Spontaneous Resolution of a New Thiogermanate Containing Chiral

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Spontaneous Resolution of a New Thiogermanate Containing Chiral Binuclear Nickel(II) Complexes with Achiral Triethylenetetramine Ligands: A Unique Water-Mediated Supramolecular Hybrid Helix Guang-Ning Liu,†,‡ Jian-Di Lin,† Zhong-Ning Xu,† Zhi-Fa Liu,† Guo-Cong Guo,*,† and Jin-Shun Huang† †

State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, P. R. China ‡ Graduate University, Chinese Academy of Sciences, Beijing 100039, P. R. China

bS Supporting Information ABSTRACT: The first homochiral binuclear metal complex cation-containing inorganic
organic hybrid chalcogenidometalates [Ni2(teta)3](Ge4S10) 3 H2O (1 and 10 ; teta = triethylenetetramine) were prepared, which spontaneously separate in enantiomers upon crystallization; a unique water-mediated hybrid supramolecular helix, and the correlation between molecular chirality and absolute helicity are observed in the entantiomers.

’ INTRODUCTION Chirality and helicity are associated with the living process and are fundamental to various biological functions.1 They are closely related with each other in a particular structure, even if they are two different concepts,2 and their close relation can be well manifested by DNA, where D-sugars always lead to the righthanded helicity. The study of chirality of molecular building blocks and the helicity in chiral structures can lead to a better understanding of the origin of asymmetry in living systems.2c Meanwhile, homochiral compounds are of great current interest for their intriguing potential applications in medicine, asymmetric heterogeneous catalysis, enantioselective synthesis, etc.3 The syntheses of homochiral compounds can be realized either by enantioselective synthesis using enantiopure chiral species, which is a tedious and expensive approach, or by spontaneous resolution using achiral species, generating a conglomerate (racemic mixture of chiral crystals),4 which is appealing but is still a relatively scarce phenomenon and cannot be predictable because the laws of physics determining the processes are not yet fully understood. Recently, increasing attention has been focused on employing chiral metal complexes (CMCs) as templates or structure directors in the syntheses of chiral inorganic
organic hybrids, where the CMCs are always mononuclear. While multinuclear metal complex are of particular interest now,5 for example, only stereochemically well-defined multinuclear metal complexes can lead to interpretable photophysical results.5b Meanwhile, in r 2011 American Chemical Society

comparison with the mononuclear one, multinuclear CMCs may have different abilities in transferring the chiral information and directing the formation of the final products. It is very attractive that multinuclear CMCs were used in the syntheses of chiral inorganic
organic hybrids. In the domain of chalcogenide-based inorganic
organic hybrids, hitherto only seven compounds containing multinuclear metal complexes were reported, and all of them crystallize in achiral space groups.6 Triethylenetetramine (teta) is a good ligand for transitionmetal (TM) ions and has been widely used in the syntheses of hybrid chalcogenidometalates, where the teta usually coordinates to a TM ion to form a mononuclear unsaturated [TM(teta)]2+ fragment that further covalently connects with chalcogenidometalate anions.7 Interestingly, we isolated a pair of teta-containing thiogermanate enantiomers [Ni2(teta)3](Ge4S10) 3 H2O (1, 10 ), where a bridging teta links two [Ni(teta)]2+ fragments to form a chiral binuclear [Ni2(teta)3]4+ complex cation. The enantiomers 1 and 10 represent the first binuclear metal complex cationcontaining hybrid chalcogenidometalates exhibiting spontaneous chiral resolution. Of particular interest, a unique watermediated hybrid supramolecular helix (left-handed for 1 and right-handed for 10 ) and a clear relationship between molecular chirality and absolute helicity can be observed. Received: May 8, 2011 Revised: June 13, 2011 Published: June 23, 2011 3318

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Table 1. Crystal and Structure Refinement Data for 1 and 10 10

1 formula

C18H56Ge4N12

C18H56Ge4N12

Ni2OS10 1185.13

1185.13

cryst syst

orthorhombic

orthorhombic

space group

P212121

P212121

Flack factor


0.013(16)

0.014(12)


3

Dcalcd (g cm )

1.860

1.876

a (Å) b (Å)

12.180(1) 16.096(1)

12.151(2) 15.996(3)

c (Å)

21.593(2)

21.588(4)

V (Å3)

4233.2(5)

4195.9(14)

Z

4

4

abs coeff (mm
1)

4.204

4.241

reflns collcd/unique (Rint)

27621/7853 (0.0625)

28481/7771 (0.0295)

data/params/restraints

5549/430/21

7200/430/9

R1a [I > 2σ(I)] wR2b [I > 2σ(I)]

0.0496 0.1114

0.0379 0.1030

goodness of fit

0.999

1.009

ΔFmax and ΔFmin (e Å
3)

0.521,
0.609

0.696,
0.768

)

R1 = ∑ Fo|
|Fc /∑|Fo|. b wR2 = {∑w[(Fo)2
(Fc)2]2/∑w[(Fo)2]2. )

a

Ni2OS10

Mr (g mol
1)

Figure 1. ORTEP drawing of 1 with 30% thermal ellipsoids and hydrogen atoms being omitted for clarity.

