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A luminescent novel octanuclear silver(I) cluster framework with potential Cr2O72 − sensing
Inorganic Chemistry Communications 70 (2016) 157–159
Contents lists available at ScienceDirect
Inorganic Chemistry Communications journal homepage: www.elsevier.com/locate/inoche
Short communication
A luminescent novel octanuclear silver(I) cluster framework with potential Cr2O27 − sensing Jun-Cheng Jin, Chen Jiang, Wen-Gui Chang, Guang-Nian Xu, Xu-Cheng Fu Technology Promotion Center of Nano Composite Material Preparation and Application, Anhui Provincial Laboratory of Biomimetic Sensor and Detecting Technology, West Anhui University, Anhui 237012, China
a r t i c l e
i n f o
Article history: Received 17 April 2016 Received in revised form 5 June 2016 Accepted 11 June 2016 Available online 13 June 2016 Keywords: Crystal engineering Silver cluster Anions sensor Fluorescence spectrum
a b s t r a c t An unique and novel octanuclear silver(I) cluster compound, [Ag8(ADC)4]n (1) (H2ADC = 1,3adamantanedicarboxylic acid), has been synthesized and characterized. Compound 1 exhibits significant Ag– Ag interactions to form 2D infinite silver layers with multiple unsaturated Ag atoms. Moreover, Luminescent investigations show that 1 can exhibit highly selective response to Cr2O2− 7 through luminescence quenching effect in aqueous solution, which make its good candidate as luminescent sensor. © 2016 Elsevier B.V. All rights reserved.
Designing and synthesis of inorganic-organic composite coordination polymers have been attracted considerable attention for exhibiting neoteric structures and properties, which have provided exciting new prospects [1,2]. Silver complexes and clusters possess unusual structural diversity and have been the subject of considerable interest [3]. To further study their structures, luminescent properties and sensors has proved that it is relevant to the structural elucidation of the metal-binding sites [4–6]. What's more, the coordination polymers have displayed a lots of promising applications in advanced materials, including the thermolytic preparation of nano-structured materials and the synthesis of monolayer-protected clusters, and so on [7–9]. We all know that silver(I) ion possesses a wide variety of coordination geometries in complexes, [10] which can be partially attributed to the lack of stereo-chemical preferences because of a d10 configuration. In addition, the weak nature of the silver-ligand bonds8 assumes that various weak interactions and then crystal packing forces could have greater influence on structure formation than that for more rigid metal-ligand systems [11]. On the other hand, carboxylates are dominant metal-binding units in coordination networks due to their negative charge significantly enhances the ability to form rigid bonds with metal centers. Some scientists have made great contributions to this field, however, it remains an interesting research realm to design and synthesized metal-cluster compounds through the self-assembly of metal ions and organic ligands. Generally, V-shaped carboxylate ligands can lead to metal-cluster frameworks, and correspondingly, a few of metal–cluster structures have been reported [12–15]. 1,3-Adamantanedicarboxylic acid (H2ADC) is a V-shaped ligand with the angle of ca. 110° for the
http://dx.doi.org/10.1016/j.inoche.2016.06.009 1387-7003/© 2016 Elsevier B.V. All rights reserved.
