 4.9043(4) Å. Each H2TPPS moiety coordinates to eight Dy(III) atoms and each Dy(III) atom links to eight H2TPPS molecules, yielding a condensed 3D porous open framework with the crystal water molecules residing in the voids, as shown in Fig. 1. It should be pointed out that complex 1 exhibits a void space of 210 Å3, occupying 9.06% of the unit-cell volume. The void space in 1
W.-T. Chen et al. / Inorganic Chemistry Communications 49 (2014) 16–18
17
Fig. 2. Nanosecond transient spectra performed in ethanol solutions.
Fig. 1. A packing diagram of the 3D porous open framework viewed down along the c-axis.
is smaller than other MOFs with porphyrin ligands found in the references [23–25]. For the sake of discovering the thermal stability of the open framework of complex 1, we carried out the TG and DTA measurements under flowing air atmosphere. 15 mg powdery sample of 1 was loaded into an alumina pan and heated with a ramp rate of 10 °C/min. Fig. S3 shows the results of the TG and DTA experiments. The TG curve of complex 1 discovers that its 3D porous open framework is thermally stable up to as high as 380 °C. From the beginning temperature to 100 °C in the TG diagram, a weight loss of 4.65% can be found, which is probably ascribed to the escape of the crystal water molecules in the voids (calcd. 4.79%). From 100 °C to 380 °C is a thermostable zone. The 3D porous open framework of complex 1 collapses at 380 °C with one endothermic peak centered at 464 °C, as shown in the DTA diagram. In general, dysprosium-containing complexes can exhibit good fluorescence property. Moreover, porphyrins can also display fluorescence in solution state, but porphyrins cannot show fluorescence in solid state due to the well-known concentration quenching effect. Based on these considerations, we measured the fluorescence spectra of complex 1 in ethanol solutions at room temperature. As shown in Fig. S4, when it was excited by the wavelength of 656 nm, complex 1 exhibits four excitation bands residing at 405, 431, 522 and 550 nm, respectively; contrariwise, upon the excitation of 550 nm, complex 1 shows a maximum fluorescent emission band at 656 nm in the red region. This fluorescent emission band at 656 nm is clearly ascribed to the characteristic band of the porphyrin moiety. Therefore, the characteristic bands of dysprosium cannot be found in the fluorescence spectra of complex 1. The reason for the lack of the characteristic emission bands of the dysprosium is probably that the H2TPPS is not a good ‘antenna’ for transferring the adsorbed light energy to the dysprosium ions. Adopting the time-correlated single photon counting method, we obtained the fluorescence lifetime of complex 1 in ethanol solutions with the use of 421 nm excitation light, because the light in such a wavelength can be effectively absorbed by porphyrins. The nanosecond transient spectra of complex 1 carried out in ethanol solutions are displayed in Fig. 2. The nanosecond transient spectra are fitted as a single exponential, in order to obtain the time-resolved fluorescent decay time. We finally found that the fluorescent lifetime of complex 1 is 136 μs in ethanol solutions. We also tested the emission quantum yield of complex 1 in ethanol solutions and the emission quantum yield is determined to be 2.7%.
As pointed out by Kadish and his colleagues, some important factors that mainly decide the redox potentials of porphyrins are the solvents, porphyrin themselves and the supporting electrolytes, and so forth. Leaning upon the kinds of porphyrins, these redox potentials could be possibly different even up to 1.0 V [26]. We carried out the cyclic voltammetry (CV) experiments of complex 1 with an ethanol solution sample (containing 0.1 mol·L− 1 TBAPF6) in argon atmosphere under room temperature. As shown in Fig. 3, a slow sweep CV of complex 1 reveals one reductive peak at − 0.33 V and one quasi-reversible wave with E1/2 = − 0.81 V (the reductive and oxidative peaks are − 0.90 V and − 0.71 V, respectively). In conclusion, using hydrothermal reactions, we have prepared and structurally analyzed a dysprosium porphyrin [Dy(H2TPPS)]n·nH3O·2nH2O (H2TPPS = tetra(4-sulfonatophenyl) porphyrin). The title complex is characterized by a robust 3D porous open framework with a void space of 210 Å3 . The 3D porous open framework of 1 is thermally stable up to 380 °C. Complex 1 displays a fluorescence emission band in the red region. The quantum yield and lifetime are determined to be 2.7% and 136 μs, respectively. CV measurements discover one quasi-reversible wave with E1/2 = − 0.81 V and one reductive peak at − 0.33 V.
