Degradation versus Expansion of the AgX Frameworks: Formation of

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Degradation versus Expansion of the AgX Frameworks: Formation of Oligomeric and Polymeric Silver Complexes from Reactions of Bulk AgX with N,N‑Bis(diphenylphosphanylmethyl)-2-aminopyridine Jü-Hua Yang,†,‡ Xin-Yi Wu,† Run-Tian He,† Zhi-Gang Ren,*,†,§ Hong-Xi Li,† Hui-Fang Wang,† and Jian-Ping Lang*,†,‡ †

College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, People’s Republic of China ‡ State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, People’s Republic of China § Institute of Materials Research and Engineering, Agency for Science, Technology and Research, 3 Research Link, Singapore 117602, Singapore S Supporting Information *

ABSTRACT: Reactions of N,N-bis(diphenylphosphanylmethyl)-2-aminopyridine (bdppmapy) with [Ag(MeCN)4]ClO4 or AgX (X = Cl, Br, I, SCN, CN) afforded a family of oligomeric and polymeric complexes: [Ag2(MeOH)(bdppmapy)2](ClO4)2 (1), [AgCl(bdppmapy)] (2), [AgBr(bdppmapy)] (3), [AgI(bdppmapy)] (4), [AgSCN(bdppmapy)] (5), [{(η2-bdppmapy)Ag(μ-CN)AgCN}2(μbdppmapy)] (6), [Ag4(μ-CN)4(μ-bdppmapy)] (7), and [Ag2(μ-CN)(μ-bdppmapy)2][Ag5(μ-CN)6] (8). Compounds 1−8 were characterized by elemental analyses, IR spectra, 1H and 31P{1H} NMR, electrospray ionization (ESI) mass spectra, powder X-ray diffraction (XRD), and single-crystal X-ray diffraction. Compounds 1−3 and 5 hold a one-dimensional (1D) chain in which [Ag(MeOH)]+ or [AgX] motifs are linked by bdppmapy bridges. Compound 6 has a tetrameric framework in which two linear [(η2-bdppmapy)Ag(μ-CN)AgCN] fragments are connected by a μ-bdppmapy ligand. Compound 7 contains a 1D staircase chain in which two zigzag [Ag(μ-CN)]n chains are linked by pairs of μ-bdppmapy bridges. Compound 8 possesses an unprecedented three-dimensional (3D) structure in which the channels of one 3D anionic [Ag10(μ-CN)12]n2n− net are plugged with 1D cationic [Ag4(μ-CN)2(μ-bdppmapy)4]n2n+ chains. The degradation versus expansion of the bulk AgX frameworks do affect the formation of [AgaXb]-based oligomers and polymers when AgX is treated with bdppmapy. The photoluminescent properties of 1−8 in the solid state were also investigated.

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INTRODUCTION In the past decades, the coordination chemistry of silver(I) halides and pseudohalides of various phosphine ligands has attracted much interest due to not only interesting structural diversity1−3 but also many potential applications in catalysis,4 potential antitumor agents,5 and luminescent materials.6 These complexes are usually prepared through their reactions with monophosphine ligands (e.g., PPh3),7 diphosphine ligands (e.g., bis(diphenylphosphino)methane (dppm))8,3a and polyphosphine ligands (e.g., N,N,N′,N′-tetra(diphenylphosphanylmethyl) ethylene diamine (dppeda)).9 As we know, bulk AgX (X = halide and pseudohalide) shows different frameworks in the solid state,10 and its framework always tends to be degraded into one or more small [AgaXb]based structural motifs in solution when it reacts with phosphine ligands. Such motifs are further combined by these ligands to generate oligomeric and polymeric [AgaXb]/ phosphine complexes.8,11 For example, the structure of bulk © 2013 American Chemical Society

AgCN consists of rows of linear [AgCN]n chains parallel to [001] with alternating long Ag−C and short Ag−N distances.10e Cracking its framework through phosphine ligands form discrete [Aga(CN)b]-based and one-dimensional (1D) [Aga(CN)b]n-based complexes.12 Che et al. reported that reactions of AgCN with equimolar tricyclohexylphosphine (PCy3) produced one 1D polymer [(Cy3P)Ag(NCAgCN)]n, whose structure contains a 1D [AgCN]n backbone, while employment of excess PCy3 yielded one discrete complex [(Cy3P)2Ag(NCAgCN)], which has a discrete [Ag2(CN)2] species in the structure. However, no reports have described the framework expansion of AgX (e.g., the 1D chain of bulk AgCN) to the 2D or 3D [AgaXb]-based net, when it reacts with phosphine ligands. Received: February 2, 2013 Revised: March 19, 2013 Published: March 20, 2013 2124

dx.doi.org/10.1021/cg4002048 | Cryst. Growth Des. 2013, 13, 2124−2134

Crystal Growth & Design

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Scheme 1. Reactions of bdppmapy with Ag(I) Salts

Besides the silver(I) phosphine complexes, it is well-known that the coordination chemistry of the silver(I) complexes of nitrogen donor ligands are also abundant.13 The combination of both N and P ends in one ligand may make its silver(I) chemistry more interesting as such Ag(I) complexes showed unique molecular architectures and physicochemical properties.14 We have been involved in the design and coordination chemistry of some tetra amino-phosphine and phosphinepyridyl ligands.15 A group of Cu(I) and Ag(I) complexes of these ligands with interesting structures including the dinuclear complexes and 1D and 2D polymeric complexes have been isolated. For example, the reactions of AgX (X = Cl, Br, I, CN, SCN, and dicyanamide (dca)) with N-diphenylphosphanylmethyl-4-aminopyridine (dppmapy) afforded a set of 1D or 2D [Ag2X2]-based coordination polymers.15a In these reactions, the framework of the bulk AgX was all broken into a [Ag2X2] species in the presence of dppmapy. The cyanide complex contains a linear [(CN)Ag(μ-CN)Ag] motif while other complexes all hold a rhombic [Ag(μ-X)2Ag] motif. Could other phosphine-pyridyl ligands induce the framework expansion of the bulk AgX to form 2D or 3D Ag/X/P coordination polymers with unique structures? In this work, we chose another P/N hybrid ligand, N,N-bis(diphenylphosphanylmethyl)-2-aminopyridine (bdppmapy), because it has different P atom numbers and steric hindrance from dppmapy and may coordinate Ag atoms via both N atom

of this pyridyl group and P atoms of the two phosphanyl groups. When it reacted with AgX (X = ClO4, Cl, Br, I, SCN, and CN), a set of 1D polymeric complexes, [Ag2(MeOH)(bdppmapy)2](ClO4)2 (1), [AgCl(bdppmapy)] (2), [AgBr(bdppmapy)] (3), [AgI(bdppmapy)] (4), [AgSCN(bdppmapy)] (5), one discrete complex [{(η2-bdppmapy)Ag(μ-CN)AgCN}2 (μ-bdppmapy)] (6), one 1D polymeric complex [Ag4(μ-CN)4(μ-bdppmapy)] (7), and one 3D polymeric complex [Ag 2 (μ-CN)(μ-bdppmapy) 2 ][Ag 5 (μCN)6] (8), were isolated. Although in the structures of 1−3 and 5−8, the AgX framework was degraded into small structural motifs like the [AgX] unit in 2−5, the [Ag(μCN)AgCN] unit in 6, and the [Ag2(μ-CN)]+ cationic unit in 8, or reformed into the 1D [Ag(μ-CN)]n chain in 7, compound 8 witnessed an unprecedented framework expansion from the 1D chain of AgCN to a 3D [Ag10(μ-CN12)n2n−-based net. Herein, we report their isolation, structural characterization, and luminescent properties.

