Observation of in Situ Ligand Reactions during the Assembly of

Publication Date (Web): December 17, 2010. Copyright © 2010 American Chemical Society. *Corresponding author. Telephone: (61 3) 9905 2378 (office). F...
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DOI: 10.1021/cg100926g

Observation of in Situ Ligand Reactions during the Assembly of Crystalline Zn-S Clusters

2011, Vol. 11 16–20

Jingli Xie,*,†,‡ Stuart R. Batten,† Yang Zou,§ and Xiaoming Ren^ †

School of Chemistry, Monash University, Clayton, Victoria 3800, Australia, Department of Chemistry, Zhejiang Sci-Tech University, Xiasha Campus, Hangzhou 310018, P. R. China, and ^College of Science, Nanjing University of Technology, Nanjing 210009, P. R. China. ‡ Present address: WestCHEM, School of Chemistry, The University of Glasgow, University Avenue, Glasgow G12 8QQ, U.K. §

Received July 13, 2010; Revised Manuscript Received November 29, 2010

ABSTRACT: Six new neutral crystalline clusters Zn8S(SC6H5)14L2 [L = pyridyl (1), 3-(phenylthio)pyridyl (2), 4-(phenylthio)pyridyl (3), 3-iodopyridyl (4), 3-butylpyridyl (5), and phenanthridyl (6)] with Zn8S cores have been assembled by a hydrothermal process. Exceptionally, in situ ligand reactions have been observed in clusters 2 and 3. There are no detectable fluorescence emissions of complexes 1-5, whereas 6 shows an emission peak at 365 nm due to the existence of terminal phenanthridyl ligands. The pursuit of new metal nanoclusters remains at the forefront of materials science because of their novel structures and potential applications.1,2 Significant research efforts in the last two decades have been dedicated to the search for new crystalline chalcogenide clusters due to their fascinating structural diversity. Examples of these include the dual hierarchical architecture exhibiting as a supersupertetrahedron in Cu-In-S species,3a 3D quaternary open-framework chalcogenides based on supertetrahedral clusters,3b intertwined helical assemblies,3c and interesting optical, electronic properties.4 In this respect, Zn-S clusters were an important subclass and the structural characteristics of a range of cluster anions such as [Zn8S(SCH2C6H5)16]2-, [Zn8Cl(SC6H5)16]-, and [Zn10S4(SC6H5)16]4- have been unambiguously clarified.5 The uncertainty of the chemical formula of the [Zn8S(SCH2Ph)12S4]2- anion given in the literature6 has been corrected in a critical review.4d Further possible Zn-S clusters have been modeled and predicted by computer simulation methods. Therefore, the range of exciting crystalline Zn-S structures is very wide indeed and could be augmented and confirmed by experimental endeavors.7 Initially, we reported three neutral crystalline clusters, Zn8S(SC6H5)14L2 capped with ligands, and their overall physical properties were affected by the presence of the terminal substituent groups (eq 1).8a

More recently, an ionic-pair charge-transfer (IPCT) salt [C15H16N3]þ[Zn8S(C6H5)15 3 H2O], featuring a fluorescent dye and an octanuclear Zn-S cluster, has been successfully assembled and shown high stability of bacterial staining, representing our first step toward the development of crystalline Zn-S clusters for biological application.8b This approach is readily extendable to the interaction of the full range of attractive fluorescent dyes with the cluster anions and could provide an interesting set of IPCT salts for further application. In the present work, we extended the study to a broader range of capped ligands in an attempt to reveal the relationship between the substituent groups on the aromatic *Corresponding author. Telephone: (61 3) 9905 2378 (office). Fax: (61 3) 9905 4597. E-mail: [email protected]. pubs.acs.org/crystal

Published on Web 12/17/2010

rings and their corresponding physical properties. More specifically, it is anticipated that changing electron-donating or electron-withdrawing groups will affect the HOMO-LUMO band gap, impacting both the wavelength and intensity of the fluorescence emission. A range of organic compounds such as X-C5H4N (X is H, m-F, m-Cl, p-Cl, p-Br, m-I, or m-C4H9) and phenanthridine have been employed as capped ligands. The corresponding products are Zn8S(SC6H5)14[C5H5N]2 (1), Zn8S(SC6H5)14[m-C6H5SC5H4N]2 (2), Zn8S(SC6H5)14[p-C6H5SC5H4N]2 (3), Zn8S(SC6H5)14[m-IC5H4N]2 (4), Zn8S(SC6H5)14[m-C4H9C5H4N]2 (5), and Zn8S(SC6H5)14[C13H9N]2 (6).

