Novel [Tp*WS3Cu2]-Based Coordination Compounds: Assembly

May 8, 2013 - Synopsis. Reactions of [Et4N][Tp*WS3] (1) with [Cu(MeCN)4]PF6 or CuCN and four N-donor ligands including pyridine (py), 4,4′-bipyridin...
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Novel [Tp*WS3Cu2]‑Based Coordination Compounds: Assembly, Crystal Structures, and Third-Order Nonlinear Optical Properties Cheng Xu,†,‡ Zhi-Yuan Zhang,† Zhi-Gang Ren,*,† Li-Kuan Zhou,† Hong-Xi Li,† Hui-Fang Wang,† Zhen-Rong Sun,*,§ and Jian-Ping Lang*,†,‡ †

Key Laboratory of Organic Synthesis of Jiangsu Province, 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 Science, Shanghai 200032, People’s Republic of China § Department of Physics, East China Normal University, Shanghai 200062, People’s Republic of China S Supporting Information *

ABSTRACT: Treatment of [Et4N][Tp*WS3] (1) (Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate) with [Cu(MeCN)4]PF6 and NH4PF6 (molar ratio = 1:2:1) in excess pyridine (py) produced one discrete trinuclear cluster [Et4N][Tp*WS3Cu2(py)3](PF6)2 (2). Reactions of 1 with [Cu(MeCN)4]PF6, NH4PF6, and 4,4′-bipyridine (4,4′-bipy) (or 1,2-bis(4-pyridyl)ethane (bpea)) (molar ratio = 1:2:1:2) afforded a two-dimensional (2D) [Tp*WS3Cu2]-based cationic polymer {[Tp*WS3Cu2(4,4′-bipy)1.5](PF6)·2MeCN}n (3·2MeCN) and a one-dimensional (1D) [Tp*WS3Cu2]based cationic polymer {[(Tp*WS 3 Cu 2 ) 2 (bpea) 3 ](PF6)2·2DMF}n (4·2DMF), respectively. Analogous reactions of 1 with CuCN, NH4PF6, and 4,4′-bipy (or 1,2-bis(4pyridyl)ethylene (bpee)) (molar ratio = 1:2:1:2) gave rise to a 2D [Tp*WS3Cu2]-based polymer {[Tp*WS3Cu2(μ-CN)(4,4′bipy)0.5]·MeCN}n (5·MeCN) and a three-dimensional (3D) [Tp*WS3Cu2]-based anionic polymer {[Et4N][(Tp*WS3Cu2)2{Cu(μ-CN)2.5}2(bpee)]·3MeCN}n (6·3MeCN), respectively. Compounds 2−6 were characterized by elemental analysis, IR, UV−vis, 1 H NMR, and single-crystal X-ray diffraction. The cluster cation of 2 has a butterfly-shaped [Tp*WS3Cu2] core structure in which one [Tp*WS3] unit binds two Cu atoms via one μ3-S and two μ-S atoms. 3 consists of one 2D (6,3) network in which butterfly-shaped [Tp*WS3Cu2] units are interlinked by the 4,4′-bipy ligands. 4 contains butterfly-shaped [Tp*WS3Cu2] units that are interconnected by bpea bridges to form one 1D zigzag chain. 5 holds another 2D (6,3) network in which the 1D [{Tp*WS3Cu2}2(μ-CN)2]n chains are bridged by 4,4′-bipy ligands. 6 possesses a 3-connected 3D (103) anionic net in which each 2D [{(Tp*WS3Cu2)2Cu2(μ-CN)4}4(μ-CN)4(bpee)2]n4n− network is interlinked to its neighboring ones via pairs of bpee ligands. The isolation of 2−6 with unstable [Tp*WS3Cu2] cores may be ascribed to the coordination of N-donor ligands or linkers at Cu(I) centers of these cores and the formation of polydimensional [Tp*WS3Cu2]-based frameworks (in the case of 3−5). The third-order nonlinear optical (NLO) properties of 2−6 in DMF were also investigated by using a femtosecond degenerate fourwave mixing (DFWM) technique at 800 nm.