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RESULTS AND DISCUSSION Synthetic and Spectral Aspects. Treatment of bdppmapy with [Ag(MeCN)4]ClO4 (molar ratio = 1: 1) in MeOH for 0.5 h at ambient temperature followed by filtration and diffusion of Et2O into the filtrate or evaporation of solvents from the filtrate led to the formation of 1 (51% yield) (Scheme 1). Analogous reactions of bdppmapy and equimolar AgX (X = Cl, Br, I) for 1 2125



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h followed by filtration and evaporation of solvents from the filtrate formed 2, 3, and 4 with less than 10% yields, which may be due to the low solubility of AgX in MeCN. Increasing the bdppmapy/AgX molar ratio to 1.5:1 at the same conditions could generate the same products 2 (79% yield), 3 (78% yield), and 4 (84% yield) (Scheme 1). Refluxing the MeCN solution containing bdppmapy and AgX (molar ratio = 1.5: 1) followed by a similar workup gave rise to white powders of 2−4 (confirmed by IR and powder XRD analyses (Supplementary Figure S1) with slightly improved yields. Treatment of a CH2Cl2 solution of bdppmapy with a suspension of equimolar AgSCN in EtOH at ambient temperature followed by filtration and diffusion of Et2O into the filtrate afforded 5 in 60% yield (Scheme 1). As discussed later in this article, the MeOH molecules are weakly coordinated at Ag centers in the cationic chain of 1. They might be replaced by other halides or pseudohalides. Complex 1 was thus mixed with two equiv of NH4X (X = Cl, Br, I, SCN) in MeCN. The resulting solution was stirred for 0.5 h at room temperature. Fast evaporation of MeCN from the solution could afford 2 (75% yield), 3 (72% yield), 4 (76% yield), and 5 (66% yield), respectively (Scheme 1). Their structures were confirmed by elemental analyses (Supplementary Table S1), IR spectra (Supplementary Figure S2), 1H NMR (Supplementary Figure S3), and powder X-ray diffraction (Supplementary Figure S4). However, attempts of analogous transformations in solid state by grinding complex 1 and two equiv of NH4X (X = Cl, Br, I, SCN) in an agate mortar for 25 min failed to generate 2−5. This is because 1 was decomposed during the period of its grinding with NH4X, which was confirmed by PXRD (Supplementary Figure S5). Intriguingly, reactions of a suspension of AgCN in MeCN with a solution of equimolar bdppmapy in CH2Cl2 at ambient temperature for 1 h followed by filtration and diffusion of Et2O into the filtrate produced a discrete tetranuclear complex 6 in 50% yield. Refluxing the MeCN solution containing bdppmapy and AgCN (molar ratio = 1:2) for 2 h followed by a standard workup produced a 1D polymeric complex 7 (colorless rhombic crystals) in 33% yield and several long column crystals of 8, which were separated under microscopy. However, extending the reflux time to 4 h for the above reactions produced a rare 3D polymeric complex 8 in 31% yield and 7 (38% yield). Further elongated reflux time did not change the ratio of 7 and 8 in this system, implying that 7 could not be converted into 8 and vice versa. In fact, we refluxed the solution of 6 or 7 (with or without bdppmapy) in MeCN for 2−4 h and could not isolate any crystals of 8. Increasing the molar ratios of bdppmapy/AgCN such as 1:4 did not form either 7 or 8, but yielded very thin plates of an unknown complex. Its PXRD patterns (Supplementary Figure S1g) could not match those of 7 and 8, implying that it might be a new compound. The poor crystal quality of this compound excluded our efforts to determine its crystal structure. These results showed the framework of the bulk AgCN could be degraded into various[Aga(CN)b]-based structural motifs in this reaction system, which definitely depends on the reaction time and the bdppmapy/AgCN molar ratios. Rational control of these conditions and careful crystallization could generate various bdppmapy/AgCN oligomeric and polymeric complexes with different topological structures. As described later in this article, in the cases of 2−5, the 3D framework of AgX was cleaved into the smallest motif [AgX]. In the case of AgCN, its linear chain was degraded into two [Ag(μ-CN)AgCN] units in 6 or reformed into two 1D zigzag [Ag(μ-CN)]n chains in 7. In 8,

part of the AgCN chain was broken into a [Ag2(μ-CN)]+ cationic unit, while another part was expanded into a rare 3D anionic [Ag10(μ-CN)12]n2n− net. These in situ-generated different [Aga(μ-CN)b] structural motifs are further combined by bdppmapy ligands, thereby forming the aforementioned products 6−8. Compounds 1−8 are stable toward air and moisture. Compound 1 is soluble in MeOH, MeCN, DMF, and DMSO, while 2−8 are slightly soluble in MeCN and DMSO but insoluble in other organic solvents. The elemental analyses are consistent with their chemical formula. In their IR spectra, the stretching vibration at 1097 cm−1 in 1 is assignable to the uncoordinated perchlorides, while a strong peak at 2090 cm−1 in 5 is the characteristic stretching vibration of the S-bonded thiocyanate. In the cases of 6−8, the CN stretching vibrations of the cyanides are located at 2138 (6), 2150 (7), and 2199/2142 (8) cm−1, respectively. Such differences may be due to the different coordination environments for the cyanides. The 1H NMR spectra of 1−8 in DMSO-d6 at room temperature all show the signals of the bdppmapy ligands including a multiplet at 7.00−7.80 ppm for the phenyl groups, a doublet at 5.60−7.00 ppm and a multiplet at 5.60−7.00 ppm for the pyridyl group, and a singlet at 4.60−5.30 ppm for the methylene group. For 1, a singlet at 3.17 ppm for the methyl group in MeOH is also discovered. In the 31P{1H}NMR spectra of 2−5, 7, and 8, only a broad peak (−4.66 ppm for 2, −2.19 ppm for 3, −8.29 ppm for 4, −1.61 ppm for 5, −1.72 ppm for 7, and 1.63 ppm for 8) is clearly observed, while in those of 1 and 6, two broad peaks (−1.14 and 1.79 ppm for 1 and −8.35 and −6.37 ppm for 6) are found, which may be related to the different coordination environments of bdppmapy ligands. Relative to that of bdppmapy (−22.811 ppm), these chemical shifts are larger, which may be due to the coupling between 107 Ag (109Ag) and 31P nuclei. The positive-ion ESI mass spectra of 1−8 in MeCN (Supplementary Figure S6) were measured to obtain some information about their behaviors in solution. The assignments were made by inspection of peak positions and isotopic distributions. In the positive-ion ESI-MS of 1, 3, and 5, two cationic peaks were found at m/z = 597.1 for the [Ag(bdppmapy)]+ cation (Figure 1a) and at m/z = 1089.3 for the [Ag(bdppmapy)2]+ cation (Figure 1b), respectively. However, in the ESI-MS of 2, 4, and 6−8, only one peak at m/z = 1089.3 for the [Ag(bdppmapy)2]+ cation was discovered. The existence of these cationic fragments in the positive-ion ESIMS of 1−8 implied that their frameworks may partially dissociate into various small cationic fragments under the ESI mass conditions. For 4, attempts to grow single crystals suitable for X-ray analysis failed. However, its PXRD patterns are similar to those of 2−3 (Supplementary Figure S1b), which, along with its data of IR, elemental analysis, and 1H NMR, suggested that 4 may have a similar structure to that of 2, 3, and 5. The identities of 1−3, 5, 6·CH2Cl2, 7·MeCN, and 8 were further confirmed by single-crystal X-ray diffraction. Crystal Structure of [Ag2(MeOH)(bdppmapy)2](ClO4)2 (1). Compound 1 crystallizes in the triclinic space group P1,̅ and its asymmetric unit contains one [(Ag0.5)2(bdppmapy)2Ag(MeOH)]2+ dication and two discrete ClO4− anions. As shown in Figure 2, Ag1 is coordinated with two P atoms from two neighboring bdppmapy ligands and one O atom of the MeOH molecule, forming an approximately trigonal planar geometry. In addition, there exists a weak interaction between Ag1 and N1 of the o-pyridyl group (2.789 Å). Both Ag2 and Ag3 adopt a 2126