Complexes 1-6 were obtained by hydrothermal synthesis,9 and their structures were determined from single-crystal X-ray diffraction (Table 1).10,11 It is clear that the Zn8S cores of 1-6 tolerate the variation of certain functional groups on the capped ligands. A representative structure of 1 shows all Zn atoms adopt a four-coordinated tetrahedral coordination. It displays the characteristic arrangement of the central SZn4 unit, which is capped on the four faces by two ZnS4 units and two ZnS3N units (Figure 1) to maintain the neutrality of overall clusters that have been demonstrated before.8a The Zn-S bond lengths of 1 range from 2.263(2) to 2.415(2) A˚, while the Zn-N distances are 2.044(7) and 2.067(7) A˚, respectively. Compared to those reported structures, the S-Zn-S and N-Zn-S angles of 1 are within the slightly broad range 98.19(7)-122.38(9) and 101.5(2)-113.5(2).8a In a sealed system, hydrothermal synthesis uses water as a solvent at elevated temperatures and pressures. This technique has been a powerful method for assembly of inorganic solid materials for many decades and, more recently, for synthesis of novel metal-organic frameworks (MOFs) exhibiting extensive structural diversity.12 Intriguingly, in situ ligand reactions have evolved only recently from hydrothermal synthesis and have rapidly become a new bridge between coordination chemistry and organic synthetic chemistry. Owing to its allowing access to new molecules that are inaccessible under mild experimental conditions, this trend-setting and exponential technique has been summarized in several recent reviews.13 By virtue of the hydrothermal synthesis, it is interesting to see that when X is -F, -Cl, or -Br, in situ ligand reactions occurred and led to C-S cross-coupling, resulting in elaborate pyridyl ligands (Scheme 1 and Figure 2). In contrast, 3-iodopyridine was stable under similar conditions. The most common strategy for constructing the C-S bond is the transition-metal-catalyzed cross-coupling reactions of thiols r 2010 American Chemical Society

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Table 1. Crystal Parameters for Complexes 1-6 formula fw cryst syst space group a/A˚ b/A˚ c/A˚ R/deg β/deg γ/deg V/A˚3 Z dcalc/(g cm-3) GOF R1 [I > 2σ(I)] wR2 [I > 2σ(I)]

1

2

3

4

5

6

C94H80N2S15Zn8 2241.46 monoclinic Cc 22.2229(11) 16.1021(8) 26.9252(14) 90 90.0620(10) 90 9634.8(8) 4 1.545 1.021 0.0543 0.1367

C106H88N2S17Zn8 2457.76 monoclinic Cc 20.663(3) 16.514(2) 31.871(4) 90 106.104(2) 90 10449(2) 4 1.562 1.178 0.0832 0.1741

C106H88N2S17Zn8 2457.76 monoclinic C2/c 60.797(16) 19.604(5) 18.548(5) 90 102.580(5) 90 21576(10) 8 1.513 1.266 0.0968 0.1835

C94H78I2N2S15Zn8 2493.24 monoclinic P21/c 26.183(12) 12.963(6) 28.952(13) 90 91.984(9) 90 9820(8) 4 1.686 1.050 0.0683 0.1513

C102H96N2S15Zn8 2353.67 monoclinic P21/n 25.9261(14) 13.2222(7) 31.9549(16) 90 101.8940(10) 90 10719.0(10) 4 1.458 1.060 0.0481 0.0839