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[EMS3]n− (E = O, n = 2; E = Cp* or Tp*, n = 1) unit may form a set of [1 + 1] to [1 + 3] products with a [EMS3Cun] (n = 1− 3) core.1d,f,5a However, such stepwise addition reactions were difficult to achieve because the [1 + 3] products like incomplete cubanelike [EMS3Cu3] clusters or complete cubanelike [EMS3Cu3X] clusters were always isolated.1d,f,5,6 Only a few examples were reported to produce the [1 + 2] products with a so-called butterfly-shaped [EMS3Cu2] core such as [Et4N][Tp*WS3(CuSCN)2], [Cp*WS3Cu2(PPh3)(μ-CN)]2, and so

INTRODUCTION

In the past few decades, the chemistry of Mo/(W)/Cu/S clusters derived from reactions of thiometallate anions [ExMS4−x]2−, [Cp*MS3]−, and [Tp*MS3]− (Cp* = pentamethylcyclopentadienyl, Tp* = hydridotris(3,5-dimethylpyrazol1-yl)borate; M = Mo, W; E = O, S; x = 0−2) with CuX (X = Cl, Br, I, NCS, CN) has been extensively investigated because of their interesting structures 1−10 and their potential applications in biological systems3 and optoelectronic materials.4−9 Theoretically, stepwise addition of one to six Cu(I) atoms onto the S−S edges of the [MS4]2− unit may afford a family of [1 + 1] to [1 + 6] products with a [MS4Cun] (n = 1− 6) core, while addition of one to three Cu(I) atoms onto the © XXXX American Chemical Society