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by two P atoms from neighboring bdppmapy ligands and one Cl (2) or Br (3) atom or one S atom from the terminal thiocyanide (5). The Ag atoms in 2, 3, and 5 are connected by the bdppmapy bridges to form a 1D chain extending along the b (for 2 and 3) (Supplementary Figures S7 and S8) and a (for 5) axis. For 2 or 3, the contact between Ag1 and the N1 is 3.775 and 3.742 Å, respectively, implying the N atom of the opyridyl group of bdppmapy in 2 or 3 remains intact. For 5, the N1 atom of the o-pyridyl group of bdppmapy in one chain keeps intact (Ag1···N1 = 3.088 Å), while the N6 atom of the opyridyl of bdppmapy in the other chain weakly binds to Ag2 (2.778 Å). The mean Ag−P bond length (2.4253(10) Å for 2, 2.4248(11) Å for 3, and 2.4422(13) Å for 5) (Table 1) is longer than that of 1 but somewhat shorter than those of the corresponding ones in the trigonally coordinated Ag(I) complexes such as [Ag(P(C6H11)3)2Cl] (2.471(3) Å), [Ag(P(C6H11)3)2Br] (2.4734(9) Å),16b and [(PPh2(CH2)6PPh2)2Ag2(SCN)2]n (2.517(12) Å).17c The Ag−X bond lengths (2.4756(10) Å for X = Cl (2); 2.5890(7) Å for X = Br (3); 2.5364(15) Å for X = S(SCN) (5)) are shorter than those of the corresponding ones in [Ag(P(C6 H 11 ) 3) 2 Cl] (2.489(1) Å), [Ag(P(C 6H 11 ) 3 ) 2Br] (2.618(1) Å), and [(PPh 2 (CH 2 ) 6 PPh 2 ) 2 Ag 2 (SCN) 2 ] n (2.677(2) Å). Crystal Structure of [{(η 2 -bdppmapy)Ag(μ-CN)AgCN} 2(μ-bdppmapy)]·CH 2Cl 2 (6·CH 2Cl2). Compound 6·CH2Cl2 crystallizes in the monoclinic space group P2/c, and its asymmetric unit contains half a [{(η2-bdppmapy)Ag(μCN)AgCN}2(μ-bdppmapy)] molecule and half a CH2Cl2 solvent molecule. As shown in Figure 4, three bdppmapy ligands in 6 reveal two different coordination modes. One mode is that bdppmapy chelates at Ag1 via the two P (P1 and P2) ends (η2-bdppmapy), whereas the other is that bdppmapy works as a bridge to link two Ag1 atoms via P3 (μ-bdppmapy). The four Ag atoms also exhibit different coordination geometries. Ag1 (or Ag1A) is tetrahedrally coordinated by three P atoms from two different bdppmapy ligands and one N atom from a cyanide. Ag2 is linearly coordinated by two C atoms from two cyanides. There is no interaction between Ag center and the N1 atom of the o-pyridyl group of bdppmapy in 6. The tetranuclear structure of 6 may be viewed as being built of two linear [(η2-bdppmapy)Ag(μ-CN)AgCN] fragments bridged by a μ-bdppmapy ligand. There is a 2-fold axis running through the N4, C32, and C35 atoms. The mean Ag−P bond length (2.4871(16) Å) (Table 1) in 6 is shorter than those containing tetrahedrally coordinated Ag such as [Ag(PPh2Cy)3(CN)]·5H2O (2.5214(14) Å, Cy = cyclohexyl)18a and [Ag(PPh3)3(dca)]·C6H5Cl (2.556(2) Å).18b The Ag1−N5 bond length (2.369(6) Å) is comparable to that of [Ag(PPh3)3(dca)]·C6H5Cl (2.338(2) Å),18b but longer than that found in [Ag2(μ-CN)(PPh3)3][Ag(CN)2]·py (2.260(2) Å).12b The [(μ-CN)AgCN]− ion binds to [(η2-bdppmapy)Ag]+ with the C50−Ag2−C49, Ag2−C50−N6, and Ag2−C49−N5 angles being 175.1(3)°, 177.4(9)°, and 174.3(7)°, suggesting the geometry of the [(μ-CN)AgCN]− moiety remains close to linearity. The Ag2−C49 and Ag2−C50 bond lengths in 6 are normal relative to those of [(Cy3P)2Ag(NCAgCN)].12a Crystal Structure of [Ag4(μ-CN)4(μ-bdppmapy)]·MeCN (7·MeCN). Compound 7·MeCN crystallizes in the monoclinic space group C2/c, and its asymmetric unit contains half a [Ag4(μ-CN)4(bdppmapy)] molecule and half a MeCN solvent molecule. Compound 7 may be viewed as having a 1D staircase chain (extending along the (1,1,1/2) direction) (Figure 5) in

Figure 1. (a) Observed (top) and calculated (bottom) isotopic patterns for the [Ag(bdppmapy)]+ cation. (b) Observed (top) and calculated (bottom) isotopic patterns for the [Ag(bdppmapy)2]+ cation.