Acknowledgments We thank the financial support of the NSF of China (21361013), the NSF of Jiangxi Province (20132BAB203010), the science and technology project of Jiangxi Provincial Department of Education (GJJ14554) and the open foundation (No. 20130014) of the State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences.
Fig. 3. CV diagram of 1 under argon atmosphere.
18
W.-T. Chen et al. / Inorganic Chemistry Communications 49 (2014) 16–18
Appendix A. Supplementary material Supplementary data to this article can be found online at http://dx. doi.org/10.1016/j.inoche.2014.09.012. These data include MOL file and InChiKey of the most important compounds described in this article.
[18]
References [1] J.A. Faiz, V. Heitz, J.P. Sauvage, Chem. Soc. Rev. 2 (2009) 422. [2] C. Bucher, C.H. Devillers, J.C. Moutet, G. Royal, E. Saint-Aman, Coord. Chem. Rev. 253 (2009) 21. [3] C. Di Natale, D. Monti, R. Paolesse, Mater. Today 13 (2010) 46. [4] K. Maeda, K.B. Henbest, F. Cintolesi, I. Kuprov, C.T. Rodgers, P.A. Liddell, D. Gust, C.R. Timmel, P.J. Hore, Nature 453 (2008) 387. [5] W. Tu, J. Lei, G. Jian, Z. Hu, H. Ju, Chem. Eur. J. 16 (2010) 4120. [6] C. Zou, C.D. Wu, Dalton Trans. 41 (2012) 3879. [7] A. Fateeva, P.A. Chater, C.P. Ireland, A.A. Tahir, Y.Z. Khimyak, P.V. Wiper, J.R. Darwent, M.J. Rosseinsky, Angew. Chem. Int. Ed. 51 (2012) 7440. [8] S. Matsunaga, N. Endo, W. Mori, Eur. J. Inorg. Chem. (2011) 4550. [9] C. Zou, M.H. Xie, G.Q. Kong, C.D. Wu, CrystEngComm 14 (2012) 4850. [10] W. Morris, B. Volosskiy, S. Demir, F. Gándara, P.L. McGrier, H. Furukawa, D. Cascio, J.F. Stoddart, O.M. Yaghi, Inorg. Chem. 51 (2012) 6443. [11] N.C. Smythe, D.P. Butler, C.E. Moore, W.R. McGowan, A.L. Rheingold, L.G. Beauvais, Dalton Trans. 41 (2012) 7855. [12] J. Demel, P. Kubát, F. Millange, J. Marrot, I. Císařová, K. Lang, Inorg. Chem. 52 (2013) 2779. [13] W.T. Chen, Y. Yamada, G.N. Liu, A. Kubota, T. Ichikawa, Y. Kojima, G.C. Guo, S. Fukuzumi, Dalton Trans. 40 (2011) 12826. [14] Y. Cui, H. Xu, Y. Yue, Z. Guo, J. Yu, Z. Chen, J. Gao, Y. Yang, G. Qian, B. Chen, J. Am. Chem. Soc. 134 (2012) 3979. [15] E. Pershagen, J. Nordholm, K.E. Borbas, J. Am. Chem. Soc. 134 (2012) 9832. [16] D.T. Thielemann, A.T. Wagner, E. Rösch, D.K. Kölmel, J.G. Heck, B. Rudat, M. Neumaier, C. Feldmann, U. Schepers, S. Bräse, P.W. Roesky, J. Am. Chem. Soc. 135 (2013) 7454. [17] Synthesis of 1: It was prepared from a mixture of DyCl3·6H2O (0.1 mmol, 38 mg), H2TPPS (0.1 mmol, 94 mg), 10 mL distilled water in a 25 mL Teflon-lined autoclave
