One-Dimensional Corrugated Tape AgI Coordination Polymers

CRYSTAL GROWTH & DESIGN

One-Dimensional Corrugated Tape AgI Coordination Polymers Constructed of Ag-C Bonds Kamran Akhbari and Ali Morsali* Department of Chemistry, Faculty of Sciences, Tarbiat Modares UniVersity, P.O. Box 14115-175, Tehran, Islamic Republic of Iran

2007 VOL. 7, NO. 10 2024-2030

ReceiVed May 19, 2007; ReVised Manuscript ReceiVed July 22, 2007

ABSTRACT: Three one-dimensional (1D) polymers assembled of Ag-C bonds, [Ag2(µ3-L)2(MeCN)]n (1-3) [L ) 4,4,4-trifluoro1-phenyl-1,3-butandione (HTFPB) (1), 4,4,4-trifluoro-1-naphthyl-1,3-butandionate (HTFNB) (2), and 4,4,4-trifluoro-1-thiophen1,3-butandione (HTFTB) (3)] have been synthesized and characterized by elemental analysis, IR, and 1H NMR spectroscopy. The thermal stability of compounds 1-3 were studied by thermal gravimetric and differential thermal analyses. The single-crystal X-ray structures of compounds 1 and 2 show two types of AgI ions with coordination numbers of five and four. The Ag atoms contain strong AgI-Cmethine bonds and thus produce 1D corrugated tape coordination polymers. Furthermore, the ligands and complexes 1-3 are luminescent in the solid state with emission maxima in the visible light region (λmax ) 470 nm). The results of studies the stoichiometry and formation of complexes 1-3 in acetonitrile solution were found to be in support of their solid-state stoichiometries. Introduction Metal coordination polymers have been studied widely as they represent an important interface between synthetic chemistry and materials science, and they have specific structures, properties, and reactivities that are not found in mononuclear compounds. The synthesis of metal coordination polymers is often guided by the quest to understand how molecules can be organized and how functions can be achieved. Many attempts have been made to prepare a variety of transitional metal complexes using different spacers, and their structures and properties have been physically and chemically determined.1-4 Previous investigations have addressed that metal-heteroatom, metal-carbon, and metal-metal interactions are three of the most important interactions in the construction of Ag polymeric networks in the solid state. (1) Extended frameworks are comprised of organic spacers containing heteroatom donors via metal-heteroatom coordination bonds.5 (2) Networks are assembled from aromatic ligands via metal-carbon bonds. For example, Ag-containing organometallic coordination polymers are generated from smaller aromatics and also polycyclic aromatic hydrocarbons based on cation-π interactions.6,35 (3) However, although the closed d10 configuration of silver(I) appears to cancel any intermetallic bonding in silver(I) complexes, there are many examples of dimeric or polymeric silver(I) complexes with definite Ag/Ag attractive forces known as argentophilic interactions.7 In this work, we wish to report on the synthesis, characterization, thermal, luminescence, crystal structures, spectrophotometric, and conductometric studies of three novel one-dimensional (1D) Ag(I) coordination polymer based on bridging methine moieties of β-dicarbonyl compounds, 4,4,4-trifluoro-1-phenyl-1,3-butandione (HTFPB), 4,4,4-trifluoro-1-naphthyl-1,3-butandione (HTFNP), and 4,4,4-trifluoro1-thiophen-1,3-butandione (HTFTB) (Scheme 1). Research in this field has been published during several years8-15 and these coordination modes of β-dicarbonyl ligands (M-C and M-O) have been reported in Ru also.16 β-dicarbonyl compounds feature a class of important and extensively employed ligands.17-18 They are very versatile and, besides the usual bidentate behavior of monoanions, exhibit a great variety of coordination modes.19 Equilibrium mixtures of the tautomeric keto and enol forms