Figure 2. View of a section of the 1D chain (extending along the (−1,1,1) direction) of 1 with a labeling scheme and 30% thermal ellipsoids. All hydrogen atoms are omitted for clarity. Symmetry code A: 1 − x, 1 − y, 1 − z.

linear geometry, coordinated with two P atoms from two neighboring bdppmapy ligands. There is a crystallographic inversion center being at Ag2. Each bdppmapy alternatively links the two-coordinated and three-coordinated Ag atoms to form a 1D cationic chain extending along the (−1,1,1) direction. The mean two-coordinated Ag−P bond length (2.374(2) Å) (Table 1) is slightly shorter than that found in the two-coordinated Ag(I) complex [(Ph 3 P) 2 Ag]BF 4 (2.4198(13) Å).16a The mean trigonally coordinated Ag−P bond length (2.3984(16) Å) is shorter than those observed in the trigonally coordinated Ag(I) complexes such as [Ag(P(C6H11)3)2Cl] (2.471(3) Å),16b [AgL(PPh3)2] (2.448(2) Å, L = 2,4,6-trichlorophenolate),17a and [Ag(H2O)L2]BF4 (2.426(3) Å, L = tris(2-furyl)phosphine).17b The Ag1−O1 bond length (2.529(5) Å) in 1 is much longer than those found in [AgL(PPh3)2] (2.235(3) Å, L = 2,4,6-trichlorophenolate) and [Ag(H2O)L2]BF4 (2.365(2) Å, L = tris(2-furyl)phosphine), indicating that the interaction of Ag(I) center with the MeOH molecule is relatively weak. Crystal Structures of [AgX(bdppmapy)] (2, X = Cl; 3, X = Br; 5, X = SCN). Compounds 2, 3, and 5 crystallize in the orthorhombic space group Pbca, and their asymmetric units contain one discrete [AgX(bdppmapy)] (2, X = Cl; 3, X = Br) molecule or two independent [AgSCN(bdppmapy)] molecules. Because their molecules are structurally similar, only the view of a section of one of the two independent 1D chains of 5 is presented in Figure 3. Each Ag1 atom is trigonally coordinated 2127



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Table 1. Selected Bond Lengths (Å) and Angles (deg) for 1−3 and 5−8a compound 1 Ag(1)−P(1) Ag(1)−P(3) Ag(3)−P(4) Ag(1)−O(1) P(3)−Ag(1)−P(1) P(4)−Ag(3)−P(4A) P(1)−Ag(1)−O(1)

2.4084(17) 2.3884(16) 2.374(2) 2.529(5) 152.75(5) 180.00(16) 95.83(13)

Ag(2)−P(2) Ag(2)−P(2A) Ag(3)−P(4A)

2.3744(14) 2.3744(14) 2.374(2)

P(2)−Ag(2)−P(2A) P(3)−Ag(1)−O(1)

180.00(1) 111.03(13)

Ag(1)−P(2A)

2.4319(10)

P(2A)−Ag(1)−Cl(1)

113.26(3)

Ag(1)−P(2A)

2.4323(11)

P(2A)−Ag(1)−Br(1)

113.07(3)

compound 2 Ag(1)−P(1) Ag(1)−Cl(1) P(1)−Ag(1)−P(2A) P(1)−Ag(1)−Cl(1)

2.4186(9) 2.4756(10) 127.57(3) 117.88(3)

Ag(1)−P(1) Ag(1)−Br(1) P(1)−Ag(1)−P(2A) P(1)−Ag(1)−Br(1)

2.4172(11) 2.5890(7) 128.32(4) 117.63(3)

compound 3

compound 5 Ag(1)−P(1) Ag(1)−S(1) P(2A)−Ag(1)−P(1) P(2A)−Ag(1)−S(1)

2.4473(14) 2.5351(16) 130.50(5) 117.59(5)

Ag(1)−P(1) Ag(1)−P(3) Ag(2)−C(50) P(2)−Ag(1)−P(1) P(3)−Ag(1)−P(2) N(5)−Ag(1)−P(2) C(50)−Ag(2)−C(49) Ag(2)−C(49)−N(5)

2.5097(16) 2.4488(16) 2.031(10) 93.87(6) 121.30(5) 97.05(17) 175.1(3) 174.3(7)

Ag(1)−P(2A)

2.4332(13)

P(1)−Ag(1)−S(1)

111.02(5)

compound 6 Ag(1)−P(2) Ag(1)−N(5) Ag(2)−C(49) P(3)−Ag(1)−P(1) N(5)−Ag(1)−P(1) N(5)−Ag(1)−P(3) Ag(1)−N(5)−C(49) Ag(2)−C(50)−N(6)

2.5027(18) 2.370(6) 2.051(8) 132.54(5) 102.22(16) 103.59(17) 151.9(6) 177.4(9)

compound 7 Ag(1)−P(1) Ag(2)−C(18) Ag(1)−N(4) N(3)−Ag(1)−P(1) N(3)−Ag(1)−N(4)

2.396(2) 2.093(9) 2.248(7) 129.65(19) 107.9(3)

Ag(1)−N(3) Ag(2)−C(19A)

2.210(7) 2.054(8)

N(4)−Ag(1)−P(1) C(19A)−Ag(2)−C(18)

121.35(19) 178.1(3)

Ag(1)−N(5) Ag(2)−N(4) Ag(3)−N(7) Ag(4)−C(33) Ag(2)−Ag(4E) N(6)−Ag(2)−N(4) N(4)−Ag(2)−N(3) C(33)−Ag(4)−C(33A)

2.181(5) 2.140(8) 2.054(7) 2.048(9) 3.3138(11) 137.1(3) 112.3(2) 171.7(4)

compound 8 Ag(1)−P(1) Ag(2)−N(3) Ag(2)−N(6) Ag(3)−C(34) Ag(4)−C(33A) N(5)−Ag(1)−P(1) N(6)−Ag(2)−N(3) C(34)−Ag(3)−N(7)

2.4509(17) 2.291(8) 2.128(7) 2.044(10) 2.048(9) 122.50(17) 110.5(3) 173.0(3)

Symmetry codes for 1 A, 1 − x, 1 − y, 1 − z; for 2 and 3 A, 1/2 − x, 1/2 + y, z; for 5 A, − 1/2 + x, y, 3/2 − z; for 7 A, x, − y, − 1/2 + z; for 8 A, −x, y, 3/2 − z; B, − x, 1 − y, 1 − z; E, − x, 1 − y, 1 − z. a

(2.916 Å) between Ag1 and N1 of the o-pyridyl group of the ligand is observed. Ag2 is linearly coordinated by two C atoms from two cyanides. The Ag1−P1 bond length (2.396(2) Å) (Table 1) in 7 is almost the same as that of 1 but shorter than those of the corresponding ones of 2, 3, and 5. The mean Ag1− N bond length (2.229(7) Å) is close to the corresponding one in [(Cy3P)Ag(NCAgCN)]n (2.235(5) Å) but shorter than that found in [(Cy3P)2Ag(NCAgCN)] (2.627(14) Å).12a The

which each 24-membered [Ag6(μ-CN)4(bdppmapy)2] macrometallocycle unit (Figure 5) is fused by sharing four silver ions and two bdppmapy ligands. Alternatively, this structure may be considered as being built of two parallel 1D zigzag [Ag(μCN)]n chains linked by the μ-bdppmapy bridges on the Ag1 atom and its symmetry-related Ag centers. The Ag centers in 7 show two different coordination geometries. Ag1 is trigonally coordinated by one P atom from the bdppmapy ligand and two N atoms from two cyanides. In addition, a weak interaction 2128