C110H88N2S15Zn8 2441.68 monoclinic P21/n 13.4355(13) 27.915(3) 55.873(5) 90 91.919(2) 90 20943(3) 8 1.549 0.973 0.1143 0.2402

Scheme 1. In Situ Ligand Reactions Observed in the Synthesis of Complexes 2 and 3:Zn8S(SC6H5)14[m- and p-C6H5SC5H4N]2 (X = 3-Fluoro, 3-Chloro, 4-Chloro, 4-Bromo)

Figure 1. Structure of complex 1:Zn8S(SC6H5)14L2 [L = pyridyl].

with aryl halides.14 In this regard, the copper-catalyzed (Ullmanntype reaction) C-S coupling is the most popular approach because of its cheap character compared with other metal catalysts. 15 Notably, the use of iron, 16 cobalt, 17 nickel,18 palladium,14,19 platinum,20 or indium21 is believed to be crucial during the reaction. Some alternative approaches have employed heteropolyacids (HPAs) such as phosphotungstic acid22 or dispersed CuO on mesoporous silica,23 as the catalysts have been developed. Surprisingly, very few reactions in the absence of the catalyst have been reported; for example, the cross-coupling process between 4-chloropyridine and thiophenol led to 4-(phenylthio)pyridine.24 Of the four halopyridines used in this study, the polarizability of the substituted groups of the pyridine rings increases steadily in the order F < Cl < Br < I, indicating that iodide ion is the best leaving group compared to other akin halides. However, under similar experimental conditions, the iodine atom on the 3-iodopyridine was stable, whereas -F, -Cl, and -Br of all other pyridine ligands were eliminated during the C-S cross-coupling reactions. This observation may account for the higher energy barrier of cross-coupling reaction between 3-iodopyridine and thiophenol, illustrated by the requirement of catalysts such as palladium on charcoal,19 indium(III) trifluoromethanesulfonate,21 copper(I) oxide,25 or microwave irradiation to make the reactions achievable.26 Additionally, considering the position of halogen atoms on the pyridine rings may affect their chemical reactivity during in situ ligand reactions, different pyridine ligands such as 2-chloropyridine, 3-chloropyridine, and 4-chloropyridine have been used under similar experimental conditions for comparison. Reactions performed by using 3-chloropyridine and 4-chloropyridine allow

easy isolation of complex Zn8S(SC6H5)14[m-C6H5SC5H4N]2 (2) and Zn8S(SC6H5)14[p-C6H5SC5H4N]2 (3), respectively.9 In contrast, given the high reactivity of 2-chloropyridine for substitution reaction, no single crystal suitable for X-ray structural characterization could be observed when using 2-chloropyridine, possibly due to the spatial hindrance of the Zn-S cluster to prevent in situ ligand reaction.27 This initial result indicated the importance of the position of halogen atoms on the pyridine rings. Apparently, this catalyst-free reaction involves the elimination of -F, -Cl, or -Br in the hydrothermal process, demonstrating the promise of in situ ligand reactions to construct functional metal nanoclusters. As revealed by the UV-vis absorption spectra (Figure S4), 1-5 all show a maximum around 268 nm, which are similar to previous observations.8a Apparently, the transitions with intraligand charge-transfer characters involving terminal thiophenolates still play a vital role regardless of different functional groups on the pyridine rings. There are no detectable fluorescence emissions of those complexes, indicating that a careful choice of the substituent groups on the aromatic rings is still a challenge. The reported [C15H16N3]þ[Zn8S(C6H5)15 3 H2O]- featuring a fluorescent dye and a Zn-S cluster showed minimal photobleaching over time due to the involvement of the cluster, although the cluster ion was isolated with the dye ion.8b With the aim of showing that the direct attachment of fluorescent dye on the cluster may promote the stability of the overall compound, complex 6 [Zn8S(SC6H5)14L2; L = phenanthridyl] has been successfully generated (Figure 3). Crystal structure analysis revealed that 6 crystallized in the P21/n space group with two crystallographically independent octanuclear Zn-S clusters in the asymmetric unit. The Zn-S and Zn-N bond lengths are within the ranges 2.279(5)-2.419(4) A˚ and 2.028(15)2.077(13) A˚, respectively, similar to the values observed in related complexes.8 The terminal phenanthridyl group keeps the planar manner as usual; for example, the mean deviation from the plane is 0.0314 A˚ and 0.0307 A˚, for the aromatic ring consisting of N1, C85 ∼ C97 atoms and N2, C98 ∼ C110 atoms, respectively. Compared to the case of the original dye, the UV-vis spectrum of complex 6 in dimethyl sulfoxide (DMSO; c = 1.0  10-5 M) is