[19] [20] [21] [22] [23] [24] [25] [26]
under autogenous pressure at 473 K for ten days. After cooling to room temperature, purple block crystals were collected by filtration and washed with distilled water in 33% yield (based on dysprosium). m/z (MALDI-TOF-MS in CHCl3 (matrix: CHCA)) 1093.46 (Dy(H2TPPS) requires 1093.97) (Fig. S5). Crystal data: C 44 H 33 DyN 4 O 15 S 4 , M = 1148.48, tetragonal, P4/mcc (No. 124), a = 15.3763(6), c = 9.8086(9) Å, V = 2319.1(2) Å 3 , Z = 2, μ(Mo Kα) = 1. 865 mm − 1 , T = 123.15 K, R 1 = 0.0448, wR 2 = 0.1249. CCDC 994078. Anal. Calcd. for C44 H 33 DyN 4 O 15 S 4 : C, 46.01; H, 2.90; N, 4.88. Found: C, 46.12; H, 2. 87; N, 4.84. IR spectra (KBr, cm − 1 ): 3428(vs), 3104(m), 2364(w), 1700(w), 1636(m), 1399(w), 1247(vs), 1178(vs), 1125(vs), 1051(vs), 1003(vs), 970(w), 855(w), 806(m), 742(vs), 669(w) and 631(vs). The single crystal Xray diffraction data of 1 were acquired with the use of a Rigaku Mercury CCD X-ray diffractometer equipped with graphite-monochromatic MoKα (λ = 0. 71073 Å) radiation using a ω scan mode. The unit cell parameters were obtained from the full-matrix least-squares refinement. Semi-empirical absorption corrections and data reduction were applied by the CrystalClear software. The crystal structure was solved by the direct methods and refined by full-matrix leastsquares on F2 with the Siemens SHELXTL™ Version 5 package of crystallographic software. Hydrogen atoms were generated geometrically, refined isotropically and allowed to ride on the parent atoms. All non-hydrogen atoms were located with successive difference Fourier syntheses and refined anisotropically. H. Ke, L. Zhao, Y. Guo, J. Tang, Eur. J. Inorg. Chem. 27 (2011) 4153. S.L. Cai, S.R. Zheng, J. Fan, J.B. Tan, T.T. Xiao, W.G. Zhang, J. Solid State Chem. 184 (2011) 3172. X.L. Hao, M.F. Luo, X. Wang, X.J. Feng, Y.G. Li, Y.H. Wang, E.B. Wang, Inorg. Chem. Commun. 14 (2011) 1698. X.Y. Xiao, Y.Q. Wei, W.X. Zheng, K.C. Wu, Chin. J. Struct. Chem. 30 (2011) 1543. H.C. Kim, Y.S. Lee, S. Huh, S.J. Lee, Y. Kim, Dalton Trans. 43 (2014) 5680. X.L. Yang, M.H. Xie, C. Zou, Y. He, B. Chen, M. O'Keeffe, C.D. Wu, J. Am. Chem. Soc. 134 (2012) 10638. X.S. Wang, M. Chrzanowski, C. Kim, W.Y. Gao, L. Wojtas, Y.S. Chen, X.P. Zhang, S. Ma, Chem. Commun. 48 (2012) 7173. K.M. Kadish, E. Van Caemelbecke, F. D'Souza, M. Lin, D.J. Nurco, C.J. Medforth, T.P. Forsyth, B. Krattinger, K.M. Smith, S. Fukuzumi, I. Nakanishi, J.A. Shelnutt, Inorg. Chem. 38 (1999) 2188.