two carboxyl groups, which would favor the formation of a metal–cluster structure. In previous work, we have successfully reported a dinuclear silver(I) cluster compound based on H2ADC [16]. In this communication, we present an unique octanuclear silver(I) cluster compound, namely [Ag8(ADC)4]n (1) [17]. The compound 1 exhibits significant Ag–Ag interactions to form 2D infinite silver layers with multiple unsaturated Ag atoms. Besides, the preliminary thermal and fluorescence experiments show that 1 possesses moderate thermal stability and strong fluorescent property. Thus, compound 1 was chosen as probe for sensing different anions, it shows that 1 has significant luminescent sensitivity to Cr2O27 − through luminescence quenching effect in aqueous solution, which makes its good candidate as luminescent sensor. Single crystal X-ray diffraction analysis shows that 1 consists of an octanuclear cluster unit. The cluster contains eight Ag(I) centers, as shown in Fig. S1. Ag1, Ag2, Ag3, Ag4 and Ag7 have the similar tetrahedral coordination geometries, defined by four oxygen atoms from ADC ligands. The average bond lengths of Ag1–O, Ag2–O, Ag3–O, Ag4–O, and Ag7–O are 2.422, 2.421, 2.428, 2.418 and 2.437 Å, respectively. Ag5, Ag6 and Ag8 have the similar {AgO3} trigonal planar coordination geometries. All the bond lengths are in agreement with those reported in other Ag(I) complexes. In 1, each completely deprotonated ADC ligand connects six silver atoms (Fig. S2). Interestingly, ten kinds of short Ag–Ag contacts can be found in compound 1 (Ag1–Ag2 = 2.981 Å, Ag2–Ag3 = 3.664 Å, Ag3–Ag8 = 3.178 Å, Ag5–Ag8 = 3.094 Å, Ag5–Ag7 = 2.995 Å, Ag6–Ag7 = 3.053 Å, Ag4– Ag6 = 3.288 Å, Ag1–Ag4 = 3.663 Å, Ag3–Ag4 = 2.980 Å, Ag6–Ag8 = 2.990 Å). As shown in Fig. 1, the silver atoms are linked into 2D infinite silver network structure, which is composed of two types of silver
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J.-C. Jin et al. / Inorganic Chemistry Communications 70 (2016) 157–159
Fig. 3. Thermogravimetric analysis (TGA) reveals that 1 can be stable up to 200 °C.
Fig. 1. The 2D infinite silver network with two types of silver closed loops.
closed loops (octagon silver ring: Ag1–Ag2–Ag3–Ag8–Ag5–Ag7–Ag6– Ag4, quadrilateral silver ring: Ag3–Ag4–Ag6–Ag8) via Ag–Ag interactions. Besides, the 2D silver cluster is decorated with ADC ligands at two sides in an outward fashion (Fig. 2). The solid-state luminescent spectra of compound 1 and ligand have been further measured at room temperature (Fig. S3). It was observed that an emission occurs at 505 nm for 1 (λex = 280 nm). However, the solid 1, 3-adamantanedicarboxylic acid is almost no luminescent. The emission of 1 may be derived from Ag–Ag interactions because 1 is an octanuclear silver(I) cluster and the nature of its emitting state strongly depends on the number of silver centre and on the interactions between them [18]. Moreover, the lifetime of compound 1 is measured at room temperature. As shown in Fig. S4. For 1 (λex = 368 nm), the lifetime at 505 nm emission shows 1.32 ns (60.50%) and 7.87 ns (39.50%) (χ2 = 1.110). The photoluminescence studies indicate that 1 can be the excellent candidate for photoactive material. Besides, The TGA indicates that 1 is stable up to 200 °C (Fig. 3). The preliminary thermal and fluorescent experiments show that 1 possesses strong fluorescent property and thermal stability. Thus, compound 1 was chosen as probe for sensing different anions. The luminescent responses of 1 (5 mg) to various anions have been investigated by dispersing in 1@H2O solutions of different sodium salts (2 mL, 0.1 mol/L: NaCl, NaNO3, NaNO2, Na2CO3, NaHCO3, Na2SO4, Na2SO3, NaH2PO4, HCOONa, NaB4O7, Na2Cr2O7). As shown in Fig. 4, the luminescent intensities are greatly determined by different anions, especially for Cr2O2− 7 , which drastically quenches the luminescence, reducing by 98.5% compared to that of the initial 1 in water. This experiment result demonstrates that the 1 can be highly effective and selective luminescent sensing for Cr2O2− 7 ion. The decreases of intensity ions and unsaturated caused by the weak interaction between Cr2O2− 7 Ag atoms in compound 1 and provide a non-radiative pathway for the
Fig. 2. The 2D silver network decorated with ADC ligands at two sides.