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Figure 2. Structure of complex 2 with the formation of 3-(phenylthio)pyridyl ligand.

Figure 3. Structure of complex 6: Zn8S(SC6H5)14L2 [L = phenanthridyl].

shown in Figure 4a. A doublet at 257 and 267 nm is observed, which suggests that within the UV range the phenanthridyl ligands and Zn-S cluster absorb together. Studies of the photoluminescence properties of 6 revealed that there is a luminescence peak with a maximum at 365 nm, as shown in Figure 4b, which is attributed to the existence of terminal phenanthridyl ligands with respect to other complexes 1-5. Obviously, the involvement of phenanthridyl groups had an effect on the optical properties of the overall complex because of the nature of the dye. Although there is no substantial argument regarding the role of the substituent groups on the aromatic rings, i.e., examination of those terminal ligands of pyridyl, 3-(phenylthio)pyridyl, 4-(phenylthio)pyridyl, 3-iodopyridyl, and 3-butylpyridyl of complexes 1-5 does not reveal correlations between the substituent groups and the spectral response, extensive research on the different pyridine and/or benzylthiolate rings toward a better understanding of the effects of the terminal ligands on the physical properties is still desirable. The investigation of the photostability of complex 6 as compared to the original dye (phenanthridine) is currently underway. In summary, six new neutral crystalline clusters with Zn8S cores have been assembled by a hydrothermal process. A very rare interaction pattern involving the elimination of halogen atoms such as -F, -Cl, or -Br in a catalyst-free reaction, that is to achieve clusters Zn8S(SC6H5)14L2 [L = 3-(phenylthio)pyridyl (2), 4-(phenylthio)pyridyl (3)], demonstrates the promise of in situ

Figure 4. (a) UV-vis absorption spectra of complex 6 (red) and phenanthridine (green) in DMSO (c = 1.0  10-5 M). (b) Excitation spectrum (red) and room temperature emission spectrum (green) of 6 in DMSO (c = 1.0  10-5 M).

ligand reactions to construct functional metal nanoclusters. Furthermore, organic solvents (solvothermal synthesis) and ionic liquids (ionothermal synthesis)28 will be used to further upgrade in situ ligand reactions and to establish new routes to crystalline clusters. Acknowledgment. Financial support by the Monash Fellowship Program (to J.X.) is gratefully acknowledged. Y.Z. and X.M.R. thank the support by the National Natural Science Foundation of China (20901067 and 20871068). Supporting Information Available: X-ray crystallographic file in CIF format for 1-6, materials and general procedures, structural diagrams of complexes 3, 4, and 5, and UV-vis absorption spectra of 1-5. This information is available free of charge via the Internet at http://pubs.acs.org.

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Crystal Growth & Design, Vol. 11, No. 1, 2011