Received: February 11, 2013 Revised: April 23, 2013

A

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collected by filtration, washed thoroughly with Et2O, and dried in vacuo. Yield: 92 mg (67% based on W). Anal. Calcd for C38H57BCu2F12N10P2S3W: C, 33.51; H, 4.21; N, 10.28. Found: C, 33.15; H, 4.28; N, 10.59. IR (KBr disk): 2567 (w), 2091 (w), 1629 (m), 1543 (s), 1448 (m), 1416 (w), 1385 (w), 1345 (w), 1219 (m), 1106 (w), 1069 (m), 843 (s), 757 (w), 698 (m), 558 (m), 476 (m), 408 (m) cm−1. UV−vis (DMF, λmax (nm (ε M−1 cm−1))): 323 (14500), 516 (2200). 1H NMR (400 MHz, CDCl3): δ 1.28−1.32 (t, 12H, CH3 in Et4N), 2.32 (s, 9H, CH3 in Tp*), 2.73 (s, 9H, CH3 in Tp*), 3.22−3.28 (q, 8H, CH2CH3), 6.14 (s, 3H, CH in Tp*), 7.36− 8.56 (m, 15H, py). Preparation of {[Tp*WS 3Cu 2(4,4′-bipy) 1.5](PF6 )·2MeCN}n (3·2MeCN). To 5 mL of MeCN solution containing 1 (75 mg, 0.1 mmol) and [Cu(MeCN)4]PF6 (75 mg, 0.2 mmol) was added 4,4′-bipy (31 mg, 0.2 mmol) and NH4PF6 (17 mg, 0.1 mmol). Some red precipitate was formed immediately. The red slurry was stirred for 10 min and filtered. A workup similar to that used for the isolation of 2 afforded red blocks of 3·2MeCN, which were collected by filtration, washed with Et2O, and dried in vacuo gave pure 3. Yield: 101 mg (47% based on W). Anal. Calcd for C30H34BCu2F6N9PS3W: C, 33.25; H, 3.16; N, 11.63. Found: C, 33.15; H, 3.28; N, 11.39. IR (KBr disk): 2563 (m), 1608 (m), 1545 (w), 1412 (m), 1354 (m), 1218 (m), 1125 (w), 1071 (m), 1035 (m), 842 (s), 692 (vs), 650 (vs), 559 (m), 476 (w), 430 (w) cm−1. UV−vis (DMF, λmax (nm (ε M−1 cm−1))): 314 (14400), 438 (4300). 1H NMR (400 MHz, DMSO-d6): δ 2.37 (s, 18H, CH3 in Tp*), 2.74 (s, 18H, CH3 in Tp*), 6.07 (s, 6H, CH in Tp*), 7.86−8.74 (m, 24H, py in 4,4′-bipy). Preparation of {[(Tp*WS 3 Cu 2 ) 2 (bpea) 3 ](PF 6 ) 2 ·2DMF} n (4·2DMF). To a DMF solution containing 1 (75 mg, 0.1 mmol) and [Cu(MeCN)4]PF6 (75 mg, 0.2 mmol) was added bpea (37 mg, 0.2 mmol) and NH4PF6 (17 mg, 0.1 mmol). A workup similar to that used for the isolation of 2 afforded red blocks of 4·2DMF, which were collected by filtration, washed with Et2O, and dried in vacuo formed pure 4. Yield: 88 mg (33% based on W). Anal. Calcd for C66H80B2Cu4F12N18P2S6W2: C, 35.21; H, 3.58; N, 11.20. Found: C, 35.35; H, 3.48; N, 11.29. IR (KBr disk): 2979 (w), 2922 (m) 2559 (m), 1617 (m), 1546 (m), 1485 (m), 1416 (m), 1353 (m), 1218 (m), 1071 (m), 1036 (m), 844 (s), 558 (m), 476 (w), 427 (w) cm−1. UV− vis (DMF, λmax (nm (ε M−1 cm−1))): 314 (28600), 436 (7600). 1H NMR (400 MHz, CDCl3): δ 2.35 (s, 18H, CH3 in Tp*), 2.89 (br, 12H, CH2 in bpea), 3.02 (s, 18H, CH3 in Tp*), 6.03 (s, 6H, CH in Tp*), 7.52−8.67 (m, 24H, py in bpea). Preparation of {[Tp*WS3Cu 2(μ-CN)(4,4′-bipy)0.5]·MeCN} n (5·MeCN). To a mixed solution of MeCN (4 mL) and CH2Cl2 (8 mL) was added 1 (75 mg, 0.1 mmol) and CuCN (18 mg, 0.2 mmol). After stirring for a few minutes, 4,4′-bipy (31 mg, 0.2 mmol) and NH4PF6 (17 mg, 0.1 mmol) were added to the solution. A workup similar to that used for the isolation of 2 afforded red blocks of 5·MeCN, which were collected by filtration, washed with Et2O, and dried in vacuo produced pure 5. Yield: 75 mg (46% based on W). Anal. Calcd for C21H26BCu2N8S3W: C, 31.20; H, 3.24; N, 13.86. Found: C, 31.28; H, 2.97; N, 13.53. IR (KBr disk): 2987 (w), 2941 (w), 2558 (m), 2098 (m), 1639 (m), 1545 (m), 1451 (m), 1409 (m), 1353 (m), 1304 (w), 1261 (w), 1217 (s), 1070 (m), 1035 (m), 842 (s), 804 (s), 692 (m), 650 (m), 619 (m), 559 (s), 476 (w), 423 (w) cm−1. UV−vis (DMF, λmax (nm (ε M−1 cm−1))): 317 (21400), 436 (5500). 1H NMR (400 MHz, DMSO-d6): δ 2.37 (s, 18H, CH3 in Tp*), 2.82 (s, 18H, CH3 in Tp*), 6.07 (s, 6H, CH in Tp*), 7.85−8.74 (m, 8H, py in 4,4′bipy). Preparation of {[Et4N][(Tp*WS3Cu2)2{Cu(μCN)2.5}2(bpee)]·3MeCN}n (6·3MeCN). To 4 mL of MeCN solution containing 1 (75 mg, 0.1 mmol) and CuCN (18 mg, 0.2 mmol) was added 8 mL of CH2Cl2 containing bpee (46 mg, 0.2 mmol) and NH4PF6 (17 mg, 0.1 mmol). The red solution was stirred for 10 min and filtered. A workup similar to that used for the isolation of 2 afforded red blocks of 6·3MeCN, which were collected by filtration, washed with Et2O, and dried in vacuo afforded pure 6. Yield: 72 mg (41% based on W). Anal. Calcd for C55H74B2Cu6N20S6W2: C, 33.39; H, 3.77; N, 14.16. Found: 33.42; H, 3.78; N, 14.27. IR (KBr disk): 2969 (w), 2923 (w),2558 (m), 2096 (m), 1614 (m), 1544 (m), 1483