excitation energy [19]. As confirmed by the powder X-ray diffraction (PXRD) patterns (Fig. S5), the crystal structures of 1 immersed in metal ions solutions remain unchanged. To further research the sensitivity, the concentration gradient experiments were performed. In titration experiment, the emission responses were adjusted by the gradual addition of Na2Cr2O7@H2O solution (0.1 mol/L) into the suspension of 1@ H2O. As demonstrated in Fig. 5, resulted in a gradual decrease of lumithe increased amount of Cr2O2− 7 nescent intensity at 505 nm, and the intensity reduced to 50% at a concentration of 10 ppm for Na2Cr2O7, which means high sensitivity to Cr2O2− 7 . In summary, we have successfully synthesized and structurally characterized an unique and novel octanuclear silver(I) cluster compound based on 1,3-adamantanedicarboxylic acid. Compound 1 exhibits significant Ag–Ag interactions to form 2D infinite silver layer with multiple unsaturated Ag atoms. Photoluminescence studies show that 1 can exhibit significant luminescent sensitivity to Cr2O2− 7 through luminescent quenching effect in aqueous solution, which make its good candidate as luminescent sensor. Acknowledgments We are grateful for financial support from the NSF of China (Grants 21401143, 21377099 and 21271141); Science and Technology Project of Anhui Province (1606c08229 and 1406c085021); Science and Technology Project of Anhui Province (1206c0805031 and
Fig. 4. The luminescent responses of 1 to various anions.
J.-C. Jin et al. / Inorganic Chemistry Communications 70 (2016) 157–159
[4]
[5]
[6]
[7] Fig. 5. Emission spectra of 1 dispersed in H2O with the titration of Na2Cr2O7.
1406c085021); Key Project of Natural Science Research of Anhui Province (KJ2016A741); Natural Science Research Project of Anhui Colleges and Universities (KJ2015A286); The Project was Supported by State Key Laboratory of Materials Processing and Die & Mould Technology, Huazhong University of Science and Technology (P201417); National Training Programs of Innovation and Entrepreneurship for Undergraduates (201510376003 and 201510376002).
[8]
[9]
[10]
Appendix A. Supplementary data
[11]
CCDC 1474464 number for 1. The additional figures and supplementary crystallographic data in CIF for this paper. These data can be obtained freely. Supplementary data associated with this article can be found in the online version, at http://dx.doi.org/10.1016/j.inoche.2016.06.009.
[12]
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Ni, Luminescent groups 10 and 11 heteropolynuclear complexes based on thiolate or alkynyl ligands, Coord. Chem. Rev. 253 (2009) 1–20. P. Yang, F. Cui, X.-J. Yang, B. Wu, Syntheses and structures of mononuclear, dinuclear and polynuclear silver(I) complexes of 2-pyrazole-substituted 1,10-phenanthroline ligands, Cryst. Growth Des 13 (2012) 186–194. J. Lee, Y. Kang, N.S. Cho, K.M. Park, Role and effect of anions in the construction of silver complexes based on a pyridylimidazole ligand with L-type coordination vectors and their photoluminescence properties, Cryst. Growth Des. 16 (2016) 996–1004. (a) M.R. Branham, A.D. Douglas, A.J. Mills, J.B. Tracy, P.S. White, R.W. Murray, Arylthiolate-protected silver quantum dots, Langmuir. Langmuir 22 (2006) 11376–11383; (b) R. Zhang, X. Hao, X. Li, Z. Zhong, J. Sun, R. Cao, Soluble silver acetylide for the construction and structural conversion of all-alkynyl-stabilized high-nuclearity homoleptic silver clusters, Cryst. 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Zhang, Cluster-organic framework materials as heterogeneous catalysts for high efficient addition reaction of diethylzinc to aromatic aldehydes, Chem. Mater. 