References (1) (a) Wang, Z. M., Ed. Toward Functional Nanomaterials; Springer: 2009. (b) Bellucci, S., Ed. Nanoparticles and Nanodevices in Biological Applications; Springer: 2009. (c) Rogach, A. L. Semiconductor Nanocrystal Quantum Dots: Synthesis, Assembly, Spectroscopy and Applications; Springer: Wien, NY, 2008. (d) Rao, C. N. R.; M€uller, A.; Cheetham, A. K. The Chemistry of Nanomaterials; Wiley-VCH Verlag GmbH & Co. KGaA: Weinheim, 2007. (2) (a) Rosi, N. L.; Mirkin, C. A. Chem. Rev. 2005, 105, 1547. (b) Burda, C.; Chen, X.; Narayanan, R.; EI-Sayed, M. A. Chem. Rev. 2005, 105, 1025. (3) (a) Wang, L.; Wu, T.; Zuo, F.; Zhao, X.; Bu, X.; Wu, J.; Feng, P. J. Am. Chem. Soc. 2010, 132, 3283. (b) Wu, T.; Wang, X.; Bu, X.; Zhao, X.; Wang, L.; Feng, P. Angew. Chem., Int. Ed. 2009, 48, 7204. (c) Zhang, Q.; Bu, X.; Zhang, J.; Wu, T.; Feng, P. J. Am. Chem. Soc. 2007, 129, 8412. (4) (a) Vaqueiro, P. Dalton Trans. 2010, 39, 5965. (b) Lips, F.; Dehnen, S. Inorg. Chem. 2008, 47, 5561. (c) Zhang, H.; Gilbert, B.; Huang, F.; Banfield, J. F. Nature 2003, 424, 1025. (d) Henkel, G.; Krebs, B. Chem. Rev. 2004, 104, 801. (e) Burth, R.; Gelinsky, M.; Vahrenkamp, H. Inorg. Chem. 1998, 37, 2833. (f) Vossmeyer, T.; Reck, G.; Katsikas, L.; Haupt, E. T. K.; Schulz, B.; Weller, H. Science 1995, 267, 1476. (g) Dance, I. G.; Fisher, K. Prog. Inorg. Chem. 1994, 41, 637. (5) (a) Burth, R.; Gelinsky, M.; Vahrenkamp, H. Inorg. Chem. 1998, 37, 2833. (b) Dance, I. G. Aust. J. Chem. 1985, 38, 1391. (c) Choy, A.; Craig, D.; Dance, I.; Scudder, M. Chem. Commun. 1982, 1246. (d) Dance, I. G.; Choy, A.; Scudder, M. L. J. Am. Chem. Soc. 1984, 106, 6285. (6) (a) Guo, S.; Ding, E.; Liu, S.-M.; Yin, Y.-Q. Polyhedron 1999, 18, 735. (b) Guo, S.; Ding, E.; Liu, S.-M.; Yin, Y.-Q. J. Inorg. Biochem. 1998, 70, 7. (7) Hamad, S.; Woodley, S. M.; Catlow, C. R. A. Mol. Simulat. 2009, 35, 1015. (8) (a) Xie, J. Inorg. Chem. 2008, 47, 5564. (b) Xie, J.; Cao, S.; Good, D.; Wei, M.; Ren, X. Inorg. Chem. 2010, 49, 1319. (9) Zn8S(SC6H5)14[C5H5N]2 (1). In a Teflon-lined stainless steel autoclave (23 mL), Zn(CH3COO)2 3 2H2O (0.878 g, 4.0 mmol), thiourea (0.038 g, 0.5 mmol), and pyridine (0.079 g, 1.0 mmol) were dissolved in 15 mL of H2O, resulting in a clear solution. Thiophenol (0.770 g, 7.0 mmol) was added, and the mixture was stirred for 30 min; a white