Scheme 1. β-dicarbonyl Type Ligands Used in the Construction of Silver(I) Coordination Polymers

obtainable in β-diketones could be favored by replacement of the terminal groups by electron-withdrawing or electronreleasing substituents.20 Experimental Section Materials and Physical Techniques. All chemicals were of reagent grade and were used as commercially obtained without further purification. IR spectra were recorded using Perkin-Elmer 597 and Nicolet 510P spectrophotometers. Microanalyses were carried out using a Heraeus CHN-O- rapid analyzer. Melting points were measured on an Electrothermal 9100 apparatus and were uncorrected. The thermal behavior was measured with PL-STA 1500 apparatus. The luminescent properties were investigated with a Shimadzu RF-5000 spectrofluorophotometer. 1H NMR spectra were measured with a BRUKER DRX500 AVANCE spectrometer at 500 MHz, and all chemical shifts were reported in δ units downfield from Me4Si. All UV-vis spectra were recorded on a computerized double-beam Shimadzu 2550 spectrophotometer, using two matched 10 mm quartz cells. In a typical procedure, 2.0 mL of ligand solution (5.0 × 10-5 M) in CH3CN was placed in the spectrophotometer cell, and the absorbance of solution was measured. Then a known amount of the concentrated solution of silver(Ι) nitrate in CH3CN (1.3 × 10-3 M) was added in a stepwise manner using a l0-µl Hamilton syringe. The absorbance spectrum of the solution was recorded after each addition. The silver(I) ion solution was continually added until the desired metal-to-ligand mole ratio was achieved. Conductometric measurements were carried out by Metrohm 712 conductometer equipped with a Julabo F12-MB circulator. In a typical experiment, 20.0 mL of silver(I) nitrate solution (5.0 × 10-5 M) in CH3CN was placed in a two-wall thermostated glass cell, the temperature was adjusted to 25.00 ( 0.05 °C, and the conductance of solution was measured. Then a known amount of the concentrated solution of ligand in CH3CN (5.0 × 10-3 M) was added in a stepwise manner using a l0 µl Hamilton syringe. The conductance of the solution was measured after each addition. The ligand solution was continually added until the desired ligand-to-metal ion mole ratio was achieved. The formation constants (Kf) of the resulting 1:1 complexes between ligand and silver(I) ion were calculated by fitting the observed absorbance,

10.1021/cg0704652 CCC: $37.00 © 2007 American Chemical Society Published on Web 09/18/2007

AgI Coordination Polymers Constructed of Ag-C Bonds

Crystal Growth & Design, Vol. 7, No. 10, 2007 2025

Table 1. Crystal Data and Structure Refinements for [Ag2(µ3-TFPB)2(MeCN)]n (1) and [Ag2(µ3-TFNB)2(MeCN)]n (2) identification code empirical formula formula weight temperature wavelength crystal system space group unit cell dimensions

volume Z density (calculated) absorption coefficient F(000) crystal size θ range for data collection index ranges reflections collected independent reflections completeness to θ absorption correction max and min transmission refinement method data/restraints/parameters goodness-of-fit on F2 final R. [I > 2σ(I)] R indices (all data) largest diff. peak, hole

1

2

C22H15Ag2F6NO4 687.09 298(2) K 0.71073 Å triclinic P1h a ) 10.077(3)Å b ) 11.465(3) Å c ) 11.957(3) Å R )115.208(5)° β )102.393(5)° γ )101.113(5)° 1155.9(5)Å3 2 1.974 Mg/m3 1.772 mm-1 668 0.18 × 0.14 × 0.07 mm3 2.00 to 25.15° -8 e h e 12 -13 e k e 11 -13 e l e 14 6135 4047 [R(int) ) 0.0178] θ ) 25.15°: 98.0% semiempirical from equivalents 0.8860 and 0.7409 full-matrix least-squares on F2 4047/0/317 1.070 R1 ) 0.0552, wR2 ) 0.1047 R1 ) 0.0694, wR2 ) 0.1111 0.849 and -0.470 e Å-3

