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Synthesis, structure, characterization and fluorescent properties of Ag+ complexes with extended π⋯π interactions
Journal of Molecular Structure 1101 (2015) 66e72
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Journal of Molecular Structure journal homepage: http://www.elsevier.com/locate/molstruc
Synthesis, structure, characterization and fluorescent properties of Agþ complexes with extended p/p interactions Ting-Hong Huang a, *, Jie Yan a, Hu Yang a, Liu Qiang b, Huai-Ming Du a a
Key Laboratories of Fine Chemicals and Surfactants in Sichuan Provincial Universities, Material Corrosion and Protection Key Laboratory of Sichuan Province, College of Materials and Chemical Engineering, Sichuan University of Science & Engineering, Zigong, 643000, China b College of Chemistry and Environmental Protection Engineering, Southwest University for Nationalities, Chengdu, 610041, China
a r t i c l e i n f o
a b s t r a c t
Article history: Received 12 February 2015 Received in revised form 8 August 2015 Accepted 10 August 2015 Available online 11 August 2015
Two mixed-ligand Ag (I) complexes, [Ag2(Phterpy)2(NO3)2(dppe)]$CH3CN (1) and [Ag4(Phterpy)2(NO3)2(dppp)2](NO3)2$6H2O (2) (dppe ¼ 1, 2-bis (diphenylphosphino) ethane, dppp ¼ 1, 3-bis (diphenylphosphino) propane, Phterpy ¼ 40 -phenyl-2, 20 :60 , 200 -terpyridine), have been synthesized and structurally characterized by IR, 1H-NMR, 31PeNMR, elemental analysis and X-ray crystal structure analysis. Structural analysis reveals that the change of bridging ligands from dppe to dppp lead to the and [Ag4(Phterpy)2 formation of centrosymmetric cations [Ag2(Phterpy)2(NO3)2(dppe)] (NO3)2(dppp)2]2þ, especially complex 2 containing two independent centrosymmetric tetramers with the central (obligate) Ag2O2 planes. Complexes 1 and 2 consist of the 1D infinite chains, with different variations in p-stacking patterns. Crystal structure of 1 contains 1D infinite chains constructed by p/p interactions between Phterpy, while 2 is built by p/p interaction of phenylene rings from dppp. All these reveal that the change of phosphine ligands might be the key of construction of different types of polynuclear structures and 1D p-stacking chain. Moreover, the solid-state emission spectra of complexes 1 and 2 display broad emission bands at 420e600 nm. © 2015 Elsevier B.V. All rights reserved.
Keywords: Agþ complexes Phosphine ligands pep Fluorescent properties
1. Introduction The design and syntheses of mixed-ligand complexes have been one of the most active research subjects [1e7], especially for supramolecular structures with this class of compounds [8e14]. Ligation of multi-pyridyl ligands to transition metal ions [15e18], especially Agþ [19,20], forming a diversity of supramolecular structures including stable planar complexes with tri[21e23] and penta-dentate multi-pyridyl ligands [24], displays a rich range of photoluminescent properties [25,26]. As a tridentate ligand, 40 -phenyl-2, 20 :60 , 200 -terpyridine (Phterpy) forms transition metal complexes by ridging a broad variety of metal ions [27e30]. Some of these complexes have been reported, especially for potential applications in the design of luminescent devices [31]. In the study of supramolecular architectures, much work has focused on the change of chelating or bridging ligand [32]. So some diverse phosphine ligands were generated to construct varieties of structures via self-assembly, including
* Corresponding author. E-mail address: [email protected] (T.-H. Huang). http://dx.doi.org/10.1016/j.molstruc.2015.08.024 0022-2860/© 2015 Elsevier B.V. All rights reserved.
mononuclear [33], dinuclear [34] and polynuclear structures [35], and to pursue highly effective luminescent complexes [36e38]. Mixed-ligand Ag (I) complexes containing both multipyridyl ligands and organic phosphine ligands have been reported as candidates [39e42]. pep stacking interactions have been widely have been extensively reported in many areas such as organic synthesis [43,44], polymer chemistry [45e47], luminescent properties [48,49], the structures of biological macromolecules [50], and so on [51,52]. The nature of pep stacking interactions is formed by electron complementarity. The stability order of p-stacking interactions is p-electron-deficientepelectron-deficient > p-electron-deficient-p-electron-rich > p-electron-richep-electron-rich [53]. That's why p-stacking interactions between electron-deficient and electron-deficient aromatic systems are easy to be investigated in self-assembly systems [54]. But the design and construction of infinite p-stacking structures, especially supramolecular structures based on different types of p-stacking interactions, are difficult. It is noteworthy that change of phosphine ligands leads to the formation of different p-stacking types and varieties of supramolecular structures. Herein, we wish to report the synthesis, structure, and luminescent properties of two Ag (I)
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complexes, [Ag2(Phterpy)2(NO3)2(dppe)]$CH3CN (1) and [Ag4(Phterpy)2(NO3)2(dppp)2] (NO3)2$6H2O (2) (dppe ¼ 1, 2-bis (diphenylphosphino) ethane, dppp ¼ 1, 3-bis (diphenylphosphino) propane, Phterpy ¼ 40 -phenyl-2, 20 :60 , 200 -terpyridine). Among our research strategies for these complexes, we also focus our attention on the formation of supramolecular structures induced by p/p stacking interactions, with the different p-stacking styles. 