sticky suspension was present. The sealed vessel was heated at 165 C for 7 days. After cooling to room temperature, colorless block crystals suitable for X-ray analysis were obtained (weight, 0.718 g; yield, 64% based on the Zn source). ε268: 8.66  104 M-1 cm-1. FTIR data (cm-1): 1607 (s, δ(CdC)), 1576 (vs, δ(CdC)), 1476 (vs, δ(CdC)), 1437 (vs, δ(CdC)), 1083 (vs, ν(C; S)), 1068 (s, ν(C;S)), 733 (vs, δ(dCH)), 686 (vs, δ(dCH)). 1H NMR (400 MHz, (CD3)2SO, 25 C): δ 6.84 (t, J=7.2 Hz, 14CH, 14H), 6.97 (m, 14C(CH)2, 28H), 7.29 (m, 14C(CH)2, 28H), 7.35 (d, J=6.8 Hz, 2CH, 2H), 7.39 (t, J=6.8 Hz, 2CH, 2H), 7.50 (t, J= 4.0 Hz, 2CH, 2H), 7.80 (t, J=4.0 Hz, 2CH, 2H), 8.55 (d, J=4.0 Hz, 2CH, 2H). Zn8S(SC6H5)14[m-C6H5SC5H4N]2 (2). The procedure was similar to that above using 3-fluoropyridine (or 3-chloropyridine), with colorless block crystals being obtained. Yield: 68%. ε269: 7.40  104 M-1 cm-1. FTIR data (cm-1): 3052 (m, ν(dCH)), 1577 (vs, δ(CdC)), 1475 (vs, δ(CdC)), 1436 (s, δ(CdC)), 1082 (vs, ν(C;S)), 1052 (s, ν(C;S)), 1023 (vs, ν(C;S)), 734 (vs, δ(dCH)), 684 (vs, δ(dCH)). 1H NMR (400 MHz, (CD3)2SO, 25 C): δ 6.84 (t, J = 7.2 Hz, 14CH, 14H), 6.97 (m, 14C(CH)2, 28H), 7.30 (m, 14C(CH)2, 28H), 7.34 (d, J = 1.6 Hz, 2C(CH)2, 4H), 7.35 (t, J = 2.0 Hz, 2C(CH)2, 4H), 7.39 (t, J = 1.6 Hz, 2CH, 2H), 7.41 (s, 2CH, 2H), 7.71 (d, J=2.4 Hz, 2CH, 2H), 7.73 (d, J=2.4 Hz, 2CH, 2H), 8.49 (t, J=5.2 Hz, 2CH, 2H). Zn8S(SC6H5)14[p-C6H5SC5H4N]2 (3). The procedure was similar to that above using 4-chloropyridine hydrochloride (or 4-bromopyridine hydrochloride), with colorless block crystals being obtained. Yield: 72%. ε268: 9.95  104 M-1 cm-1. FTIR data (cm-1): 3052 (m, ν(dCH)), 1600 (s, δ(CdC)), 1578 (vs, δ(CdC)), 1476 (vs, δ(CdC)), 1437 (s, δ(CdC)), 1083 (s, ν(C;S)), 1064 (s, ν(C;S)), 1023 (vs, ν(C;S)), 734 (vs, δ(dCH)), 686 (vs, δ(dCH)). 1H NMR (400 MHz, (CD3)2SO, 25 C): δ 6.84 (t, J=7.2 Hz, 14CH, 14H), 6.97 (m, 14C(CH)2, 28H), 7.03 (d, J=5.6 Hz, 2C(CH)2, 4H), 7.30 (m, 14C(CH)2, 28H), 7.37 (t, J=5.6 Hz, 2C(CH)2, 4H), 7.51 (d, J=8.0 Hz, 2C(CH)2, 4H), 7.59 (t, J=3.2 Hz, 2C(CH)2, 4H), 8.33 (t, J=4.8 Hz, 2CH, 2H). Zn8S(SC6H5)14[m-IC5H4N]2 (4). The procedure was similar to that above using 3-iodopyridine, with colorless block crystals being obtained. Yield: 75%. ε266: 4.93  104 M-1 cm-1. FTIR data (cm-1): 3047 (m, ν(dCH)), 1575 (vs,