24 (2012) 4711–4716; (b) J.T. Petty, O.O. Sergev, D.A. Nicholson, J.T. Petty, A silver cluster–DNA equilibrium, Anal Chem. 85 (2013) 9868–9876; (c) B. Liu, W.P. Wu, L. Hou, Y.Y. Wang, Four uncommon nanocage-based Ln-MOFs: highly selective luminescent sensing for Cu2+ ions and selective CO2 capture, Chem. Commun. 50 (2014) 8731–8734. W.-H. Fang, L. Cheng, L. Huang, G.-Y. Yang, A series of lanthanide-based cluster organic frameworks made of heptanuclear trigonal-prismatic cluster units, Inorg. Chem. 52 (2012) 6–8. S. Vajda, M.G. White, Catalysis applications of size-selected cluster deposition, ACS Catalysis 5 (2015) 7152–7176. Y. Yong, C. Li, X. Li, T. Li, H. Cui, S. Lv, Ag7Au6 cluster as a potential gas sensor for CO, HCN, and NO detection, J. Phys. Chem. C 119 (2015) 7534–7540. J.-C. Jin, W.-G. Chang, J.-Q. Liu, C.-G. Xie, J. Wu, A new 3D helical silver(I) cluster metal–organic framework with microporous structure and luminescent property, Inorg. Chem. Commun. 34 (2013) 68–70. A mixture of 1,3-adamantanedicarboxylic acid (0.10 mmol, 22.4 mg), 1,2,3-Triazole4,5-dicarboxylic acid (0.10 mmol, 15.7 mg) in 4 mL CH3OH was layered onto a solution of AgNO3 (0.20 mmol, 34.0 mg) in 3 mL H2O, and then was kept in darkness at room temperature resulting in colorless block crystals formation after one week. Yield: 50%. Anal. Calcd for C48H56Ag8O16: C, 32.91; H, 3.22. Found: C, 32.53; H, 3.74. IR (KBr, cm−1): 3374(m), 2900(s), 2839(m), 2724(w), 1687(w), 1552(w), 1450(s), 1378(m), 1301(m), 1121(w), 1024(w), 981(w), 870(w), 813(w), 759(m), 702(s), 668(w), 525(w), 484(w), 450(w). Crystal data for 1: [Ag8(ADC)4]n, T = 293(2) K, M = 1751.89, monoclinic, space group Cc, a = 13.826(4) Å, b = 13.843(4) Å, c = 23.990(7) Å, α = 90°, β = 99.094°, γ = 90°. V = 4534 Å3, Z = 4, R1 = 0.0266, wR2 = 0.0655, S = 1.014. A. Barbieri, G. Accorsi, N. Armaroli, Luminescent complexes beyond the platinum group: the d10 avenue, Chem. Commun. 19 (2008) 2185–2193. K. Jayaramulu, R.P. Narayanan, S.J. George, T.K. Maji, Luminescent microporous metal–organic framework with functional Lewis basic sites on the pore surface: specific sensing and removal of metal ions, Inorg. Chem. 51 (2012) 10089–10091.
Contents lists available at ScienceDirect
Inorganic Chemistry Communications journal homepage: www.elsevier.com/locate/inoche
Short communication
A luminescent novel octanuclear silver(I) cluster framework with potential Cr2O27 − sensing Jun-Cheng Jin, Chen Jiang, Wen-Gui Chang, Guang-Nian Xu, Xu-Cheng Fu Technology Promotion Center of Nano Composite Material Preparation and Application, Anhui Provincial Laboratory of Biomimetic Sensor and Detecting Technology, West Anhui University, Anhui 237012, China
a r t i c l e
i n f o
Article history: Received 17 April 2016 Received in revised form 5 June 2016 Accepted 11 June 2016 Available online 13 June 2016 Keywords: Crystal engineering Silver cluster Anions sensor Fluorescence spectrum
a b s t r a c t An unique and novel octanuclear silver(I) cluster compound, [Ag8(ADC)4]n (1) (H2ADC = 1,3adamantanedicarboxylic acid), has been synthesized and characterized. Compound 1 exhibits significant Ag– Ag interactions to form 2D infinite silver layers with multiple unsaturated Ag atoms. Moreover, Luminescent investigations show that 1 can exhibit highly selective response to Cr2O2− 7 through luminescence quenching effect in aqueous solution, which make its good candidate as luminescent sensor. © 2016 Elsevier B.V. All rights reserved.