2. Result and discussion 2.1. Syntheses The reaction of AgNO3 with dppe and Phterpy in a ratio of 2:1:2 afforded dinuclear Ag(I) complexes 1, while the tetranuclear complex 2 is obtained by reaction of silver(I) salt and dppp Phterpy with the ratio of 2:1:1. At the room temperature, complexes 1 and 2 are soluble in DMF, DMSO, CH3CN, slightly soluble in CH2Cl2 and CHCl3, and hardly soluble in toluene. The IR spectra for complexes 1 and 2 mainly reflect the binding patterns of phosphine ligands (dppe or dppp), Phterpy and NO 3 moieties. The absorption peaks near 1435 cm1 are yPh(PePh) of PPh2 groups, while strong absorption peaks near 1385 and 1392 cm1 are attributed to NeO stretches of NO 3 groups. The absorption peaks near 1475 cm1, in the range 886e693 cm1 and near 510 cm1 are dCeCH (in the plane), dCeC (in and out the plane) and yAgep. The 1H NMR spectra of 1 and 2 reveal expected resonances typical for the coordinated phosphine ligands and Phterpy. The 31P NMR spectra show one singlet at 6.15 ppm for 1 and two singles at 1.17 and 15.15 ppm for 2. The different chemical shifts of 1 and 2 in the 31P NMR spectra may be due to their different electronic environment (1: AgN2OP, 2: AgN2OP and AgNO2P). In 2, a shift to higher frequencies occurs due to the deshielding effect of one O 31 1 atom from NO P{ H} 3 coordinated to silver. So, the singlet in the NMR spectra may be a result of both steric and electronic factors. 2.2. Crystal structures The single crystal X-ray diffraction analysis shows that the asymmetric unit of complex 1 contains half a dppe, one Phterpy, one Agþ, one NO 3 counterion and one CH3CN molecule. Two silver atoms are bridged by the dppe ligand, generating a dinuclear cation, while each of Agþ ion is coordinated by two N atoms from Phterpy, one O atom from NO 3 , one P atom from dppe, forming a
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distorted tetrahedral geometry (Fig. 1). The AgeN, AgeO and AgeP bond lengths are 2.331(2)e2.410(2) Å, 2.554(3) Å and 2.3674(7) Å within the normal ranges [55], and the metal ions are separated by a Ag/Ag distance of 7.105 Å. Corresponding NeAgeN and PeAgeO bond angles are 70.24(7) Å and 117.14(7) Å, while the NeAgeO and NeAgeP bond angles are 91.30(9)e94.27(8)Å and 121.21(5)e 146.31(6) Å. In 1, there are intramolecular p/p interactions between one pyridyl ring of Phterpy and the phenyl ring from dppe, respectively, with the ring centroids distance of 3.95 Å and the dihedral angle of 7.34 (Fig. 2a). Moreover, the intramolecular edgeface (CeH/p) interactions are also observed with CH/p distances of 2.97 Å [CeH/C < 3.1 Å, CeH/centroid < 3.4 Å] [56,57] and angles of 160 (Fig. 2b). This weak interactions (p/p and CeH/p) would play a stabilizing role for conformation. In the solid state, intermolecular Phterpy planes adopt p/p stacking interactions to link the cations into one-dimensional (1D) infinite chains along the c axis. The planes of Phterpy involved in pstacking are approximately parallel, respectively, with centroid distances of 3.68e3.87 Å and dihedral angles of 1.11e9.59 . The short contacts of atom/atom between rings are in the range from 3.668 to 4.023 Å, which are close to the sums of the van der Waals radii [58], revealing typical p/p stacking interactions (Fig. 3). In the packing structure, the weak interactions of CeH/O hydrogen bonds are ruled out in Table 3. For 2, the overall structure formed is different from 1, which is due to taking dppp instead of dppe to participate in the reaction. XRay diffraction analysis reveals that the complex 2 consists of two independent centrosymmetric tetramers with the central (obligate) Ag2O2 planes. One half of each pertaining to the asymmetric unit, Ag (1) is coordinated by two N atoms from Phterpy, one P atom from dppp and one O atom from nitrate, forming a distorted tetrahedral geometry. The other AgeP interaction to the asymmetric unit is bridged by the Phterpy ligand, the latter binding to the second phosphorus of the ligand and the peripheral oxygens of the nitrate (Fig. 4). The Phterpy bridges two Ag(I) atoms behaves as a bidentate ligand to one of the metal atoms and in a monodentate mode to the other one, while the dppp takes a cis coordination mode to bridge two Ag(I) atoms and is not coplanar with the PCCCP spine. Furthermore, four-membered bimetallic ring, Ag2O2 core, is also formed by two silver (I) ions linked by two oxygens of the nitrate bridges. The Ag1$$$Ag2 distance (3.382 Å) is shorter than the sum of the van der Waals radii of two silver(I) atoms (3.44 A) and, thus Ag$$$Ag interaction is observed. The bond distances of
Fig. 1. Cation structure of complex 1. Hydrogen atoms are deleted for clarity.
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Fig. 2. (a) Intramolecular p/p stacking interactions in 1; (b) Intramolecular CeH/p stacking interactions in 1. Hydrogen atoms are deleted for clarity.
the AgeN [2.286(3), 2.297(3) and 2.384(2) Å, respectively], AgeP [2.3729(8) and 2.3781(8) Å] and AgeO [2.486(2) Å, 2.642 Å and 2.668 Å] are within the normal ranges [59]. Corresponding NeAgeN and NeAgeO bond angles are 70.32(9) and 93.72(9) , while the NeAgeP and PeAgeO bond angles range from 119.20(7) to 147.06(7) . In addition, intramolecular p$$$p interactions are observed with centroid$$$centroid distances of 3.86 Å and dihedral angles of 9.06 , which are shorter than the corresponding values in complex 1 (Fig. 5a). In packing structure, p-stacking manner in 2 is much different from 1, which is due to taking dppp instead of dppe to participate in the reaction. Intermolecular p/p stacking interactions between phenylene rings from dppp, as shown in Fig. 5b, link the cations into one-dimensional infinite chains along the c axis (centroid/centroid distance: 3.78 Å). It is worth noting that no intermolecular p/p stacking interaction between Phterpy is observed
in the packing structure. The change of bridging ligands are likely responsible for the steric hindrance to inhibit intermolecular p/p stacking interactions. Similarly to complex 1, the weak interactions of CeH/O hydrogen bonds in the packing structure are ruled out in Table 4. 2.3. Photoluminescent properties Ag (I) complexes may emit a considerably weaker fluorescence at low temperature, however, examples emit at room temperature are rarely observed [60]. As shown in Fig. 6a and Fig. 6b, the solidstate excitation and emission spectra of complexes 1 and 2 at room temperature were studied. Complex 1, upon excitation at 384 nm, shows a relatively emission with lmax at 452 and 553 nm in the solid state at room temperature, similarly to the previously report, which may be assigned to ligand-based intramolecular charge
Fig. 3. Intermolecular p/p stacking interaction of complex 1. Hydrogen atoms are deleted for clarity.