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(15) (16) (17) (18) (19) (20) (21) (22)

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δ(CdC)), 1563 (vs, δ(CdC)), 1476 (vs, δ(CdC)), 1437 (s, δ(CdC)), 1085 (s, ν(C;S)), 1069 (m, ν(C;S)), 1022 (vs, ν(C;S)), 732 (vs, δ(dCH)), 686 (vs, δ(dCH)). 1H NMR (400 MHz, (CD3)2SO, 25 C): δ 6.84 (t, J=8.0 Hz, 14CH, 14H), 6.97 (m, 14C(CH)2, 28H), 7.28 (m, 14C(CH)2, 28H), 8.18 (d, J=4.0 Hz, 2CH, 2H), 8.49 (t, J = 4.0 Hz, 2CH, 2H), 8.55 (d, J = 4.0 Hz, 2CH, 2H), 8.80 (s, 2CH, 2H). Zn8S(SC6H5)14[m-C4H9C5H4N]2 (5). The procedure was similar to that above using 3-butylpyridine, with colorless block crystals being obtained. Yield: 78%. ε267: 4.33  104 M-1 cm-1. FTIR data (cm-1): 3053 (m, ν(dCH)), 2955 (m, ν(-CH3)), 2928 (m, ν(-CH2)), 2860 (m, ν(-CH3)), 1577 (vs, δ(CdC)), 1476 (vs, δ(CdC)), 1436 (s, δ(CdC)), 1378 (m, ν(-CH3)), 1084 (s, ν(C;S)), 1068 (m, ν(C;S)), 1023 (vs, ν(C;S)), 734 (vs, δ(dCH)), 686 (vs, δ(dCH)). 1 H NMR (400 MHz, (CD3)2SO, 25 C): δ 0.87 (t, J=7.2 Hz, 2CH3, 6H), 1.27 (d, J=7.2 Hz, 2CH2, 4H), 1.52 (d, J=7.2 Hz, 2CH2, 4H), 2.56 (t, J=8.0 Hz, 2CH2, 4H), 6.84 (t, J=7.2 Hz, 14CH, 14H), 6.96 (m, 14C(CH)2, 28H), 7.29 (m, 14C(CH)2, 28H), 8.19 (d, J=4.0 Hz, 2CH, 2H), 8.37 (t, J=4.0 Hz, 2CH, 2H), 8.57 (d, J=4.0 Hz, 2CH, 2H), 8.78 (s, 2CH, 2H). Zn8S(SC6H5)14[C13H9N]2 (6). The procedure was similar to that above using phenanthridine, with pale-yellow block crystals being obtained. Yield: 66%. ε257: 1.31  105 M-1 cm-1. ε267: 1.24  105 M-1 cm-1. FTIR data (cm-1): 3047 (m, ν(dCH)), 1575 (vs, δ(CdC)), 1563 (vs, δ(CdC)), 1476 (vs, δ(CdC)), 1437 (s, δ(CdC)), 1348 (m, δ(CdC)), 1087 (s, ν(C;S)), 1070 (m, ν(C;S)), 1023 (vs, ν(C;S)), 744 (vs, δ(dCH)), 732 (vs, δ(dCH)), 693 (vs, δ(dCH)). 684 (vs, δ(dCH)). 1H NMR (400 MHz, (CD3)2SO, 25 C): δ 6.83 (t, J=8.0 Hz, 14CH, 14H), 6.96 (m, 14C(CH)2, 28H), 7.28 (m, 14C(CH)2, 28H), 7.36 (t, J = 8.0 Hz, 2CH, 2H), 7.49 (t, J = 8.0 Hz, 2CH, 2H), 7.56 (d, J=4.0 Hz, 2CH, 2H), 7.77 (t, J=8.0 Hz, 2CH, 2H), 7.94 (d, J=1.0 Hz, 2CH, 2H), 8.09 (d, J=8.0 Hz, 2CH, 2H), 8.21 (d, J=8.0 Hz, 2CH, 2H), 8.81 (t, J=8.0 Hz, 2CH, 2H), 9.35 (s, 2CH, 2H). (a) Sheldrick, G. M. SHELXTL V5.1 Software Reference Manual; Bruker AXS, Inc.: Madison, WI, 1997. (b) Sheldrick, G. M. SHELX97, Programs for Crystal Structure Analysis; Instit€ut f€ur Anorganische Chemie der Universit€at: G€ottingen, Germany, 1998. (a) Sheldrick, G. M. SADABS, V2.01, Empirical Absorption Correction Program; Instit€ ut f€ ur Anorganische Chemie der Universit€at: G€ ottingen, Germany, 1996. (b) As for complex 3, the -SC6H5 group with an S17 atom is disordered over two sites, and this is responsible for the elevated agreement values (R values) found for its structure. However, the atomic positions are well resolved in the crystal structure analysis. (a) Cheetham, A. K.; Rao, C. N. R.; Feller, R. K. Chem. Commun. 