Designing and synthesis of inorganic-organic composite coordination polymers have been attracted considerable attention for exhibiting neoteric structures and properties, which have provided exciting new prospects [1,2]. Silver complexes and clusters possess unusual structural diversity and have been the subject of considerable interest [3]. To further study their structures, luminescent properties and sensors has proved that it is relevant to the structural elucidation of the metal-binding sites [4–6]. What's more, the coordination polymers have displayed a lots of promising applications in advanced materials, including the thermolytic preparation of nano-structured materials and the synthesis of monolayer-protected clusters, and so on [7–9]. We all know that silver(I) ion possesses a wide variety of coordination geometries in complexes, [10] which can be partially attributed to the lack of stereo-chemical preferences because of a d10 configuration. In addition, the weak nature of the silver-ligand bonds8 assumes that various weak interactions and then crystal packing forces could have greater influence on structure formation than that for more rigid metal-ligand systems [11]. On the other hand, carboxylates are dominant metal-binding units in coordination networks due to their negative charge significantly enhances the ability to form rigid bonds with metal centers. Some scientists have made great contributions to this field, however, it remains an interesting research realm to design and synthesized metal-cluster compounds through the self-assembly of metal ions and organic ligands. Generally, V-shaped carboxylate ligands can lead to metal-cluster frameworks, and correspondingly, a few of metal–cluster structures have been reported [12–15]. 1,3-Adamantanedicarboxylic acid (H2ADC) is a V-shaped ligand with the angle of ca. 110° for the
http://dx.doi.org/10.1016/j.inoche.2016.06.009 1387-7003/© 2016 Elsevier B.V. All rights reserved.
two carboxyl groups, which would favor the formation of a metal–cluster structure. In previous work, we have successfully reported a dinuclear silver(I) cluster compound based on H2ADC [16]. In this communication, we present an unique octanuclear silver(I) cluster compound, namely [Ag8(ADC)4]n (1) [17]. The compound 1 exhibits significant Ag–Ag interactions to form 2D infinite silver layers with multiple unsaturated Ag atoms. Besides, the preliminary thermal and fluorescence experiments show that 1 possesses moderate thermal stability and strong fluorescent property. Thus, compound 1 was chosen as probe for sensing different anions, it shows that 1 has significant luminescent sensitivity to Cr2O27 − through luminescence quenching effect in aqueous solution, which makes its good candidate as luminescent sensor. Single crystal X-ray diffraction analysis shows that 1 consists of an octanuclear cluster unit. The cluster contains eight Ag(I) centers, as shown in Fig. S1. Ag1, Ag2, Ag3, Ag4 and Ag7 have the similar tetrahedral coordination geometries, defined by four oxygen atoms from ADC ligands. The average bond lengths of Ag1–O, Ag2–O, Ag3–O, Ag4–O, and Ag7–O are 2.422, 2.421, 2.428, 2.418 and 2.437 Å, respectively. Ag5, Ag6 and Ag8 have the similar {AgO3} trigonal planar coordination geometries. All the bond lengths are in agreement with those reported in other Ag(I) complexes. In 1, each completely deprotonated ADC ligand connects six silver atoms (Fig. S2). Interestingly, ten kinds of short Ag–Ag contacts can be found in compound 1 (Ag1–Ag2 = 2.981 Å, Ag2–Ag3 = 3.664 Å, Ag3–Ag8 = 3.178 Å, Ag5–Ag8 = 3.094 Å, Ag5–Ag7 = 2.995 Å, Ag6–Ag7 = 3.053 Å, Ag4– Ag6 = 3.288 Å, Ag1–Ag4 = 3.663 Å, Ag3–Ag4 = 2.980 Å, Ag6–Ag8 = 2.990 Å). As shown in Fig. 1, the silver atoms are linked into 2D infinite silver network structure, which is composed of two types of silver
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J.-C. Jin et al. / Inorganic Chemistry Communications 70 (2016) 157–159
Fig. 3. Thermogravimetric analysis (TGA) reveals that 1 can be stable up to 200 °C.
Fig. 1. The 2D infinite silver network with two types of silver closed loops.