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Table 1 Crystal data and structure refinement details of complexes 1e2. Complex
1
2
Empirical formula Formula weight Crystal system Space group a/Å b/Å c/Å a ( ) b ( ) g ( ) Volume (Å3), Z rcalc/g cm3 m/mm1 F(000) q range/ Reflections collected Independent reflections Data/restraints/parameters Goodness-of-fit on F2 Final R indices [I > 2s (I)] R indices (all data) Largest difference peak and hole (e Å3)
C70H54Ag2 N9O6P2 1394.90 Monoclinic C2/c 11.7259(9) 21.3228(16) 24.9518(18) 90 97.905(4) 90 6179.4(8), 4 1.499 0.748 2836 1.91e27.78 28966 7324[R(int) ¼ 0.0285] 7234/0/403 1.042 R1 ¼ 0.0353, wR2 ¼ 0.0907 R1 ¼ 0.0498, wR2 ¼ 0.0987 0.641 and 0.520
C96H82Ag4 N10O18P4 2219.08 Triclinic P-1 10.8585(10) 14.4515(12) 16.9788(13) 110.883(4) 92.066(5) 105.942(5) 2366.8(3), 1 1.557 0.956 1120 2.31e27.79 22615 10814 [R(int) ¼ 0.0225] 10814/6/595 1.013 R1 ¼ 0.0373, wR2 ¼ 0.0951 R1 ¼ 0.0560, wR2 ¼ 0.1068 0.609 and 0.512
Table 2 Selected bond lengths (Å) and angles ( ) for complexes 1e2. 1 Ag(1)eN(1) Ag(1)eP(1) Ag(1)eN(2) Ag(1)eO(1)
2.331(2) 2.3674(7) 2.410(2) 2.554(3)
N(1)eAg(1)eP(1) N(1)eAg(1)eN(2) P(1)eAg(1)eN(2) N(1)eAg(1)eO(1) P(1)eAg(1)eO(1) N(2)eAg(1)eO(1)
146.31(6) 70.24(7) 121.21(5) 91.30(9) 117.14(7) 94.27(8)
2 Ag(1)eN(3) Ag(1)eP(1) Ag(1)eN(2) Ag(2)eN(1) Ag(2)eP(2) Ag(2)eO(2)
2.297(3) 2.3781(8) 2.384(2) 2.286(3) 2.3729(8) 2.486(2)
N(3)eAg(1)eP(1) N(3)eAg(1)eN(2) P(1)eAg(1)eN(2) N(1)eAg(2)eP(2) N(1)eAg(2)eO(2) P(2)eAg(2)eO(2)
141.20(7) 70.32(9) 136.79(6) 147.06(7) 93.72(9) 119.20(7)
corresponding centrosymmetric cations [Ag2(Phterpy)2(NO3)2(dppe)] and [Ag4(Phterpy)2(NO3)2 (dppp)2]2þ ions are obtained in CH3CN solution. In particular, two independent centrosymmetric tetramers with the central (obligate) Ag2O2 planes in 2 are observed. Furthermore, complex 1 is organized into one-dimensional infinite chains by p/p interactions between Phterpy, while complex 2 is formed by p/p interaction of phenylene rings from dppp. All these indicate that the change of phosphine ligands may be the key of the steric hindrance to inhibit intermolecular p/p stacking interactions. Moreover, the solidstate emission spectra of complexes 1 and 2 display broad emission bands centered at 553 and 480 nm. 4. Experimental section 4.1. General methods and materials
transfer (ICT) [61]. In 2, the weak emission peak centered at 480 nm was attributed to ICT excited states [62], which reveals that the emission spectra of 2, compared to 1, is evidently blue-shift (Fig. 6). In addition, the solid-state emission spectra of complexes 1 and 2 reveal a broad orangeered emission band at room temperature with excitation at 397 nm (Fig. 7). The emission spectra of 1 and 2 are recorded at 467 and 545 nm, and 480 nm, showing that bridging dppp instead of dppe offered an avenue for electron transfer. So, the change of bridging ligand may play a role of blue shift with the variation of supramolecular structures.
All chemicals were of A. R. grade and were used as received without further purification. IR spectra were recorded as KBr pellets on a Nicolet 6700 spectrometer in the range 4000e450 cm1. Elemental analyses were measured on a Carlo ERBA 1106 analyzer. 1 H and 31P{1H} spectra were recorded on a Bruker 400 spectrometer at 400.15 and 161.98 MHz, respectively. The luminescent spectra were performed with an FL3-P-TCSPC spectrophotometer at room temperature. 4.2. Synthesis of [Ag2(Phterpy)2(NO3)2(dppe)]·CH3CN (1)
3. Conclusion Two mixed-ligand new Ag (I) complexes have been synthesized and characterized. The study of MS result through the change of bridging ligands from dppe to dppp suggests that the
Table 3 Hydrogen-bond geometry of the complex 1 (Å, ). DeH/A
DeH
H/A
D/A
DeH/A
C(4)eH(4A)/O(1)i C(11)eH(11A)/O(3)ii C(31)eH(31A)/O(3)iii
0.93 0.93 0.93
2.55 2.46 2.52
3.43 3.36 3.34
158 163 148
Symmetry codes: (i) 1 x,y,1/2 z; (ii) 1/2 þ x,1/2 y,1/2 þ z; (iii) 1 þ x,y,z.