C30H19Ag2F6NO4 787.20 100(2) K 0.71073 Å triclinic P1h a ) 10.1623(6) Å b ) 11.6994(7) Å c ) 13.3822(12) Å R ) 104.428(5)° β ) 103.912(5)° γ ) 108.466(5)° 1370.37(19) Å3 2 1.908 Mg/m3 1.508 mm-1 772 0.35 × 0.25 × 0.25 mm3 1.68 to 29.00°. -13 e h e 13 -15 e k e 15 -18 e l e 18 15802 7189 [R(int) ) 0.0211] θ ) 29.00°: 98.8% semiempirical from equivalents 0.690 and 0.645 full-matrix least-squares on F2 7189/27/430 0.992 R1 ) 0.0294, wR2 ) 0.0711 R1 ) 0.0377, wR2 ) 0.0767 1.383 and -0.907 e Å-3

Aobs, (in spectrophotometry), and molar conductance, Λobs, (in conductometry) at various mole ratios to the previously derived equations, which express the Aobs21 Λobs22 as a function of the free and complexed metal ions using a nonlinear least-squares program KINFIT.23 Crystallographic measurements were made using a Bruker SMART APEX2 CCD area detector. The structures were solved and refined with the program system SHELXTL. Plots were prepared with ORTEP III.24 Crystallographic data and details of the data collection and structure refinements are listed in Table 1. Synthesis of [Ag2(µ3-TFPB)2(MeCN)]n (1). An acetonitrile solution (25 mL) of HTFPB (0.5 mmol, 0.108 g) was added dropwise at 2 h to a stirred acetonitrile solution (35 mL) of AgNO3 (0.5 mmol, 0.085 g), and the mixture was refluxed with stirring at 60 °C for 4 h, which immediately changed to clear solution. The slow evaporation of the solvent in 10 days and in a dark place leads to a yellow crystal. (0.055 g, yield 50%), d.p. 189 °C. Found: C, 38.25; H, 2.50; N, 2.50; Ag, 31.70%. Calculated for C22H15Ag2F6NO4: C, 38.42; H, 2.18; N, 2.04; Ag, 31.43%. IR (cm-1): 552 (m), 676 (m), 775 (s), 1086 (vs), 1187 (vs), 1272 (vs), 1503 (vs), 1636 (vs), 1997 (s), 3075 (w), 3250 (3270 and 3430 for HTFPB). 1H NMR (DMSO, δ): 4.20-4.45 (br, 1H), 6.00 (s, 1H), 7.30-7.70 (m, 3H), and 7.70-7.90 (d, 2H) ppm. Synthesis of [Ag2(µ3-TFNB)2(MeCN)]n (2) and [Ag2(µ3-TFTB)2(MeCN)]n (3). The compounds 2 and 3 were prepared via the method analogous to that used for [Ag2(µ3-TFPB)2(MeCN)]n (1). (a) Product 2. Reactant materials: HTFNP and silver(I) nitrate (1: 1), yellow crystals, d.p. 185 °C. Yield: 0.075 g, 55%. Found: C, 47.25; H, 2.70; N, 1.60; Ag, 27.50%. Calculated for C30H19Ag2F6NO4: C, 47.73; H, 2.41; N, 1.78; Ag, 27.43%. IR (cm-1): 561 (m), 680 (m), 780 (s), 1086 (m), 1127 (vs), 1187 (vs), 1284 (vs), 1474 (s), 1509 (s), 1606 (vs), 1998 (s), 3040 (w), 3255 (3275 and 3429 for HTFNB). 1H NMR (DMSO, δ): 4.30-4.55 (br, 1H), 6.20 (s, 1H), 7.55-7.75 (m, 2H), 7.80-8.22 (m, 4H), and 6.41 (s, 1H) ppm. (b) Product 3. Reactant materials: HTFTB and silver(I) nitrate (1: 1), yellow powder, d.p. 175 °C. Yield: 0.0.60 g, 55%. Found: C, 30.65; H, 1.50; N, 2.30; Ag, 30.60%. Calculated for C18H11Ag2F6NSO4: C, 30.90; H, 1.57; N, 2.00; Ag, 30.90%. IR (cm-1): 569 (w), 690 (m), 769 (m), 1099 (m), 1129 (s), 1187 (s), 1277 (s), 1383 (vs), 1527 (s), 1619 (s), 1996 (s), 3040 (w), 3258 (3273 and 3434 for HTFTB). 1H NMR (DMSO, δ): 4.25-4.40 (br, 1H), 7.30-8.50 (d, 1H), 8.108.20 (d, 1H), 8.30-8.50 (t, 1H), and 6.50 (s, 1H) ppm.