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Crystal Structure of [Ag2(μ-CN)(μ-bdppmapy)2][Ag5(μCN)6] (8). Compound 8 crystallizes in the monoclinic space group C2/c and its asymmetric unit consists of half a [Ag2(μCN)(μ-bdppmapy)2]+ cation and half a [Ag5(μ-CN)6]− anion. As shown in Figure 6a, two [Ag2(μ-CN)]+ fragments are linked by a pair of bdppmapy bridges to form one 18-membered cationic [Ag4(μ-CN)2(μ-bdppmapy)2]2+ macrometallocycle unit. Such a unit is further connected to other equivalent ones by two couples of bdppmapy bridges to yield a 1D laddertype cationic [Ag4(μ-CN)2(μ-bdppmapy)4]n2n+ chain extended along the c axis (Figure 6b). Ag1 in this chain is trigonally coordinated with two P atoms from the neighboring bdppmapy ligands and a C(N) atom from a cyanide. The mean Ag−P bond length (2.4618(17) Å) (Table 1) in 8 is in-between that of 1 (or 7) and that of [Ag(CN)(P(C6H11)3)2] (2.4803(9) Å).16b The Ag1···N1 contact is ca. 3.448 Å, suggesting no interaction between Ag1 and N1 of the o-pyridyl group of bdppmapy. The mean Ag1−C and Ag1−N bond lengths are normal. As shown in Figure 6c, 12 silver (I) ions combine 12 cyanides to form a 36-membered [Ag12(μ-CN)12] macrometallocycle unit (Figure 6c). The Ag atoms in the unit show two different coordination modes. Ag2 is trigonally coordinated by two N and one C(N) atoms from three cyanides, while Ag3 and Ag4 are two-coordinated by one C atom and one C(N) atom from two cyanides. Such a unit is further fused with its equivalent ones to create a 2D (6,3) anionic [Ag10(μCN)12]n2n− corrugated network extending along the ac plane (Figure 6d). Interestingly, this 2D network is interpenetrated with its symmetry-related ones to generate a unique 3D [Ag10(μ-CN)12]n2n− net with 1D rhombic channels extending along the c axis (Figure 6e). The volume of these channels is calculated to be 5913.2 Å3 (84.8%) per unit cell (calculated by using Platon program19). Each channel has a section area of 17.37 × 12.93 Å2 and is filled with one ladder-shaped cationic

Figure 3. View of a section of the 1D chain (extending along the a axis) of 5 with a labeling scheme and 30% thermal ellipsoids. All hydrogen atoms are omitted for clarity. Symmetry code A: − 1/2 + x, y, 3/2 − z.

Figure 4. View of the molecular structure of 6 with a labeling scheme and 30% thermal ellipsoids. All hydrogen atoms are omitted for clarity. Symmetry code A: − x, y, −1/2 − z.

[Ag(μ-CN)2]− unit is approximately linear and the Ag2−C bond lengths are also normal relative to those of 6.

Figure 5. View of a section of the 1D staircase chain (extending along the (1,1,1/2) direction) of 7. The circled part shows one 24-membered [Ag6(μ-CN)4(μ-bdppmapy)2] macrometallocycle of 7, with a labeling scheme and 30% thermal ellipsoids. All H atoms are omitted for clarity. Atom color codes: Ag, turquiose; P, pink; N, blue; C, black. Symmetry codes: A, x, − y, − 1/2 + z; B, 1 − x, y, 3/2 − z; C, 1 − x, − y, 1 − z. 2129



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Figure 6. (a) View of the 18-membered cationic [Ag4(μ-CN)2(μ-bdppmapy)2]2+ macrometallocycle in 8. Symmetry codes: A, x, 1 − y, −1/2 + z; B, 1 − x, 1 − y, 1 − z; C, 1 − x, y, 3/2 − z. (b) View of a portion of the 1D ladder-type cationic [Ag4(μ-CN)2(μ-bdppmapy)4]n2n+ chain (extending along the c axis) in 8. (c) View of the 36-membered [Ag12(μ-CN)12] macrometallocycle in 8. Symmetry codes: A −x, y, 3/2 − z; B 1/2 − x, 3/2 − y, 1 − z; C 1/2 + x, 3/2 − y, 1/2 − z; D −x, y, 1/2 − z. (d) View of the 2D (6,3) anionic [Ag10(μ-CN)12]n2n− corrugated network in 8 along the ac plane. See Figure 5 for color codes. (e) View of the 3D anionic [Ag10(μ-CN)12]n2n− net formed by interpenetration of the 2D networks in 8. (f) View of the 1D channels of the 3D anionic [Ag10(μ-CN)12]n2n− net filled by the 1D cationic [Ag4(μ-CN)2(μ-bdppmapy)4]n2n+ chains in 8. All hydrogen atoms are omitted for clarity.

[Ag4(μ-CN)2(μ-bdppmapy)4]n2n+ chain (Figure 6f). To our knowledge, this is the first example that one ladder-shaped cationic chain is encapsulated into the channels of a 3D anionic [Ag 10 (μ-CN) 12 ] n 2n− net. This Ag2···Ag4E separation (3.3138(11) Å; symmetry code for E, − x, 1 − y, 1 − z) between 2D networks is longer than those found in [Ag2(μdcpm)( μ-O 2 C CF 3 ) 2 ] ( 2 . 8 8 9 ( 1 ) Å , d c p m = bi s (dicyclohexylphosphino)methane),20 suggesting no existence of a metal−metal interaction in 8.

Photoluminescent Properties. The photoluminescent properties of 1−8 along with bdppmapy in the solid state at room temperature were studied (Figure 7). Upon excitation at 244 (1), 320 (2 and 3), 345 (4), 320 (5), 334 (6), and 340 nm (7 and 8), 1−8 exhibited photoluminescence with emission maxima at 386 (1), 372 (2), 374 (3), 389 (4), 366 (5), 366 (6), 369 (7), and 371 nm (8), respectively. The emission maxima of 5−8 are red-shifted relative to those of 2−4. When compared to the emission peak of bdppmapy at 370 nm, those of 1−4 are 2130



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expanded. It is understandable that AgCN could undergo its framework expansion to a 3D net in 8 because it has a 1D linear chain. The degradation versus expansion of the AgCN framework depends on many factors. The different structural frameworks of 6−8 might be ascribed to the ways of the rearrangement of the resulting [Aga(CN)b] species and the ways of bdppmapy ligands linking these species. The reaction temperature and time are also very critical in the formation of these three complexes. Of course, other factors such as AgCN/ bdppmapy molar ratios and solvents that affect their formation may not be ruled out. The photoluminescent properties of these complexes were influenced by the different electrondonating abilities of halides or pesudohalides. The methodology reported in this article is anticipated to apply in the preparation of new metal cyanide-based oligomers and polymers through cooperative degradation and expansion of the polydimensional frameworks of metal cyanides such as AuCN, CuCN, and Pt(CN)2 via the P and N hybrid ligands like bdppmapy. Further work in this direction is in progress.