To a stirred solution of AgNO3 (0.0169 g, 0.1 mmol) in CH3CN/ DMF, dppe (0.0199 g, 0.05 mmol) was added. The mixture was stirred for 0.5 h and then Phterpy (0.0309 g, 0.1 mmol) was added and was allowed to stir for 1 h at room temperature. The vapor diffusion of diethyl ether into the solution gave white prism crystals. The complex was obtained by filtration, washed with diethyl ether and dried in vacuo. Yield: 0.0418 g (60%). Anal. Calcd for C70H57Ag2N9O6P2, C, 60.14; H, 4.11; N, 9.02. Found: C, 59.07; H, 4.97; N, 9.43. IR (cm1): 3419 (br), 3057 (m), 1603 (m), 1583 (m), 1506 (w), 1475 (m), 1436 (s), 1392 (s), 1307 (s), 1098 (m), 999 (m), (884) (m), 824 (m), 792 (s), 763 (s), 742(s), 693 (s), 508 (s). 1H-NMR (CD3SOCD3, 25 C, TMS): d ¼ 7.14e8.86 (50H, Phterpy þ PPh2). 31P {1H}eNMR (CD3SOCD3, 25 C, TMS): 6.15 ppm.
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Fig. 4. Cation structure of complex 2. Hydrogen atoms and phenyl rings of dppp are deleted for clarity.
Fig. 5. (a) Intramolecular p/p stacking interactions in 2; (b) Intermolecular p/p stacking interactions between one molecule and the neighboring molecule in 2. Hydrogen atoms are deleted for clarity.
4.3. Synthesis of [Ag4(Phterpy)2(NO3)2(dppp)2](NO3)2∙6H2O (2) To a stirred solution of AgNO3 (0.0169 g, 0.1 mmol) in CH3CN/ DMF, dppp (0.0206 g, 0.05 mmol) was added. The mixture was stirred for 0.5 h and then Phterpy (0.0155 g, 0.0.05 mmol) was added and was allowed to stir for 1 h at room temperature. The vapor diffusion of diethyl ether into the solution gave white prism crystals. The complex was obtained by filtration, washed with diethyl ether and dried in vacuo. Yield: 0.0249 g (45%). Anal. Calcd for C96H94Ag4 N10O18P4, C, 51.68; H, 4.25; N, 6.28. Found: C, 50.35; H, 5.13; N, 5.69. IR (cm1): 3432 (br), 3054 (m), 2972 (w), 2856 (w),
Table 4 Hydrogen-bond geometry of the complex 2 (Å, ). DeH/A
DeH
H/A
D/A
DeH/A
C(4)eH(4)/O(4)i C(13)eH(13)/O(6) ii C(18)eH(18)/O(5)ii C(38)eH(38)/O(1)iii
0.93 0.93 0.93 0.93
2.49 2.25 2.43 2.56
3.40 3.05 3.29 3.30
168 144 155 137
Symmetry codes: (i) x,1 y,-z; (ii) x,1 þ y,z; (iii) 1 þ x,y,z.
1607 (m), 1569 (w), 1547 (w), 1476 (m), 1435 (s), 1385 (s), 1336 (s), 1287 (s), 1101 (m), 1003 (m), (886) (m), 826 (m), 793 (s), 763 (s), 746(s), 694 (s), 510(s). 1H-NMR (CD3SOCD3, 25 C, TMS): d ¼ 7.11e8.76 (70H, Phterpy þ PPh2). 31P{1H}eNMR (CD3SOCD3, 25 C, TMS): 1.17, 5.57 ppm.
4.4. X-ray crystallography Crystals suitable for X-ray structure analysis obtained by vapor diffusion of diethyl ether into a solution of complexes 1 and 2. Reflection intensity data were collected on a Bruker APEX CCD diffractometer with graphite monochromated MoeKa radiation (l ¼ 0.71073 Å) using the u technique at 296 K. All structures were solved by direct methods and refined by full-matrix least-squares on all F2 data using SHELXTL. Most of hydrogen atoms were generated geometrically, assigned fixed isotropic thermal parameters, and included in structure factor calculations. No hydrogen atoms were assigned on the solvent molecules (CH3CN and H2O). The crystal of 2 was very small and the data is of poor quality. Despite the fact that the ratio of data completeness is 0.96, the molecule structure of 2 can be determined. Crystal and structure
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Fig. 6. (a) Room temperature solid-state excitation spectra of complexes 1 (e) and 2 (—) with maximum emission; (b) Room temperature solid-state emission spectra of complexes 1 (e) and 2 (—) with maximum excitation.
References
Fig. 7. Emission spectra of complexes 1 (e) and 2 (—) in the solid state at room temperature, upon excited at 397 nm.
refinement data are summarized in Table 1. Selected bond lengths and bond angles are ruled out in Table 2. Acknowledgments This work is financially sponsored by Talent Introduction Funds of Sichuan University of Science and Engineering (No. 2014RC29), Key Project of Sichuan Education Department (No. 15ZA0223), the Opening Project of Key Laboratories of Fine Chemicals and Surfactants in Sichuan Provincial Universities (2015JXZ01) and the Opening Project of Material Corrosion and Protection Key Laboratory of Sichuan Province (No. 2015CL03). Supplemental material CCDC 1019631e1019632 contain the supplementary crystallographic data for complexes 1 and 2. These data can be obtained free of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (þ44) 1223-336-033; or e-mail: [email protected].