on.5a,6b,c,e,10 Generally, such a butterfly-shaped core is not stable and tends to have one more Cu(I) added onto its framework to form incomplete or complete cubanelike structures.5a Considering that many M/Cu/S-based coordination polymers could be generated via using various nitrogen donor ligands,2d−h,5b,6a,d−f,7 is it possible to employ these donor ligands to stabilize such unstable [EMS3Cu2] cores accompanied by the formation of the corresponding [EMS3Cu2]-supported coordination polymers? With this question in mind, we deliberately selected four N-donor ligands: a terminal ligand pyridine (py), two rigid bidentate ligands (4,4′-bipyridine (4,4′-bipy) and 1,2bis(4-pyridyl)ethylene (bpee)), and a flexible ligand 1,2-bis(4pyridyl)ethane (bpea) (Scheme 1), and carried out the Scheme 1. Structures of py, 4,4′-bipy, bpea, and bpee

reactions of [Et4N][Tp*WS3] (1)11 with 2 equiv of [Cu(MeCN)4]PF6 or CuCN and these N-donor ligands in the presence of NH4PF6. Five novel [Tp*WS3Cu2]-based coordination compounds, [Et4N][Tp*WS3Cu2(py)3](PF6)2 (2), {[Tp*WS3Cu2(4,4′-bipy)1.5](PF6)}n (3), {[(Tp*WS3Cu2)2(bpea)3](PF6)2}n (4), {[Tp*WS3Cu2(μ-CN)(4,4′-bipy)0.5]}n (5), and {[Et4N][(Tp*WS3Cu2)2{Cu(μCN)2.5}2(bpee)]}n (6) were isolated therefrom. On the other hand, many Mo(W)/Cu/S clusters, especially those incomplete or complete cubanelike [EWS3Cu3] clusters,5b,6a,7 are known to possess good third-order nonlinear optical (NLO) performances.1d,e,h,i,2g−j,4−9 However, those with butterfly-shaped [EWS3Cu2] cores seem less explored due to their limitation in number.5a,6b,e We thus measured their third-order NLO properties in DMF by using the femtosecond degenerate fourwave mixing (DFWM) technique with 80 fs pulse width at 800 nm and found that they exhibited better NLO performances than 1. In this paper, we report their syntheses, structures, and third-order NLO properties.

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MATERIALS AND METHODS

General Procedure. All manipulations were performed under an argon atmosphere using standard Schlenk-line techniques. Compound 1 was prepared as reported previously.11 All solvents were predried over activated molecular sieves and refluxed over the appropriate drying agents under argon. IR spectra were recorded on a Varian 1000 FT-IR spectrometer as KBr disks (4000−400 cm−1). Electronic spectra were measured on a Varian 50 spectrophotometer. Elemental analyses for C, H, and N were performed on a Carlo-Erba CHNO-S microanalyzer. 1H NMR spectra were recorded at ambient temperature on a Varain UNITYplus-400 spectrometer. The 1H NMR chemical shifts were referenced to TMS in CDCl3 or to the deuterated dimethyl sulfoxide (DMSO-d6) signal. Preparation of [Et4N][Tp*WS3Cu2(py)3](PF6)2 (2). To a solution of 1 (75 mg, 0.1 mmol) in 5 mL of pyridine was added [Cu(MeCN)4]PF6 (75 mg, 0.2 mmol) and NH4PF6 (17 mg, 0.1 mmol). The mixture was stirred for half an hour and filtered. Diethyl ether (4 mL) was carefully layered onto the surface of the purple-red filtrate (2 mL). Dark red prisms of 2 were formed after a few weeks, B

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Table 1. Crystal Data and Structure Refinement Parameters for 2, 3·2MeCN, 4·2DMF, 5·MeCN, and 6·3MeCN compound

2

3·2MeCN

4·2DMF

5·MeCN

6·3MeCN

empirical formula formula weight crystal system space group a (Å) b (Å) c (Å) β (°) V (Å3) Z T (K) ρcalc (g/cm3) F(000) μ (MoKα, mm−1) total reflections unique reflections no. of observations no. of parameters R1a wR2b GOFc

C38H57BCu2F12N10P2S3W 1361.80 monoclinic P21/c 19.913(4) 16.786(3) 15.830(3) 101.76(3) 5180.1(18) 4 223(2) 1.746 2712 3.295 28878 11798 (Rint = 0.0389) 9547 611 0.0436 0.1039 1.069

C34H40BCu2F6N11PS3W 2331.32 monoclinic P21/c 13.179(3) 19.463(4) 17.204(3) 103.49(3) 4291.0(15) 4 223(2) 1.804 2300 3.907 24366 9763 (Rint = 0.0751) 7652 544 0.0774 0.1225 1.171