Figure 7. Emission spectra of 1−8 and bdppmapy in the solid state.

red-shifted, while those of 5−8 are blue-shifted. Compared with other halides and pseudohalides, cyanide is the strongest electron-withdrawing and weakest electron-donating group, which generates the largest transition energy and thus exhibits the shortest λmax at 366−371 nm in 6−8. As iodide and the O atom of the coordinated MeOH molecule are stronger electron-donating groups than chloride and bromide, the emission maxima of 1 and 4 are red-shifted relative to those of 2 and 3. Currently, it is difficult to find obvious relations among the topological structures and the photoluminescent properties of 1−8. Their emission origins may be assignable to be halide (or pseudohalide)-to-ligand charge-transfer (XLCT).21a,b

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EXPERIMENTAL SECTION

General Procedures. All manipulations were carried out in open air. The ligand bdppmapy was prepared according to the literature method.21c Other chemicals were obtained from commercial sources and used as received. IR spectra were recorded on a Varian Scamiter1000 spectrometer (4000−400 cm−1) with a KBr disk. The elemental analyses for C, H, N were performed on a Carlo-Erba CHNO-S microanalyzer. 1H and 31P{1H} NMR spectra were recorded at ambient temperature on a Varian UNITY-300 spectrometer. Chemical shifts are quoted relative to the solvent signal in DMSO-d6 (1H) or to H3PO4 (85%) (31P external). ESI mass spectra were performed on an Aglinent 1200/6200 mass spectrometer using MeCN as the mobile phase. (Caution! Perchlorate salts of metal complexes with organic ligands are potentially explosive. A small amount was used in all the reactions and handled with great caution. All perchlorate compounds were tested and found to be resistant to shock.) Synthesis. [Ag2(bdppmapy)2(MeOH)](ClO4)2 (1). To a solution of [Ag(MeCN)4]ClO4 (37 mg, 0.1 mmol) in MeOH (5 mL) was added a solution of bdppmapy (49 mg, 0.1 mmol) in MeOH (5 mL). The mixture was stirred for 30 min and then filtered. Diethyl ether (20 mL) was allowed to diffuse into the filtrate to form colorless blocks of 1 one week later, which were collected by filtration, washed by Et2O, and dried in vacuo. Yield: 45 mg (51% based on Ag). Anal. Calcd. for C63H60Ag2Cl2N4O9P4: C, 53.00; H, 4.24; N, 3.92. Found: C, 52.59; H, 3.83; N, 4.03. IR (KBr disk): 3052 (w), 1592 (m), 1477 (s), 1435 (s), 1378 (w), 1323 (w), 1223 (m), 1163 (w), 1097 (s), 999 (w), 867 (w), 743 (m), 695 (m), 623 (m), 510 (m), 473 (w). 1H NMR (DMSO-d6, 300 MHz, ppm): δ 3.17 (s, 3H, −CH3), 5.00 (s, 4H, −CH2−), 6.37 (s, 3H, −py), 7.24−7.49 (m, 20H, −Ph), 7.70 (s 1H, −py). 31P{1H} NMR (300 MHz, ppm): δ −1.14 (br), 1.79 (br). [AgCl(bdppmapy)] (2). To a solution of bdppmapy (74 mg, 0.15 mmol) in MeCN (10 mL) was added AgCl (14 mg, 0.1 mmol). The mixture was stirred for 1 h and then filtered. Slow evaporation of the solvents from the filtrate afforded colorless prisms of 2 after 3 days, which were collected by filtration, washed by Et2O, and dried in vacuo. Yield: 50 mg (79% based on Ag). Anal. Calcd. for C31H28AgClN2P2: C, 58.74; H, 4.45; N, 4.42. Found: C, 58.63; H, 4.24; N, 4.54. IR (KBr disk): 2910 (w), 1591 (s), 1476 (s), 1434 (s), 1384 (w), 1319 (m), 1278 (w), 1158 (m), 1096 (m), 1037 (w), 852 (m), 743 (s), 693 (s), 617 (w), 546 (w), 511 (m), 472 (w). 1H NMR (DMSO-d6, 300 MHz, ppm): δ 4.97 (s, 4H, −CH2−), 5.97 (s, 1H, −py), 6.34 (d, 1H, −py), 6.92 (t, 1H, −py), 7.31−7.42 (m, 20H, −Ph), 7.63 (s, 1H, −py). 31 1 P{ H} NMR (300 MHz, ppm): δ −4.66 (br). [AgBr(bdppmapy)] (3). Compound 3 was prepared as colorless blocks in a similar manner to that used for the preparation of 2, using bdppmapy (74 mg, 0.15 mmol) and AgBr (19 mg, 0.1 mmol). Yield: 53 mg (78% based on Ag). Anal. Calcd. for C31H28AgBrN2P2: C,

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CONCLUSIONS In this article, we demonstrated the reactivity of a P,Ncontaining ligand bdppmapy toward various Ag(I) salts. Treatment of [Ag(MeCN)4]ClO4 with bdppmapy generated one 1D cationic polymer 1. When the bulk AgX (X = Cl, Br, I, SCN) reacted with bdppmapy, their 3D structures were broken into [AgX] units that are linked by bdppmapy to form 1D polymers 2−5. In these cases, only the framework degradation of the bulk AgX was observed, which is probably due to the fact that, relative to cyanide, halides and thiocyanide are weaker donor ligands and easily replaced by bdppmapy. Intriguingly, the linear chain of AgCN was cleaved into a [Ag(μ-CN)AgCN] species in the tetramer 6 when it reacted with bdppmapy at room temperature. Refluxing a mixture of AgCN and bdppmapy for 2 or 4 h yielded a 1D polymer 7 and a 3D polymer 8, respectively. In the former case, the linear chain of AgCN was turned into a zigzag chain, two of which are linked by bdppmapy bridges to form a 1D staircase chain. Such a chain reformation may be ascribed to the steric hindrance caused by introducing the bulky bdppmapy ligands between the two zigzag chains. In the latter case, the framework of AgCN undergoes very complicated structural changes. First, its linear chain was partly cleaved into [Ag2(μ-CN)]+ cationic units, which are picked up by pairs of bdppmapy to afford a 1D ladder-type cationic chain. Second, the AgCN chain was partly broken into various [Aga(CN)b] species, which are rearranged into a 2D anionic [Ag10(μ-CN)12]n2n− wavelike network, which is further interpenetrated with other equivalent ones to form a 3D [Ag10(μ-CN)12]n2n−-based net. This process conveys an unprecedented framework expansion from the 1D chain of bulk AgCN to the 3D [Ag10(μ-CN)12]n2n−-based anionic net. Third, the 1D cationic chain was enclosed into the channels of the 3D anionic net, which makes the AgCN framework be more 2131



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Table 2. Crystal Data and Structure Refinement Parameters for 1−3, 5, 6·CH2Cl2, 7·MeCN, and 8 1 chemical formula formula weight crystal system space group a (Å) b (Å) c (Å) α (deg) β (deg) γ (deg) V (Å3) Z T/K Dcalcd (g cm−3) λ(Mo Kα) (Å) μ (mm−1) F(000) no. of reflns collected no. of unique reflns no. of obsd. reflns no. of variables Ra wRb GOFc

2

C63H60Ag2Cl2N4O9P4 1427.67 triclinic P1̅ 10.936(2) 16.060(3) 19.474(4) 77.21(3) 76.03(3) 72.09(3) 3117.9(10) 2 223(2) 1.521 0.71073 0.876 1452 28710 14036 (Rint = 0.0437) 9903 (I > 2.00σ(I)) 815 0.0829 0.1648 1.101 6·CH2Cl2

5 chemical formula formula weight crystal system space group a (Å) b (Å) c (Å) α (deg) β (deg) γ (deg) V (Å3) Z T (K) Dcalcd (g cm−3) F(000) no. of reflns collected no. of unique reflns no. of obsd. reflns no. of variables Ra wRb GOFc