Attempts to isolate suitable single crystals of compound 3 were not successful.

Results and Discussion Synthesis and Spectroscopy. The reaction between the HTFPB, HTFNB, and HTFTB with AgI(NO3) provided crystalline materials of the general formula [Ag2(µ3-L)2(MeCN)]n [L ) HTFPB (1), HTFNB (2) and HTFTB (3)]. IR spectra display characteristic absorption bands for ligands TFPB-, TFNB-, TFTB- and MeCN. The relatively weak absorption bands around ca. 3025 cm-1 are due to the C-H modes involving the aromatic ring hydrogen atoms. The absorption bands with variable intensity in the frequency range 1400-1600 cm-1 correspond to vibrations of the phenyl, naphthyl, and thiophen rings. The absorption band of the -CHmethine moieties is observed as relatively weak at 3250 cm-1 and significantly shifted to the lower frequency region, compared to the HTFPB in compound 1, HTFNB in compound 2, and HTFTB in compound 3 (ca. 3270 and 3430 cm-1). The relatively low frequency of the band is indicative of Ag-CH bonding. The IR spectra of compounds 1-3 show sharp strong single bands at ca. 1997 cm-1, which is in accord with -CN of the acetonitrile molecule in complexes that is unambiguously confirmed by the crystal structure of complexes 1 and 2. In the 1H NMR spectra, the signals due to the ligands show different patterns with respect to those found for the free ligands, confirming the existence of the complexes in solution. For example, in the 1H NMR spectra the bridging methine resonance appears as broad singlets between 4.20 and 4.50 ppm downfield shifted with respect to those found in the free ligands. Structure Description. Determination of the structure of compounds 1 and 2 by X-ray crystallography (Table 1) showed that the compounds are 1D corrugated tape polymers (Figures 1 and 2) and that there are two types of Ag+ ions, Ag1 and

2026 Crystal Growth & Design, Vol. 7, No. 10, 2007

Akhbari and Morsali

Figure 1. A general view of compounds (a) [Ag2(µ3-TFPB)2(MeCN)]n (1) and (b) [Ag2(µ3-TFNB)2(MeCN)]n (2) in representation of atoms with ellipsoids 50% probability. One of the naphthyl groups of compound 2 is disordered.

Ag2, with the coordination numbers of four (AgO2NC) and five (AgO4C). Each TFPB- and TFNB- anion acts as a bidentate and a bridging ligand (Figure 2c,d). The dionate groups of the TFPB- and TFNB- ligands act as both bidentate-chelating and -bridging groups where two oxygen atoms of the dionate groups coordinate to a silver(I) ion; also, one of the oxygen atoms links to one other silver atom. One acetonitrile molecule coordinates to one of the silver atoms (Ag1) in both compounds (Figure 1a,b). A search was generally made for Ag-C approaches in both compounds, and it appears that Ag1 and Ag2 atoms in these compounds may interestingly be involved in an η1 interaction with the Cmethine atom of neighboring molecules. Thus, the Ag1 and Ag2 atoms in these compounds are linked to the carbon atom of methine moieties of TFPB- and TFNB- with distances Ag(1)-C(3), Ag(2)-C(13)#2 (#2, -x + 1, -y, -z + 2) of 2.463(6) and 2.431(6) Å, respectively, (Figure 2c) in compound 1 and with distances Ag(1)-C(12)#1, Ag(2)-C(12A)#2 (#1, -x + 1, -y, -z and #2, -x + 2, -y, -z) of 2.451(2) and 2.391(2) Å, respectively (Figure 2d) in compound 2. Hence, the AgI coordination spheres are completed and rather than Ag1O2N and Ag2O4 coordination spheres, the compounds 1 and 2 can be considered to contain monohapto (O5CAg1 and O2NCAg2) centers with coordination numbers of five and four. The reported Ag-C bond length range is 2.40-2.70 Å in reported species;25-28 for example, in the [Ag(benzene)ClO4] the bond lengths are 2.496 and 2.634 Å.27 Some other Ag(I) polycyclic aromatic polymeric complexes containing the AgC(sp2) bond with the mean Ag-arene distance of 2.82-3.37 Å29-35 have been reported. Thus, strong monohapto aromatic coordination of Ag atoms in the compounds 1 and 2 appears to be yet another factor that can make varying contributions to the construction of an organic-inorganic coordination polymer. One of naphthyl groups in compound 2 is disordered. The Ag1Ag2 distance in the compounds 1 and 2 are 3.675 and 3.686 Å, respectively and are considerably longer than in the other polymeric structure.36