C72H94B2Cu4F12N20O2P2S6W2 2397.46 monoclinic P21/c 13.682(3) 17.344(3) 20.525(4) 105.99(3) 4682.1(16) 4 223(2) 1.701 2379 3.584 42922 10587 (Rint = 0.0996) 7399 563 0.0540 0.1406 0.990

C23H29Bcu2N9S3W 1698.95 monoclinic C2/c 18.016(4) 11.681(2) 29.185(6) 99.71(3) 6054(2) 8 223(2) 1.864 3319 5.421 16010 6709 (Rint = 0.0385) 4698 360 0.0383 0.0913 1.023

C61H83B2Cu6N23S6W2 2101.42 monoclinic C2/c 30.404(6) 19.657(4) 19.683(4) 127.63(3) 9316(3) 4 223(2) 1.498 4152 3.980 42302 8187 (Rint = 0.0841) 5957 420 0.0690 0.1855 1.180

a R1 = Σ∥Fo − |Fc∥/Σ|Fo|. bwR2 = {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.

collected data were reduced by using the program CrystalClear (Rigaku and MSC, version 1.3, 2001), and an absorption correction (multiscan) was applied. The reflection data were also corrected for Lorentz and polarization effects. The crystal structures were solved by direct methods12a,b refined on 2 F by full-matrix least-squares. For 2, the ethyl groups of the Et4N+ cation were disordered over two positions with occupations of 0.64/ 0.36 for C31−C38/C31A−C38A. For 5·MeCN, the MeCN solvent molecule was disordered over two sites with occupations of 0.60/0.40 for C22−C23−N9/C22A−C23A−N9A. All non-hydrogen atoms except those disordered ones in 2 and 5·MeCN were refined anisotropically. For 5·MeCN, the H atoms of the disordered MeCN molecule were not located. For 6·3MeCN, one cyanide was disordered over two orientations with equal occupancy factors for C24−N10A/ C24A−N10. The solvent accessible void occupies a volume of 2194 Å3 (23.6% of the total cell volume) and was filled with highly disordered MeCN solvents based on the FT-IR spectra (2161 cm−1). Since the disorder model did not give satisfactory results, the solvent contribution to the scattering factors has been taken into account with PLATON/SQUEEZE.12c A total of 280 electrons were found in each unit cell, corresponding to approximate 12 MeCN molecules per unit cell. However, the crystal data reported in this paper did not include the contribution of these disordered solvent molecules. By taking into account the partial occupation of the MeCN solvent molecules, the following values were obtained for those parameters: C55H74B2Cu6N20S6W2·3MeCN (Z = 4), fw = 2101.42, μ = 3.980 mm−1, F000 = 4152, and Dcalcd = 1.498 g/cm3. The H atoms located at the B atom in all these compounds were located from the Fourier map, while all other H atoms were placed in geometrically idealized positions (C−H = 0.98 Å for methyl groups, C−H = 0.95 Å for pyridyl, phenyl, and ethylene groups and C−H = 0.99 Å for methylene groups) and constrained to ride on their parent atoms with Uiso(H) = 1.2−1.5Ueq(C,N). Crystal data along with data collection and refinement parameters for 2, 3·2MeCN, 4·2DMF, 5·MeCN, and 6·3MeCN are summarized in Table 1, while their selected bond lengths were listed in Table 2.