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Journal of Molecular Structure journal homepage: http://www.elsevier.com/locate/molstruc
Synthesis, structure, characterization and fluorescent properties of Agþ complexes with extended p/p interactions Ting-Hong Huang a, *, Jie Yan a, Hu Yang a, Liu Qiang b, Huai-Ming Du a a
Key Laboratories of Fine Chemicals and Surfactants in Sichuan Provincial Universities, Material Corrosion and Protection Key Laboratory of Sichuan Province, College of Materials and Chemical Engineering, Sichuan University of Science & Engineering, Zigong, 643000, China b College of Chemistry and Environmental Protection Engineering, Southwest University for Nationalities, Chengdu, 610041, China
a r t i c l e i n f o
a b s t r a c t
Article history: Received 12 February 2015 Received in revised form 8 August 2015 Accepted 10 August 2015 Available online 11 August 2015
Two mixed-ligand Ag (I) complexes, [Ag2(Phterpy)2(NO3)2(dppe)]$CH3CN (1) and [Ag4(Phterpy)2(NO3)2(dppp)2](NO3)2$6H2O (2) (dppe ¼ 1, 2-bis (diphenylphosphino) ethane, dppp ¼ 1, 3-bis (diphenylphosphino) propane, Phterpy ¼ 40 -phenyl-2, 20 :60 , 200 -terpyridine), have been synthesized and structurally characterized by IR, 1H-NMR, 31PeNMR, elemental analysis and X-ray crystal structure analysis. Structural analysis reveals that the change of bridging ligands from dppe to dppp lead to the and [Ag4(Phterpy)2 formation of centrosymmetric cations [Ag2(Phterpy)2(NO3)2(dppe)] (NO3)2(dppp)2]2þ, especially complex 2 containing two independent centrosymmetric tetramers with the central (obligate) Ag2O2 planes. Complexes 1 and 2 consist of the 1D infinite chains, with different variations in p-stacking patterns. Crystal structure of 1 contains 1D infinite chains constructed by p/p interactions between Phterpy, while 2 is built by p/p interaction of phenylene rings from dppp. All these reveal that the change of phosphine ligands might be the key of construction of different types of polynuclear structures and 1D p-stacking chain. Moreover, the solid-state emission spectra of complexes 1 and 2 display broad emission bands at 420e600 nm. © 2015 Elsevier B.V. All rights reserved.
Keywords: Agþ complexes Phosphine ligands pep Fluorescent properties
1. Introduction The design and syntheses of mixed-ligand complexes have been one of the most active research subjects [1e7], especially for supramolecular structures with this class of compounds [8e14]. Ligation of multi-pyridyl ligands to transition metal ions [15e18], especially Agþ [19,20], forming a diversity of supramolecular structures including stable planar complexes with tri[21e23] and penta-dentate multi-pyridyl ligands [24], displays a rich range of photoluminescent properties [25,26]. As a tridentate ligand, 40 -phenyl-2, 20 :60 , 200 -terpyridine (Phterpy) forms transition metal complexes by ridging a broad variety of metal ions [27e30]. Some of these complexes have been reported, especially for potential applications in the design of luminescent devices [31]. In the study of supramolecular architectures, much work has focused on the change of chelating or bridging ligand [32]. So some diverse phosphine ligands were generated to construct varieties of structures via self-assembly, including
* Corresponding author. E-mail address: [email protected] (T.-H. Huang). http://dx.doi.org/10.1016/j.molstruc.2015.08.024 0022-2860/© 2015 Elsevier B.V. All rights reserved.
mononuclear [33], dinuclear [34] and polynuclear structures [35], and to pursue highly effective luminescent complexes [36e38]. Mixed-ligand Ag (I) complexes containing both multipyridyl ligands and organic phosphine ligands have been reported as candidates [39e42]. pep stacking interactions have been widely have been extensively reported in many areas such as organic synthesis [43,44], polymer chemistry [45e47], luminescent properties [48,49], the structures of biological macromolecules [50], and so on [51,52]. The nature of pep stacking interactions is formed by electron complementarity. The stability order of p-stacking interactions is p-electron-deficientepelectron-deficient > p-electron-deficient-p-electron-rich > p-electron-richep-electron-rich [53]. That's why p-stacking interactions between electron-deficient and electron-deficient aromatic systems are easy to be investigated in self-assembly systems [54]. But the design and construction of infinite p-stacking structures, especially supramolecular structures based on different types of p-stacking interactions, are difficult. It is noteworthy that change of phosphine ligands leads to the formation of different p-stacking types and varieties of supramolecular structures. Herein, we wish to report the synthesis, structure, and luminescent properties of two Ag (I)
T.-H. Huang et al. / Journal of Molecular Structure 1101 (2015) 66e72
complexes, [Ag2(Phterpy)2(NO3)2(dppe)]$CH3CN (1) and [Ag4(Phterpy)2(NO3)2(dppp)2] (NO3)2$6H2O (2) (dppe ¼ 1, 2-bis (diphenylphosphino) ethane, dppp ¼ 1, 3-bis (diphenylphosphino) propane, Phterpy ¼ 40 -phenyl-2, 20 :60 , 200 -terpyridine). Among our research strategies for these complexes, we also focus our attention on the formation of supramolecular structures induced by p/p stacking interactions, with the different p-stacking styles. 2. Result and discussion 2.1. Syntheses The reaction of AgNO3 with dppe and Phterpy in a ratio of 2:1:2 afforded dinuclear Ag(I) complexes 1, while the tetranuclear complex 2 is obtained by reaction of silver(I) salt and dppp Phterpy with the ratio of 2:1:1. At the room temperature, complexes 1 and 2 are soluble in DMF, DMSO, CH3CN, slightly soluble in CH2Cl2 and CHCl3, and hardly soluble in toluene. The IR spectra for complexes 1 and 2 mainly reflect the binding patterns of phosphine ligands (dppe or dppp), Phterpy and NO 3 moieties. The absorption peaks near 1435 cm1 are yPh(PePh) of PPh2 groups, while strong absorption peaks near 1385 and 1392 cm1 are attributed to NeO stretches of NO 3 groups. The absorption peaks near 1475 cm1, in the range 886e693 cm1 and near 510 cm1 are dCeCH (in the plane), dCeC (in and out the plane) and yAgep. The 1H NMR spectra of 1 and 2 reveal expected resonances typical for the coordinated phosphine ligands and Phterpy. The 31P NMR spectra show one singlet at 6.15 ppm for 1 and two singles at 1.17 and 15.15 ppm for 2. The different chemical shifts of 1 and 2 in the 31P NMR spectra may be due to their different electronic environment (1: AgN2OP, 2: AgN2OP and AgNO2P). In 2, a shift to higher frequencies occurs due to the deshielding effect of one O 31 1 atom from NO P{ H} 3 coordinated to silver. So, the singlet in the NMR spectra may be a result of both steric and electronic factors. 