Each TFPB- anion in compound 1 acts as a tetradonor bridging ligand, connecting three AgI ions in a µ-3, 3 mode (Scheme 2). The carbonyl groups of the TFPB- ligand act as both a bidentate-chelating and -bridging group via one O- and one C-atoms, a very novel and interesting coordination mode of this type compounds. The X-ray analyses of compound 2 show that the coordination mode of TFNB- anion is also similar to the TFPB- anion (Figures 1and 2), and it anticipates that the coordination mode of TFTB- may be the same as TFPB- and TFNB- anions. Thermogravimetric Analysis. To examine the thermal stability of the three new compounds, thermal gravimetric (TG) and differential thermal analyses (DTA) were carried out between 30 and 700 °C in the static atmosphere of air (Supporting Information, Figures S1-S3). Compound 1 is stable up to 189 °C at which temperature it begins to decompose. The TG curve of compound 1 exhibits a distinct decomposition stage, and in this stage, exothermic decomposition of TFPB- and CH3CN occurs between 189 and 522 °C with a mass loss of 65.5% (calcd. 66.2%). The DTA curve displays one endothermic peak at 156 °C and two exothermic peaks at 165 and 340 °C (Supporting Information, Figure S1). Compound 2 does not melt and is stable up to 185 °C at which temperature it begins to decompose. The TG curve of compound 2 exhibits a distinct decomposition stage, and in this stage exothermic decomposition of TFNB- and CH3CN occurs between 151 and 535 °C with a mass loss of 71.3% (calcd. 70.6%). The DTA curve displays three exothermic peaks at 183, 194, and 416 °C (Supporting Information, Figure S2). Compound 3 is stable up to 174 °C at which temperature it begins to decompose. TG curve of compound 3 exhibits a distinct decomposition stage, and exothermic decomposition of TFTB- and CH3CN occurs between between 174 and 641 °C with a mass loss of 65.1% (calcd. 64.7%). DTA curve of compound 3 displays five distinct exothermic peaks at 182, 193, 232, 429, and 636 °C and two endothermic peaks at 135 and 301 °C (Supporting Information, Figure S3). In summary, mass loss calculations of the end



Figure 3. Solid-state luminescence spectra of compounds 1-3 and ligands HTFPB, HTFNB, and HTFTB. Bands 1 for compound [Ag2(µ3-TFNB)2(MeCN)]n, 2 for compound [Ag2(µ3-TFTB)2(MeCN)]n, 3 for compound [Ag2(µ3-TFPB)2(MeCN)]n, 4 for ligand HTFTB, 5 for ligand HTFPB, and 6 for ligand HTFNB; room temperature, λexc ) 300 nm.

Figure 4. (a) Electronic absorption spectra of ligand in CH3CN (5 × 10-5 M) in the presence of increasing concentration of silver(I) ion at room temperature for compound 1. (b) Corresponding mole ratio plot at 270 nm for compound 1.

Figure 2. (a,b) Fragment of the coordination polymers showing the corrugated tape pattern in the compounds [Ag2(µ3-TFPB)2(MeCN)]n (1) and [Ag2(µ3-TFNB)2(MeCN)]n (2), respectively. (c,d) View of the Ag environments in the compounds 1 and 2, respectively; the -CF3, phenyl, and naphthyl groups of the ligands TFPB- and TFNB- have been omitted for clarity. Only the coordinated nitrogen atom (N1s) of acetonitrile has been shown. i: -x, -y, -z.