2006, 4780. (b) Han, L.; Bu, X.; Zhang, Q.; Feng, P. Inorg. Chem. 2006, 45, 5736. (c) Li, J.; Chen, Z.; Wang, R. J.; Proserpio, D. M. Coord. Chem. Rev. 1999, 190-192, 707. (d) Hagrman, P. J.; Hagrman, D.; Zubieta, J. Angew. Chem., Int. Ed. 1999, 38, 2638. (a) Zhang, J.-P.; Chen, X.-M.Chapter 3: Crystal Engineering of Coordination Polymers via Solvothermal In Situ MetalLigand Reactions. Hong, M.-C., Chen, L., Eds.; Design and construction of Coordination Polymers; John Wiley & Sons, Inc.: Hoboken, NJ, 2009. (b) Chen, X.-M.; Tong, M.-L. Acc. Chem. Res. 2007, 40, 162. (c) Zhang, X.-M. Coord. Chem. Rev. 2005, 249, 1201. (a) Alvaro, E.; Hartwig, J. F. J. Am. Chem. Soc. 2009, 131, 7858. (b) Fernandez-Rodríguez, M. A.; Shen, Q.; Hartwig, J. F. Chem.;Eur. J. 2006, 12, 7782. (c) Mispelaere-Canivet, C.; Spindler, J.-F.; Perrio, S.; Beslin, P. Tetrahedron 2005, 61, 5253. (d) Kondo, T.; Mitsudo, T.-a. Chem. Rev. 2000, 100, 3205. (a) Bagley, M. C.; Davis, T.; Dix, M. C.; Fusillo, V.; Pigeaux, M.; Rokicki, M. J.; Kipling, D. J. Org. Chem. 2009, 74, 8336. (b) Zhang, H.; Cao, W.; Ma, D. Synth. Commun. 2007, 37, 25. (a) Wu, J.-R.; Lin, C.-H.; Lee, C.-F. Chem. Commun. 2009, 4450. (b) Correa, A.; Carril, M.; Bolm, C. Angew. Chem., Int. Ed. 2008, 47, 2880. Wong, Y.-C.; Jayanth, T. T.; Cheng, C.-H. Org. Lett. 2006, 8, 5613. Zhang, Y.; Ngeow, K. C.; Ying, J. Y. Org. Lett. 2007, 9, 3495. Jiang, Z.; She, J.; Lin, X. Adv. Synth. Catal. 2009, 351, 2558. Hirai, T.; Kuniyasu, H.; Kambe, N. Tetrahedron Lett. 2005, 46, 117. Reddy, V. P.; Swapna, K.; Kumar, A. V.; Rao, K. R. J. Org. Chem. 2009, 74, 3189. Kumar, A.; Singh, P.; Kumar, S.; Chandra, R.; Mozumdar, S. J. Mol. Catal. A: Chem. 2007, 276, 95.

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Crystal Growth & Design, Vol. 11, No. 1, 2011

(23) Chen, C.-K.; Chen, Y.-W.; Lin, C.-H.; Lin, H.-P.; Lee, C.-F. Chem. Commun. 2010, 46, 282. (24) Sprague, R. H.; Brooker, L. G. S. J. Am. Chem. Soc. 1937, 59 (12), 2697. (25) (a) Xu, H.-J.; Zhao, X.-Y.; Ding, J.; Fu, Y.; Feng, Y.-S. Tetrahedron Lett. 2009, 50, 434. (b) Xu, H.-J.; Zhao, X.-Y.; Fu, Y.; Feng, Y.-S. Synlett 2008, 19, 3063. (26) Cherng, Y.-J. Tetrahedron 2002, 58, 4931.

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