2.2. Crystal structures The single crystal X-ray diffraction analysis shows that the asymmetric unit of complex 1 contains half a dppe, one Phterpy, one Agþ, one NO 3 counterion and one CH3CN molecule. Two silver atoms are bridged by the dppe ligand, generating a dinuclear cation, while each of Agþ ion is coordinated by two N atoms from Phterpy, one O atom from NO 3 , one P atom from dppe, forming a
67
distorted tetrahedral geometry (Fig. 1). The AgeN, AgeO and AgeP bond lengths are 2.331(2)e2.410(2) Å, 2.554(3) Å and 2.3674(7) Å within the normal ranges [55], and the metal ions are separated by a Ag/Ag distance of 7.105 Å. Corresponding NeAgeN and PeAgeO bond angles are 70.24(7) Å and 117.14(7) Å, while the NeAgeO and NeAgeP bond angles are 91.30(9)e94.27(8)Å and 121.21(5)e 146.31(6) Å. In 1, there are intramolecular p/p interactions between one pyridyl ring of Phterpy and the phenyl ring from dppe, respectively, with the ring centroids distance of 3.95 Å and the dihedral angle of 7.34 (Fig. 2a). Moreover, the intramolecular edgeface (CeH/p) interactions are also observed with CH/p distances of 2.97 Å [CeH/C < 3.1 Å, CeH/centroid < 3.4 Å] [56,57] and angles of 160 (Fig. 2b). This weak interactions (p/p and CeH/p) would play a stabilizing role for conformation. In the solid state, intermolecular Phterpy planes adopt p/p stacking interactions to link the cations into one-dimensional (1D) infinite chains along the c axis. The planes of Phterpy involved in pstacking are approximately parallel, respectively, with centroid distances of 3.68e3.87 Å and dihedral angles of 1.11e9.59 . The short contacts of atom/atom between rings are in the range from 3.668 to 4.023 Å, which are close to the sums of the van der Waals radii [58], revealing typical p/p stacking interactions (Fig. 3). In the packing structure, the weak interactions of CeH/O hydrogen bonds are ruled out in Table 3. For 2, the overall structure formed is different from 1, which is due to taking dppp instead of dppe to participate in the reaction. XRay diffraction analysis reveals that the complex 2 consists of two independent centrosymmetric tetramers with the central (obligate) Ag2O2 planes. One half of each pertaining to the asymmetric unit, Ag (1) is coordinated by two N atoms from Phterpy, one P atom from dppp and one O atom from nitrate, forming a distorted tetrahedral geometry. The other AgeP interaction to the asymmetric unit is bridged by the Phterpy ligand, the latter binding to the second phosphorus of the ligand and the peripheral oxygens of the nitrate (Fig. 4). The Phterpy bridges two Ag(I) atoms behaves as a bidentate ligand to one of the metal atoms and in a monodentate mode to the other one, while the dppp takes a cis coordination mode to bridge two Ag(I) atoms and is not coplanar with the PCCCP spine. Furthermore, four-membered bimetallic ring, Ag2O2 core, is also formed by two silver (I) ions linked by two oxygens of the nitrate bridges. The Ag1$$$Ag2 distance (3.382 Å) is shorter than the sum of the van der Waals radii of two silver(I) atoms (3.44 A) and, thus Ag$$$Ag interaction is observed. The bond distances of
Fig. 1. Cation structure of complex 1. Hydrogen atoms are deleted for clarity.
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Fig. 2. (a) Intramolecular p/p stacking interactions in 1; (b) Intramolecular CeH/p stacking interactions in 1. Hydrogen atoms are deleted for clarity.
the AgeN [2.286(3), 2.297(3) and 2.384(2) Å, respectively], AgeP [2.3729(8) and 2.3781(8) Å] and AgeO [2.486(2) Å, 2.642 Å and 2.668 Å] are within the normal ranges [59]. Corresponding NeAgeN and NeAgeO bond angles are 70.32(9) and 93.72(9) , while the NeAgeP and PeAgeO bond angles range from 119.20(7) to 147.06(7) . In addition, intramolecular p$$$p interactions are observed with centroid$$$centroid distances of 3.86 Å and dihedral angles of 9.06 , which are shorter than the corresponding values in complex 1 (Fig. 5a). In packing structure, p-stacking manner in 2 is much different from 1, which is due to taking dppp instead of dppe to participate in the reaction. Intermolecular p/p stacking interactions between phenylene rings from dppp, as shown in Fig. 5b, link the cations into one-dimensional infinite chains along the c axis (centroid/centroid distance: 3.78 Å). It is worth noting that no intermolecular p/p stacking interaction between Phterpy is observed
in the packing structure. The change of bridging ligands are likely responsible for the steric hindrance to inhibit intermolecular p/p stacking interactions. Similarly to complex 1, the weak interactions of CeH/O hydrogen bonds in the packing structure are ruled out in Table 4. 2.3. Photoluminescent properties Ag (I) complexes may emit a considerably weaker fluorescence at low temperature, however, examples emit at room temperature are rarely observed [60]. As shown in Fig. 6a and Fig. 6b, the solidstate excitation and emission spectra of complexes 1 and 2 at room temperature were studied. Complex 1, upon excitation at 384 nm, shows a relatively emission with lmax at 452 and 553 nm in the solid state at room temperature, similarly to the previously report, which may be assigned to ligand-based intramolecular charge
Fig. 3. Intermolecular p/p stacking interaction of complex 1. Hydrogen atoms are deleted for clarity.