Scheme 2. The Coordination Mode of Ligand TFPB- in Compound 1

residues of compounds 1-3 show that the final decomposition products are Ag2O. Luminescent Properties. Emission studies of compounds 1-3 and their ligands were carried out in solid state. Both


ligands and compounds 1-3 have shown the broad emission bands with the maximum intensity at 470 nm upon excitation at 300 nm (Figure 3, bands 1-6). Furthermore, emission intensity of complexes 1-3 are significantly weaker than that of ligands HTFPB, HTFNB, and HTFTB, which can be attributed to the heavy atom effect37,38 due to the coordination of the ligand to a heavy Ag(I) center. The emission maxima of ligands HTFPB, HTFNB, and HTFTB, as well as compounds 1-3 in the solid state, is in the blue region, and the emission

2028 Crystal Growth & Design, Vol. 7, No. 10, 2007

Akhbari and Morsali Table 3. Selected Bond Lengths (Å) and Angles (°) for Compound 2a


Ag(1)-N(1S) Ag(1)-O(1A) Ag(1)-O(2) Ag(1)-C(12)#1 Ag(2)-O(1) Ag(2)-O(2A) Ag(2)-O(2) Ag(2)-C(12A)#2 Ag(2)-O(1A) N(1S)-Ag(1)-O(1A) N(1S)-Ag(1)-O(2) O(1A)-Ag(1)-O(2) N(1S)-Ag(1)-C(12)# O(1A)-Ag(1)-C(12)#1 O(2)-Ag(1)-C(12)#1 O(1)-Ag(2)-O(2A) O(1)-Ag(2)-O(2) O(2A)-Ag(2)-O(2) O(1)-Ag(2)-C(12A)#2 O(2A)-Ag(2)-C(12A)#2 O(2)-Ag(2)-C(12A)#2 O(1)-Ag(2)-O(1A) O(2A)-Ag(2)-O(1A) O(2)-Ag(2)-O(1A) C(12A)#2-Ag(2)-O(1A)

2.218(2) 2.3226(17) 2.4089(18) 2.451(2) 2.3197(19) 2.3410(19) 2.3840(18) 2.391(2) 2.4516(18) 131.14(8) 125.39(8) 80.20(6) 109.14(9) 106.30(8) 98.28(7) 99.43(7) 76.69(6) 130.00(6) 106.91(8) 110.28(8) 118.58(7) 141.55(6) 75.60(6) 78.15(6) 110.55(8)

a Symmetry transformations used to generate equivalent atoms: #1, -x + 1, -y, -z; #2, -x + 2, -y, -z

Figure 7. Conductivity vs [L]/[Ag+] mole ratio plot in CH3CN solution for compounds 1-3. Table 2. Selected Bond Lengths (Å) and Angles (°) for Compound 1a Ag(1)-N(1) Ag(1)-O(4) Ag(1)-O(1)#1 Ag(1)-C(3) Ag(2)-O(2)#1 Ag(2)-O(3) Ag(2)-O(4) Ag(2)-O(1)#1 Ag(2)-C(13)#2 N(1)-Ag(1)-O(4) N(1)-Ag(1)-O(1)#1 O(4)-Ag(1)-O(1)#1 N(1)-Ag(1)-C(3) O(4)-Ag(1)-C(3) O(1)#1-Ag(1)-C(3) O(2)#1-Ag(2)-O(3) O(2)#1-Ag(2)-O(4) O(3)-Ag(2)-O(4) O(2)#1-Ag(2)-O(1)#1 O(3)-Ag(2)-O(1)#1 O(4)-Ag(2)-O(1)#1 O(2)#1-Ag(2)-C(13)#2 O(3)-Ag(2)-C(13)#2 O(4)-Ag(2)-C(13)#2 O(1)#1-Ag(2)-C(13)#2

2.208(6) 2.341(4) 2.399(4) 2.463(6) 2.305(4) 2.388(5) 2.412(4) 2.412(4) 2.431(6) 124.5(2) 124.9(2) 80.36(14) 112.6(2) 103.87(18) 105.26(18) 102.18(16) 143.45(16) 76.07(15) 75.78(14) 131.38(16) 78.69(14) 107.07(19) 110.97(19) 107.47(18) 116.00(18)

a Symmetry transformations used to generate equivalent atoms: #1, -x, -y, -z + 2; #2, -x + 1, -y, -z + 2.