closed loops (octagon silver ring: Ag1–Ag2–Ag3–Ag8–Ag5–Ag7–Ag6– Ag4, quadrilateral silver ring: Ag3–Ag4–Ag6–Ag8) via Ag–Ag interactions. Besides, the 2D silver cluster is decorated with ADC ligands at two sides in an outward fashion (Fig. 2). The solid-state luminescent spectra of compound 1 and ligand have been further measured at room temperature (Fig. S3). It was observed that an emission occurs at 505 nm for 1 (λex = 280 nm). However, the solid 1, 3-adamantanedicarboxylic acid is almost no luminescent. The emission of 1 may be derived from Ag–Ag interactions because 1 is an octanuclear silver(I) cluster and the nature of its emitting state strongly depends on the number of silver centre and on the interactions between them [18]. Moreover, the lifetime of compound 1 is measured at room temperature. As shown in Fig. S4. For 1 (λex = 368 nm), the lifetime at 505 nm emission shows 1.32 ns (60.50%) and 7.87 ns (39.50%) (χ2 = 1.110). The photoluminescence studies indicate that 1 can be the excellent candidate for photoactive material. Besides, The TGA indicates that 1 is stable up to 200 °C (Fig. 3). The preliminary thermal and fluorescent experiments show that 1 possesses strong fluorescent property and thermal stability. Thus, compound 1 was chosen as probe for sensing different anions. The luminescent responses of 1 (5 mg) to various anions have been investigated by dispersing in 1@H2O solutions of different sodium salts (2 mL, 0.1 mol/L: NaCl, NaNO3, NaNO2, Na2CO3, NaHCO3, Na2SO4, Na2SO3, NaH2PO4, HCOONa, NaB4O7, Na2Cr2O7). As shown in Fig. 4, the luminescent intensities are greatly determined by different anions, especially for Cr2O2− 7 , which drastically quenches the luminescence, reducing by 98.5% compared to that of the initial 1 in water. This experiment result demonstrates that the 1 can be highly effective and selective luminescent sensing for Cr2O2− 7 ion. The decreases of intensity ions and unsaturated caused by the weak interaction between Cr2O2− 7 Ag atoms in compound 1 and provide a non-radiative pathway for the
Fig. 2. The 2D silver network decorated with ADC ligands at two sides.
excitation energy [19]. As confirmed by the powder X-ray diffraction (PXRD) patterns (Fig. S5), the crystal structures of 1 immersed in metal ions solutions remain unchanged. To further research the sensitivity, the concentration gradient experiments were performed. In titration experiment, the emission responses were adjusted by the gradual addition of Na2Cr2O7@H2O solution (0.1 mol/L) into the suspension of 1@ H2O. As demonstrated in Fig. 5, resulted in a gradual decrease of lumithe increased amount of Cr2O2− 7 nescent intensity at 505 nm, and the intensity reduced to 50% at a concentration of 10 ppm for Na2Cr2O7, which means high sensitivity to Cr2O2− 7 . In summary, we have successfully synthesized and structurally characterized an unique and novel octanuclear silver(I) cluster compound based on 1,3-adamantanedicarboxylic acid. Compound 1 exhibits significant Ag–Ag interactions to form 2D infinite silver layer with multiple unsaturated Ag atoms. Photoluminescence studies show that 1 can exhibit significant luminescent sensitivity to Cr2O2− 7 through luminescent quenching effect in aqueous solution, which make its good candidate as luminescent sensor. Acknowledgments We are grateful for financial support from the NSF of China (Grants 21401143, 21377099 and 21271141); Science and Technology Project of Anhui Province (1606c08229 and 1406c085021); Science and Technology Project of Anhui Province (1206c0805031 and
Fig. 4. The luminescent responses of 1 to various anions.
J.-C. Jin et al. / Inorganic Chemistry Communications 70 (2016) 157–159
[4]
[5]
[6]
[7] Fig. 5. Emission spectra of 1 dispersed in H2O with the titration of Na2Cr2O7.
1406c085021); Key Project of Natural Science Research of Anhui Province (KJ2016A741); Natural Science Research Project of Anhui Colleges and Universities (KJ2015A286); The Project was Supported by State Key Laboratory of Materials Processing and Die & Mould Technology, Huazhong University of Science and Technology (P201417); National Training Programs of Innovation and Entrepreneurship for Undergraduates (201510376003 and 201510376002).
[8]
[9]
[10]
Appendix A. Supplementary data
[11]
CCDC 1474464 number for 1. The additional figures and supplementary crystallographic data in CIF for this paper. These data can be obtained freely. Supplementary data associated with this article can be found in the online version, at http://dx.doi.org/10.1016/j.inoche.2016.06.009.
[12]
References
[13]
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