(w), 1415 (m), 1349 (s), 1218 (m), 1124 (s), 1071 (m), 1035 (s), 977 (s), 844 (s), 690 (w), 558 (m), 476 (w), 415 (w) cm−1. UV−vis (DMF, λmax (nm (ε M−1 cm−1))): 309 (11300), 420 (3900). 1H NMR (400 MHz, DMSO-d6): δ 1.07−1.17 (t, 12H, CH3 in Et4N), 2.36 (s, 18H, CH3 in Tp*), 2.83 (s, 18H, CH3 in Tp*), 3.17−3.22 (q, 8H, CH2CH3), 6.08 (s, 6H, CH in Tp*), 7.20 (br, 2H, CH in bpee), 7.55− 8.65 (m, 10H, py in bpee). Reactions of 1 with [Cu(MeCN)4]PF6 and bpee. To a DMF (4 mL) solution containing 1 (75 mg, 0.1 mmol) and [Cu(MeCN)4]PF6 (75 mg, 0.2 mmol) was added a CH2Cl2 (8 mL) solution containing bpee (46 mg, 0.2 mmol) and NH4PF6 (17 mg, 0.1 mmol). After stirring for a few minutes, a large amount of red precipitates were formed, which was collected by filtration, washed with Et2O, and dried in vacuo. Yield: 54 mg. Anal. Calcd for C27H32BCu2F6N8PS3W ([Tp*WS3Cu2(bpee)](PF6)): C, 31.44; H, 3.13; N, 10.86. Found: C, 31.41; H, 3.14; N, 10.71. IR (KBr disk): 2559 (m), 1648 (m), 1612 (m), 1545 (m), 1442 (m), 1385 (m), 1353 (m), 1220 (m), 1071 (m), 1036 (m), 842 (s), 558 (m), 476 (w), 432 (w) cm−1. Reactions of 1 with CuCN and bpea. To a mixed solution of MeCN (4 mL) and CH2Cl2 (8 mL) was added 1 (75 mg, 0.1 mmol) and CuCN (18 mg, 0.2 mmol). After stirring for a few minutes, bpea (37 mg, 0.2 mmol) and NH4PF6 (17 mg, 0.1 mmol) were added to the solution. A workup similar to that used for the isolation of 2 afforded a large quantity of red powder after a few weeks, which was collected by filtration, washed with Et2O, and dried in vacuo. Yield: 92 mg. Anal. Calcd for C44H56B2Cu4N16S6W2 ([(Tp*WS3Cu2)2(CN)2(bpea)]): C, 32.13; H, 3.43; N, 13.62. Found: C, 32.24; H, 3.51; N, 13.47. IR (KBr disk): 2978 (w), 2951 (w), 2558 (m), 2364 (m), 2158 (m), 2088 (m), 1629 (m), 1545 (m), 1450 (m), 1412 (m), 1353 (m), 1218 (s), 1070 (m), 1035 (m), 843 (s), 785 (w), 692 (m), 650 (m), 619 (m), 559 (s), 477 (w), 428 (w) cm−1. X-ray Crystal Structure Determination. Single crystals of 2, 3·2MeCN, 4·2DMF, 5·MeCN, and 6·3MeCN 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 = 0.071073 nm). Each single crystal was mounted on glass fibers and cooled at 223 K in a liquid nitrogen stream. Diffraction data were collected at ω mode with a detector distance of 35 mm to the crystal. Cell parameters were refined by using the program CrystalClear (Rigaku and MSC, version 1.3, 2001). The

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RESULTS AND DISCUSSION Synthetic and Spectral Aspects. Treatment of 1 with 2 equiv of [Cu(MeCN)4]PF6 in pyridine without NH4PF6 C

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Table 2. Selected Bond Lengths (Å) for 2−6a

suggested that the presence of NH4PF6 might be beneficial to the assembly of Mo(W)/Cu/S clusters. Thus we also introduced NH4PF6 into the above-mentioned reaction systems. Upon addition of equimolar NH4PF6, the reactions of 1 with [Cu(MeCN)4]PF6 (molar ratio = 1:1:2) in excess pyridine could generate 2 in a higher yield (67%), while analogous reactions of 1 with [Cu(MeCN)4]PF6 (or CuCN), 4,4′-bipy (or bpee or bpea) and NH4PF6 (molar ratio = 1:2:2:1) successfully produced 3 (47% yield) and 4 (33% yield), 5 (46% yield) and 6 (41% yield), respectively. However, reactions of 1 with [Cu(MeCN)4]PF6 and bpee and those of 1 with CuCN and bpea even in the presence of NH4PF6 still afforded a large amount of red insoluble precipitates, whose chemical formulas were tentatively assumed to be [Tp*WS3Cu2(bpee)](PF6) and [(Tp*WS3Cu2)2(CN)2(bpea)] based on their elemental analysis and X-ray fluorescence analysis. As described later in this article, compounds 2−6 all contain unstable butterfly-shaped [Tp*WS3Cu2] cores in their structures. The existence of these unstable cluster cores may be ascribed to carefully controlling the 1:2:2:1 molar ratio of 1/ Cu(I) salt/N-donor ligand/NH4PF6 and the N-donor ligands stabilizing these cores via their coordination at their Cu(I) centers and the formation of various polydimensional [Tp*WS3Cu2]-supported supramolecular architectures. Compounds 2 and 4 were soluble in common solvents such as MeCN, CH2Cl2, CHCl3, DMF, and DMSO, while 3, 5, and 6 were slightly soluble in DMF and DMSO. The elemental analyses were consistent with the chemical formulas of 2−6. In the IR spectra of 2−6, bands at 408 (2), 430 (3), 427 (4), 423 (5), 415 (6) cm−1 were assigned as the bridging W−S stretching vibrations. The spectra also showed the B−H stretching vibrations at ca. 2558 cm−1 and the pyrazolyl rings at ca. 1545, 1450, and 1415 cm−1, while bands at 2098 (5) and 2096 (6) cm−1 were assigned to be the CN stretching vibrations. The UV−vis spectra of 2−6 in DMF were characterized by two bands (Figure 1). Relative to the band