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Table 1 Crystal data and structure refinement details of complexes 1e2. Complex
1
2
Empirical formula Formula weight Crystal system Space group a/Å b/Å c/Å a ( ) b ( ) g ( ) Volume (Å3), Z rcalc/g cm3 m/mm1 F(000) q range/ Reflections collected Independent reflections Data/restraints/parameters Goodness-of-fit on F2 Final R indices [I > 2s (I)] R indices (all data) Largest difference peak and hole (e Å3)
C70H54Ag2 N9O6P2 1394.90 Monoclinic C2/c 11.7259(9) 21.3228(16) 24.9518(18) 90 97.905(4) 90 6179.4(8), 4 1.499 0.748 2836 1.91e27.78 28966 7324[R(int) ¼ 0.0285] 7234/0/403 1.042 R1 ¼ 0.0353, wR2 ¼ 0.0907 R1 ¼ 0.0498, wR2 ¼ 0.0987 0.641 and 0.520
C96H82Ag4 N10O18P4 2219.08 Triclinic P-1 10.8585(10) 14.4515(12) 16.9788(13) 110.883(4) 92.066(5) 105.942(5) 2366.8(3), 1 1.557 0.956 1120 2.31e27.79 22615 10814 [R(int) ¼ 0.0225] 10814/6/595 1.013 R1 ¼ 0.0373, wR2 ¼ 0.0951 R1 ¼ 0.0560, wR2 ¼ 0.1068 0.609 and 0.512
Table 2 Selected bond lengths (Å) and angles ( ) for complexes 1e2. 1 Ag(1)eN(1) Ag(1)eP(1) Ag(1)eN(2) Ag(1)eO(1)
2.331(2) 2.3674(7) 2.410(2) 2.554(3)
N(1)eAg(1)eP(1) N(1)eAg(1)eN(2) P(1)eAg(1)eN(2) N(1)eAg(1)eO(1) P(1)eAg(1)eO(1) N(2)eAg(1)eO(1)
146.31(6) 70.24(7) 121.21(5) 91.30(9) 117.14(7) 94.27(8)
2 Ag(1)eN(3) Ag(1)eP(1) Ag(1)eN(2) Ag(2)eN(1) Ag(2)eP(2) Ag(2)eO(2)
2.297(3) 2.3781(8) 2.384(2) 2.286(3) 2.3729(8) 2.486(2)
N(3)eAg(1)eP(1) N(3)eAg(1)eN(2) P(1)eAg(1)eN(2) N(1)eAg(2)eP(2) N(1)eAg(2)eO(2) P(2)eAg(2)eO(2)
141.20(7) 70.32(9) 136.79(6) 147.06(7) 93.72(9) 119.20(7)
corresponding centrosymmetric cations [Ag2(Phterpy)2(NO3)2(dppe)] and [Ag4(Phterpy)2(NO3)2 (dppp)2]2þ ions are obtained in CH3CN solution. In particular, two independent centrosymmetric tetramers with the central (obligate) Ag2O2 planes in 2 are observed. Furthermore, complex 1 is organized into one-dimensional infinite chains by p/p interactions between Phterpy, while complex 2 is formed by p/p interaction of phenylene rings from dppp. All these indicate that the change of phosphine ligands may be the key of the steric hindrance to inhibit intermolecular p/p stacking interactions. Moreover, the solidstate emission spectra of complexes 1 and 2 display broad emission bands centered at 553 and 480 nm. 4. Experimental section 4.1. General methods and materials
transfer (ICT) [61]. In 2, the weak emission peak centered at 480 nm was attributed to ICT excited states [62], which reveals that the emission spectra of 2, compared to 1, is evidently blue-shift (Fig. 6). In addition, the solid-state emission spectra of complexes 1 and 2 reveal a broad orangeered emission band at room temperature with excitation at 397 nm (Fig. 7). The emission spectra of 1 and 2 are recorded at 467 and 545 nm, and 480 nm, showing that bridging dppp instead of dppe offered an avenue for electron transfer. So, the change of bridging ligand may play a role of blue shift with the variation of supramolecular structures.
All chemicals were of A. R. grade and were used as received without further purification. IR spectra were recorded as KBr pellets on a Nicolet 6700 spectrometer in the range 4000e450 cm1. Elemental analyses were measured on a Carlo ERBA 1106 analyzer. 1 H and 31P{1H} spectra were recorded on a Bruker 400 spectrometer at 400.15 and 161.98 MHz, respectively. The luminescent spectra were performed with an FL3-P-TCSPC spectrophotometer at room temperature. 4.2. Synthesis of [Ag2(Phterpy)2(NO3)2(dppe)]·CH3CN (1)
3. Conclusion Two mixed-ligand new Ag (I) complexes have been synthesized and characterized. The study of MS result through the change of bridging ligands from dppe to dppp suggests that the
Table 3 Hydrogen-bond geometry of the complex 1 (Å, ). DeH/A
DeH
H/A
D/A
DeH/A
C(4)eH(4A)/O(1)i C(11)eH(11A)/O(3)ii C(31)eH(31A)/O(3)iii
0.93 0.93 0.93
2.55 2.46 2.52
3.43 3.36 3.34
158 163 148
Symmetry codes: (i) 1 x,y,1/2 z; (ii) 1/2 þ x,1/2 y,1/2 þ z; (iii) 1 þ x,y,z.