C64H56Ag2N6P4S2 1312.89 orthorhombic Pbca 13.815(3) 20.767(4) 41.214(8) 11824(4) 8 223(2) 1.475 0.71073 0.887 5344 33290 12515 (Rint = 0.0416) 5482 (I > 2.00σ(I)) 703 0.0665 0.1368 1.191

C98H86Ag4Cl2N10P6 2091.97 monoclinic P2/c 20.499(4) 11.142(2) 26.080(10) 123.51(2) 4967(2) 2 223(2) 1.399 0.71073 0.976 2112 38005 8615 (Rint = 0.0644) 7112 (I > 2.00σ(I)) 447 0.0685 0.1758 1.074

3

C31H28AgClN2P2 633.81 orthorhombic Pbca 20.415(4) 13.369(3) 20.967(4)

C31H28AgBrN2P2 678.27 orthorhombic Pbca 20.619(4) 13.453(3) 21.059(4)

5722(2) 8 223(2) 1.471 0.71073 0.933 2576 21464 6514 (Rint = 0.034) 5764 (I > 2.00σ(I)) 334 0.0534 0.0922 1.189 7·MeCN

5841(2) 8 223(2) 1.542 0.71073 2.190 2720 31687 6649 (Rint = 0.0517) 5914 (I > 2.00σ(I)) 334 0.0559 0.1064 1.244 8

C37H31Ag4N7P2 1067.11 monoclinic C2/c 24.932(4) 11.2178(7) 18.016(3) 129.11(3) 3909.5(9) 4 223(2) 1.813 0.71073 2.092 2080 7564 3443 (Rint = 0.0514) 2684 (I > 2.00σ(I)) 196 0.0743 0.1832 1.054

C69H56Ag7N11P4 1918.22 monoclinic C2/c 26.794(5) 20.802(4) 14.632(3) 121.21(3) 6975(2) 4 223(2) 1.827 0.71073 2.065 3744 15562 6135 (Rint = 0.0551) 4046 (I > 2.00σ(I)) 381 0.0554 0.0971 1.022

a R = Σ∥Fo| − |Fc∥/Σ|Fo|. bwR = {Σw(Fo2 − Fc2)2/Σw(Fo2)2}1/2. cGOF = {Σw((Fo2 − Fc2)2)/(n − p)}1/2, where n = number of reflections and p = total numbers of parameters refined.

54.89; H, 4.16; N, 4.13. Found: C, 54.85; H, 3.93; N, 4.17. IR (KBr disk): 2912 (w), 1592 (s), 1476 (s), 1434 (s), 1380 (w), 1318 (m), 1278(w), 1222 (m), 1159 (m), 1097 (m), 854 (m), 742 (s), 694 (s), 625 (w), 504 (m), 477 (m). 1H NMR (DMSO-d6, 300 MHz, ppm): δ 4.91 (s, 4H, −CH2−), 6.15 (d, 1H, −py), 6.39 (s, 1H, −py), 7.03 (s, 1H, −py), 7.33−7.69 (m, 21H, −Ph and −py). 31P{1H} NMR (300 MHz, ppm): δ −2.19 (br). [AgI(bdppmapy)] (4). Compound 4 was prepared as white powder in a similar manner to that used for the preparation of 2, using bdppmapy (74 mg, 0.15 mmol) and AgI (23 mg, 0.1 mmol). Yield: 60 mg (84% based on Ag). Anal. Calcd. for C31H28AgIN2P2: C, 51.34; H,

3.89; N, 3.86. Found: C, 51.37; H, 3.75; N, 3.99. IR (KBr disk): 1594 (s), 1472 (s), 1433 (s), 1376 (m), 1307 (w), 1275 (m), 1223 (m), 1160 (w), 1095 (m), 1026 (w), 914 (w), 853 (m), 745 (s), 692 (s), 493 (m). 1H NMR (DMSO-d6, 300 MHz, ppm): δ 5.02 (s, 4H, −CH2−), 5.88 (d, 1H, −py), 6.34 (s, 1H, −py), 6.90 (d, 1H, −py), 7.27−7.61 (m, 21H, −Ph and −py). 31P{1H} NMR (300 MHz, ppm): δ −8.29 (br). [AgSCN(bdppmapy)] (5). To a suspension of AgSCN (17 mg, 0.1 mmol) in EtOH (5 mL) was added a solution of bdppmapy (49 mg, 0.1 mmol) in CH2Cl2 (5 mL). The mixture was stirred for 30 min and then filtered. Diethyl ether (20 mL) was allowed to diffuse into the 2132