Complex 2 W(1)···Cu(1) W(1)−S(1) W(1)−S(3) Cu(1)−N(9) Cu(1)−S(3) Cu(2)−N(8) Cu(2)−S(3)

2.6749(7) W(1)···Cu(2) 2.2293(12) W(1)−S(2) 2.3360(12) Cu(1)−N(7) 2.193(4) Cu(1)−S(1) 2.2781(13) Cu(1)···Cu(2) 1.938(4) Cu(2)−S(2) 2.1946(14) Complex 3

2.6051(8) 2.2449(13) 1.988(4) 2.2217(13) 2.8418(12) 2.1874(13)

W(1)···Cu(1) W(1)−S(1) W(1)−S(3) Cu(1)−N(7) Cu(1)−S(3) Cu(2)−N(8) Cu(2)−S(3)

2.6837(13) W(1)···Cu(2) 2.219(2) W(1)−S(2) 2.328(2) Cu(1)−N(9A) 2.190(7) Cu(1)−S(1) 2.246(2) Cu(1)−Cu(2) 1.956(7) Cu(2)−S(2) 2.220(2) Complex 4

2.6150(11) 2.246(2) 2.008(6) 2.233(3) 2.8178(15) 2.175(3)

W(1)···Cu(1) W(1)−S(1) W(1)−S(3) Cu(1)−N(9A) Cu(1)−S(3) Cu(2)−N(8) Cu(2)−S(3)

2.6468(9) 2.2204(18) 2.3480(16) 2.156(5) 2.2567(19) 1.929(5) 2.2058(18) Complex

W(1)···Cu(2) W(1)−S(2) Cu(1)−N(7) Cu(1)−S(1) Cu(1)−Cu(2) Cu(2)−S(2)

2.6029(9) 2.2475(17) 1.983(5) 2.2033(18) 2.8217(13) 2.1746(18)

5

W(1)···Cu(1) W(1)−S(1) W(1)−S(3) Cu(1)−N(8A) Cu(1)−S(3) Cu(2)−C(21) Cu(2)−S(2)

2.6609(10) 2.2156(15) 2.3275(15) 1.925(6) 2.2399(17) 1.899(5) 2.2067(17) Complex

W(1)···Cu(2) W(1)−S(2) Cu(1)−N(7) Cu(1)−S(1) Cu(1)−Cu(2) Cu(2)−N(7) Cu(2)−S(3) 6

2.6468(9) 2.2406(15) 2.416(6) 2.2174(18) 2.8113(12) 2.574(6) 2.2285(17)

W(1)···Cu(1) W(1)−S(1) W(1)−S(3) Cu(1)−S(1) Cu(1)−Cu(2) Cu(2)−S(2) Cu(3)−N(7) Cu(3)−N(9A)

2.6461(13) 2.246(3) 2.325(3) 2.197(3) 2.804(2) 2.195(3) 2.164(8) 1.970(8)

W(1)···Cu(2) W(1)−S(2) Cu(1)−C(22) Cu(1)−S(3) Cu(2)−C(23) Cu(2)−S(3) Cu(3)−N(8) Cu(3)−N(10)

2.6333(15) 2.236(3) 1.877(11) 2.221(3) 1.875(10) 2.220(3) 1.978(10) 1.961(9)

a Symmetry codes for 3: A: − x, y + 1/2, − z + 1/2; for 4: A: − x + 1, − y + 1, − z; for 5: A: − x + 1/2, y + 1/2, − z + 1/2; for 6: A: − x + 1/2, − y + 1/2, − z + 1.

afforded 2 in a relatively low yield (