To a stirred solution of AgNO3 (0.0169 g, 0.1 mmol) in CH3CN/ DMF, dppe (0.0199 g, 0.05 mmol) was added. The mixture was stirred for 0.5 h and then Phterpy (0.0309 g, 0.1 mmol) was added and was allowed to stir for 1 h at room temperature. The vapor diffusion of diethyl ether into the solution gave white prism crystals. The complex was obtained by filtration, washed with diethyl ether and dried in vacuo. Yield: 0.0418 g (60%). Anal. Calcd for C70H57Ag2N9O6P2, C, 60.14; H, 4.11; N, 9.02. Found: C, 59.07; H, 4.97; N, 9.43. IR (cm1): 3419 (br), 3057 (m), 1603 (m), 1583 (m), 1506 (w), 1475 (m), 1436 (s), 1392 (s), 1307 (s), 1098 (m), 999 (m), (884) (m), 824 (m), 792 (s), 763 (s), 742(s), 693 (s), 508 (s). 1H-NMR (CD3SOCD3, 25 C, TMS): d ¼ 7.14e8.86 (50H, Phterpy þ PPh2). 31P {1H}eNMR (CD3SOCD3, 25 C, TMS): 6.15 ppm.
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Fig. 4. Cation structure of complex 2. Hydrogen atoms and phenyl rings of dppp are deleted for clarity.
Fig. 5. (a) Intramolecular p/p stacking interactions in 2; (b) Intermolecular p/p stacking interactions between one molecule and the neighboring molecule in 2. Hydrogen atoms are deleted for clarity.
4.3. Synthesis of [Ag4(Phterpy)2(NO3)2(dppp)2](NO3)2∙6H2O (2) To a stirred solution of AgNO3 (0.0169 g, 0.1 mmol) in CH3CN/ DMF, dppp (0.0206 g, 0.05 mmol) was added. The mixture was stirred for 0.5 h and then Phterpy (0.0155 g, 0.0.05 mmol) was added and was allowed to stir for 1 h at room temperature. The vapor diffusion of diethyl ether into the solution gave white prism crystals. The complex was obtained by filtration, washed with diethyl ether and dried in vacuo. Yield: 0.0249 g (45%). Anal. Calcd for C96H94Ag4 N10O18P4, C, 51.68; H, 4.25; N, 6.28. Found: C, 50.35; H, 5.13; N, 5.69. IR (cm1): 3432 (br), 3054 (m), 2972 (w), 2856 (w),
Table 4 Hydrogen-bond geometry of the complex 2 (Å, ). DeH/A
DeH
H/A
D/A
DeH/A
C(4)eH(4)/O(4)i C(13)eH(13)/O(6) ii C(18)eH(18)/O(5)ii C(38)eH(38)/O(1)iii
0.93 0.93 0.93 0.93
2.49 2.25 2.43 2.56
3.40 3.05 3.29 3.30
168 144 155 137
Symmetry codes: (i) x,1 y,-z; (ii) x,1 þ y,z; (iii) 1 þ x,y,z.
1607 (m), 1569 (w), 1547 (w), 1476 (m), 1435 (s), 1385 (s), 1336 (s), 1287 (s), 1101 (m), 1003 (m), (886) (m), 826 (m), 793 (s), 763 (s), 746(s), 694 (s), 510(s). 1H-NMR (CD3SOCD3, 25 C, TMS): d ¼ 7.11e8.76 (70H, Phterpy þ PPh2). 31P{1H}eNMR (CD3SOCD3, 25 C, TMS): 1.17, 5.57 ppm.
4.4. X-ray crystallography Crystals suitable for X-ray structure analysis obtained by vapor diffusion of diethyl ether into a solution of complexes 1 and 2. Reflection intensity data were collected on a Bruker APEX CCD diffractometer with graphite monochromated MoeKa radiation (l ¼ 0.71073 Å) using the u technique at 296 K. All structures were solved by direct methods and refined by full-matrix least-squares on all F2 data using SHELXTL. Most of hydrogen atoms were generated geometrically, assigned fixed isotropic thermal parameters, and included in structure factor calculations. No hydrogen atoms were assigned on the solvent molecules (CH3CN and H2O). The crystal of 2 was very small and the data is of poor quality. Despite the fact that the ratio of data completeness is 0.96, the molecule structure of 2 can be determined. Crystal and structure
T.-H. Huang et al. / Journal of Molecular Structure 1101 (2015) 66e72
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Fig. 6. (a) Room temperature solid-state excitation spectra of complexes 1 (e) and 2 (—) with maximum emission; (b) Room temperature solid-state emission spectra of complexes 1 (e) and 2 (—) with maximum excitation.
References
Fig. 7. Emission spectra of complexes 1 (e) and 2 (—) in the solid state at room temperature, upon excited at 397 nm.
refinement data are summarized in Table 1. Selected bond lengths and bond angles are ruled out in Table 2. Acknowledgments This work is financially sponsored by Talent Introduction Funds of Sichuan University of Science and Engineering (No. 2014RC29), Key Project of Sichuan Education Department (No. 15ZA0223), the Opening Project of Key Laboratories of Fine Chemicals and Surfactants in Sichuan Provincial Universities (2015JXZ01) and the Opening Project of Material Corrosion and Protection Key Laboratory of Sichuan Province (No. 2015CL03). Supplemental material CCDC 1019631e1019632 contain the supplementary crystallographic data for complexes 1 and 2. These data can be obtained free of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (þ44) 1223-336-033; or e-mail: [email protected].
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