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filtrate to form colorless blocks of 5 after two weeks, which were collected by filtration, washed by Et2O, and dried in vacuo. Yield: 40 mg (60% based on Ag). Anal. Calcd. for C32H28AgN3P2S: C, 58.55; H, 4.30; N, 6.40. Found: C, 58.09; H, 4.18; N, 6.21. IR (KBr disk): 2922 (w), 2090 (s), 1593 (s), 1480 (s), 1433 (s), 1379 (w), 1320 (w), 1276 (w), 1224 (m), 1159 (m), 1096 (m), 856 (m), 741 (m), 694 (s), 625 (w), 507 (m), 473(w). 1H NMR (DMSO-d6, 300 MHz, ppm): δ 4.96 (s, 4H, −CH2−), 5.93 (d, 1H, −py), 6.34 (d, 1H, −py), 6.90 (s, 1H, −py), 7.35−7.63 (m, 21H, −Ph and −py). 31P{1H} NMR (300 MHz, ppm): δ −1.61 (br). [{(η2-bdppmapy)Ag(μ-CN)AgCN}2(μ-bdppmapy)] (6). To a suspension of AgCN (14 mg, 0.1 mmol) in MeCN (5 mL) was added a solution of bdppmapy (49 mg, 0.1 mmol) in CH2Cl2 (5 mL). The mixture was stirred for 1 h and then filtered. Diethyl ether (20 mL) was allowed to diffuse into the filtrate to form colorless blocks of 6·CH2Cl2 after 5 days, which were collected by filtration, washed by Et2O, and dried in vacuo. Yield: 27 mg (50% based on Ag). Anal. Calcd. for C97H84Ag4N10P6: C, 58.05; H, 4.22; N, 6.98. Found: C, 57.87; H, 4.61; N, 6.54. IR (KBr disk): 3050 (w), 2138 (w), 1597 (s), 1481 (s), 1434 (s), 1380 (m), 1318 (w), 1279 (w), 1225 (m), 1163 (m), 1101 (m), 1000 (w), 854 (m), 746 (s), 691 (s), 506 (w), 475 (w). 1H NMR (DMSO-d6, 300 MHz, ppm): δ 5.03 (s, 4H, −CH2−), 5.76 (s, 1H, −py), 5.93 (d, 1H, −py), 6.34 (s, 1H, −py), 6.91−7.40 (m, 21H, −Ph and −py). 31P{1H} NMR (300 MHz, ppm): δ −8.35 (br), −6.37 (br). [Ag4(μ-CN)4(μ-bdppmapy)] (7). The mixture of bdppmapy (49 mg, 0.1 mmol) and AgCN (27 mg, 0.2 mmol) in MeCN (5 mL) was refluxed for 2 h. Then, the resulting solution was cooled to room temperature and filtered. Diethyl ether (20 mL) was allowed to diffuse into the filtrate to form colorless rhombic crystals of 7·MeCN mixed with several long columns of 8 after three days, which were collected by filtration and separated under microscopy. Crystals of 7·MeCN were further washed by Et2O and dried in vacuo. Yield: 17 mg (33% based on Ag). Anal. Calcd. for C35H28Ag4N6P2: C, 40.97; H, 2.75; N, 8.19. Found: C, 41.33; H, 2.34; N, 8.52. IR (KBr disk): 3049 (w), 2931 (w), 2150 (m), 1592 (s), 1481 (s), 1434 (s), 1370 (w), 1320 (m), 1277 (w), 1213 (w), 1159 (m), 1096 (m), 1037 (w), 858 (m), 739 (m), 692 (s), 503 (m). 1H NMR (DMSO-d6, 400 MHz, ppm): δ 4.71 (s, 4H, −CH2−), 6.32−6.44 (d, 2H, −py), 7.09 (s, 1H, −py), 7.44−7.61 (m, 21H, −Ph and −py). 31P{1H} NMR (300 MHz, ppm): δ −1.72 (br). [Ag2(μ-CN)(μ-bdppmapy)2][Ag5(μ-CN)6] (8). A mixture containing bdppmapy (49 mg, 0.1 mmol) and AgCN (27 mg, 0.2 mmol) in MeCN (5 mL) was refluxed for 4 h. It was then cooled to room temperature and filtered. Diethyl ether (20 mL) was allowed to diffuse into the filtrate to form colorless long columns of 8 mixed with rhombic crystals of 7·MeCN after three days, which were collected by filtration and separated under microscopy. Crystals of 8 and 7·MeCN were washed by Et2O and dried in vacuo. Yield for 7: 20 mg (38% based on Ag). Yield for 8: 17 mg (31% based on Ag). Anal. Calcd. for C69H56Ag7N11P4: C, 43.20; H, 2.94; N, 8.03. Found: C, 42.83; H, 2.69; N, 8.50. IR (KBr disk): 3053 (w), 2928 (w), 2199 (w), 2142 (m), 1636 (w), 1595 (m), 1479 (s), 1434 (s), 1384 (m), 1314 (w), 1219 (w), 1158 (w), 1097 (m), 998 (w), 865 (m), 743 (s), 696 (s), 507 (m), 471 (w). 1H NMR (DMSO-d6, 300 MHz, ppm): δ 4.83 (s, 4H, −CH2−), 6.18 (d, 1H, −py), 6.40 (s, 1H, −py), 7.02 (s, 1H, −py), 7.41−7.62 (m, 21H, −Ph and −py). 31P{1H} NMR (300 MHz, ppm): δ −1.63 (br). Conversion of 1 to 2−5. To a solution of 1 (143 mg, 0.1 mmol) in MeCN (10 mL) was added NH4Cl (11 mg, 0.2 mmol). The mixture was stirred for 30 min to produce white powder of 2, which were collected by filtration, washed by Et2O, and dried in air. Yield: 95 mg (75% based on 1). Compounds 3−5 could be prepared in a similar manner to that used for the preparation of 2, using 1 (143 mg, 0.1 mmol) and NH4Br (20 mg, 0.2 mmol), NH4I (29 mg, 0.2 mmol), or NH4SCN (15 mg, 0.2 mmol) in MeCN (10 mL). Yield: 98 mg for 3 (72%), 109 mg for 4 (76%), and 87 mg (66%) for 5. X-ray Structure Determinations. Single crystals of 1-3, 5, 6·CH2Cl2, 7·MeCN, and 8 suitable for X-ray analysis were obtained directly from the above preparations. All measurements were made on

a Rigaku Mercury CCD X-ray diffractometer by using graphite monochromated Mo Kα (λ = 0.71073 Å) radiation. Each single crystal was mounted with grease at the top of a glass fiber and cooled at 223 K in a liquid nitrogen stream. Cell parameters were refined by using the program Crystalclear (Rigaku and MSc, Ver. 1.3, 2001) on all observed reflections. The collected data were reduced by using the program CrystalClear (Rigaku and MSc, Ver. 1.3, 2001), and an absorption correction (multiscan) was applied. The reflection data were also corrected for Lorentz and polarization effects. All crystal structures were solved by direct methods and refined on F2 by full-matrix least-squares methods with the SHELXTL-97 program.22 There were complicated disorder problems in the structures of these compounds. For 1, one phenyl group of the −PPh2 is disordered over two sites with the occupancy factor of 0.60/ 0.40 for C57−C62/C57A−C62A. For 6·CH2Cl2, one pyridyl group is disordered over two positions (C32−C35−C34A−N3/C32A− C35A−C34−N3) by rotating about the N4−C32 bond with equal occupancy factors. Besides, the CH2Cl2 solvent molecule is also disordered over two orientations with equal occupancy factors for Cl1−Cl2/Cl2−Cl2A. For 7·MeCN, one phenyl group of the −PPh2 is disordered over two sites with equal occupancy factors for C6−C11/ C6A−C11A. One pyridyl group (C1−C4, C3A, and N1) is also disordered over two positions by rotating about the N2−C1 bond with equal occupancy factors, while, in the case of 8, three cyanides are disordered over two orientations with equal occupancy factors for C32−N5A/C32A−N5, C35−N6A/C35A−N6 and C36−N7A/ C36A/N7. All non-hydrogen atoms were refined anisotropically except for those of the disordered CH2Cl2 molecule in 6·CH2Cl2, and the phenyl group in 7·MeCN were refined isotropically. The hydrogen atoms of the MeOH molecule in 1, the disordered CH2Cl2 solvent molecule, and the C33 atom of the disordered pyridine group in 6 were not located. All other hydrogen atoms were placed in geometrically idealized positions (C−H = 0.97 Å for methyl groups, C−H = 0.95 Å for pyridyl, phenyl, and ethylene groups, C−H = 0.99 Å for methylene groups, and N−H = 0.87 Å for −NH− groups) and constrained to ride on their parent atoms with Uiso(H) = 1.2− 1.5Ueq(C,N). Important crystal data and collection and refinement parameters for 1−3, 5, 6·CH2Cl2, 7·MeCN, and 8 are given in Table 2.

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ASSOCIATED CONTENT

S Supporting Information *

Crystallographic data of 1, 2, 3, 5, 6·CH2Cl2, 7·MeCN, and 8 (CIF). This material is available free of charge via the Internet at http://pubs.acs.org.

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AUTHOR INFORMATION

Corresponding Author

*(J.-P.L.) E-mail: [email protected]. (Z.-G.R.) E-mail: [email protected]. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS We thank the National Natural Science Foundation of China (20901054, 21271134, and 21171124) and the State Key Laboratory of Organometallic Chemistry of Shanghai Institute of Organic Chemistry (201201006) for financial support. J.-P.L. also highly appreciates the support for the Qin-Lan Project and the “333” Project of Jiangsu Province, the Priority Academic Program Development of Jiangsu Higher Education Institutions, and the “SooChow Scholar” Program of Suzhou University. We are also greatly thankful for the helpful comments from the editor and the reviewers. 2133



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Article

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