bands cover much of the blue region, giving the observed blue luminescence. Thus, complexes 1-3 may have potential applications as a luminescent material in organic light-emitting devices. Generally, the intraligand emission wavelength is determined by the energy gap between π and π* molecular orbitals of the free ligand, which is related to the extent of π*

conjugation in the system.38 In a similar work, optical properties of thallium(I), lead(II), and bismuth(II) hexafluoroacetylacetonates were reported.39 These compounds show emission bonds with the maximum intensity at 472, 467, and 472 nm, respectively, upon excitation at 300 nm, the same conditions that our emission studies were done; these emission bonds originate from hfac intraligand triplet and are in good agreements with our studies and confirm the intraligand luminescence properties of compounds 1-3. Solution Studies. The electronic absorption spectra of the ligand HTFPB, HTFNB, and HTFTB in the presence of increasing concentration of silver(I) ion in CH3CN at room temperature are shown in Figures 4-6, respectively. As is obvious, the strong absorption of ligands at 270, 270, and 353 nm increases with increasing concentration of the metal ion. The resulting absorbance (at 270, 270, and 353 nm, respectively) against [Ag+]/[L] mole ratio plot, shown in the inset of Figures 4-6, revealed a distinct inflection point at a metal-to-ligand molar ratio of about 1, emphasizing the formation of a 1:1 complex in solution. The formation and stoichiometry of the 1-3 complexes in CH3CN solution was also investigated by a conductometric method. The conductivity of a 5.0 × 10-5 M solution of silver(I) nitrate solution in CH3CN was monitored as a function of [L]/[Ag+] mole ratio at 25.00 ( 0.05 °C and the resulting plot is shown in Figure 7. As it is seen, the initial conductivity has a sharp increase. Addition of the ligand to the metal salt solution then causes a decrease in the solution conductivity possessing a rather distinct inflection point at a molar ratio of about one, indicating the formation of a 1:1 Ag+-L complexes in solution. For evaluation of the conditional formation constants, the mole ratio data obtained by the two different physicochemical methods employed were fitted to the previously reported equations21-22 using a nonlinear least-squares curve fitting program KINFIT.23 The conditional formation constants of the complex were evaluated as 4.06 ( 0.02, 4.81 ( 0.01, and 4.06 ( 0.03 from the spectrophotometric, and 4.09 ( 0.02, 4.61 ( 0.03, and 3.95 ( 0.02 from the conductometric methods for compound 1-3, respectively.



Conclusions Three new organosilver(I) complexes with aromatic β-dicarbonyl ligands based coordination networks, [Ag2(µ3-L)2(MeCN)]n (1-3) [L ) HTFPB (1), HTFNB (2), and HTFTB (3)], were synthesized and characterized. The compounds are structurally similar showing 1D corrugated tape pattern motifs. The β-dicarbonyl groups in these complexes exhibit the η1coordination mode of the methine group. Several relevant papers have been reported that show such silver-π.35,40-43 All three compounds, 1-3, have shown luminescent properties in solid state. For evaluation of the stoichiometry and conditional formation constants in the solution state were employed by two different physicochemical methods, spectrophotometric and conductometric. This work provides a new strategy to the preparation of air-stable multidimensional metallorganic coordination polymers with metal-carbon interaction, which may exhibit a strong blue photoluminescence behavior at room temperature.

(4)

(5)

(6)

Acknowledgment. Support of this investigation by Iran National Science Foundation, INSF (project number 84118) is gratefully acknowledged. Supporting Information Available: Complete bond lengths and angles, coordinates, and displacement parameters have been deposited at Cambridge Crystallography Data Center. Supplementary data are available from the CCDC, 12 Union Road, Cambridge CB2 1EZ, UK on request, quoting the deposition numbers 639122 and 639123 for compounds 1 and 2, respectively. This material is available free of charge via the Internet at http://pubs.acs.org.

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