Single-Crystal Structure Determination. The intensity data sets of 1 and 10 were collected on a Rigaku SCXmini CCD diffractometer equipped with graphite-monochromated Mo KR radiation (λ = 0.71073 Å) using an ω-scan technique at 293 K. The data sets were reduced by the CrystalClear program.9 The structures were solved by direct methods using the Siemens SHELXL package of crystallographic software.10 The difference Fourier maps created on the basis of these atomic positions yielded the other non-hydrogen atoms. The structure was refined using a full-matrix least-squares refinement on F2. All nonhydrogen atoms were refined anisotropically. The hydrogen atoms of teta ligands were added geometrically and refined using the riding model. The hydrogen atoms of lattice water molecules were located by different Fourier maps and refined with O
H distances to a target value of 0.85 Å and Uiso(H) = 1.5Ueq(O). Crystallographic data and structural refinements for 1 and 10 are summarized in Table 1.

’ EXPERIMENTAL SECTION Materials and Instruments. All reagents were purchased commercially and used without further purification. Elemental analyses of C, H, and N were performed on an Elementar Vario EL III microanalyzer. Powder X-ray diffraction (PXRD) patterns were recorded on a Rigaku MiniFlex II diffractometer using Cu KR radiation. The FT-IR spectra were obtained on a Perkin-Elmer spectrophotometer using a KBr disk in the range 4000
400 cm
1. The solid-state fluorescence emission spectra were measured on an Edinberg EI920 fluorescence spectrophotometer at room temperature with a wavelength increment of 1.0 nm and an integration time of 0.2 s. Optical diffuse reflectance spectra were measured at room temperature with a PE Lambda 900 UV
vis spectrophotometer. The instrument was equipped with an integrating sphere and controlled with a personal computer. The samples were ground into fine powders and pressed onto a thin glass slide holder. A BaSO4 plate was used as a standard (100% reflectance). The absorption spectra were calculated from reflectance spectra using the Kubelka
Munk function: R/S = (1
R)2/2R,8 where R is the absorption coefficient, S is the scattering coefficient (which is practically wavelength independent when the particle size is larger than 5 μm), and R is the reflectance. Preparation of 1 and 10 . A mixture of GeO2 (0.105 g, 1.0 mmol), NiCl2 3 6H2O (0.238 g, 1.0 mmol), and S (0.096 g, 3.0 mmol) in 4 mL of a teta/H2O solution (V/V = 4/1, teta = triethylenetetramine) was sealed in a 25-mL poly(tetrafluoroethylene)-lined stainless steel container under autogenous pressure and then heated at 200 °C for 6 days and finally cooled to room temperature. The enantiomers 1 and 10 crystallize in very small amounts. Yield: 3% (based on Ge). Attempts to increase the yield by varying broadly the synthesis conditions, such as temperature, ratio of V(teta)/V(H2O), molar ratio of the starting materials, and different metal sources (e.g., Ni instead of NiCl2 3 6H2O, Ge instead of GeO2), have not yet been successful. The product consists of purple prismatic crystals of 1 (and 10 ) and a few bits of indefinite dark-red powder. The crystals were selected by hand and washed with ethanol and diethyl ether. The crystals are stable in air and insoluble in common solvents. Anal. Cald for C18H56Ge4N12Ni2OS10: C, 18.24; H, 4.76; N, 14.18. Found: C, 18.01; H, 4.60; N, 14.24.

’ RESULTS AND DISCUSSION Single crystal X-ray diffraction analyses reveal that enantiomers 1 and 10 crystallize in the same chiral space group P212121 with Flack parameters of
0.013(16) and 0.014(12), respectively, indicating enantiomeric purity of the single crystals despite the use of achiral reagents. Here we only describe the detailed crystal structure of 1, which comprises a discrete thiogermanate anion (Ge4S10)4
(T2 cluster), a binuclear [Ni2(teta)3]4+ cation, and a lattice water molecule in the asymmetric unit (Figure 1). The T2 cluster results from the condensation of four (GeS4)4
tetrahedra sharing corners with an average Ge
St (St = terminal S atom) bond distance of 2.124 Å and a Ge
μ2-S bond distance of 2.197 Å, which are consistent with the corresponding values reported in the literature.11 The Ni1 and Ni2 centers in the binuclear [Ni2(teta)3]4+ cation are homochiral, and each is in a distorted octahedral environment and coordinated by six N atoms of two teta ligands with the absolute configuration described as Λ(δδλδ). The Ni 3 3 3 Ni distance of 7.352(1) Å and the Ni
N bond distances in the range 2.097(3)
2.179(3) Å within the binuclear complex in 1 are comparable with those found in the related compounds containing binuclear [Ni2(teta)3]4+ complexes.12 The most remarkable structural feature of 1 is that the water molecules, Λ(δδλδ)Λ(δδλδ)-Ni2 complexes, and (Ge4S10)4
T2 clusters interact with each other through the O
H 3 3 3 S, N
H 3 3 3 O, and C
H 3 3 3 S hydrogen bonds to form a lefthanded supramolecular hybrid helix (Figure 2a). These helixes with a pitch of 12.180(4) Å extending along the a direction are stacked in a parallel manner and further stabilized by the interhelix N
H 3 3 3 S and O
H 3 3 3 S hydrogen bonds to produce a homochiral 3-D supramolecular structure (Figure 2b). Water-mediated hydrogen-bonding helical chains, which are closely relevant to many biological processes and also to new crystalline materials have attracted substantial attention.13 Some 3319

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Figure 2. (a) Polyhedral view of the M-helix (left-handed helix) in 1 and the P-helix (right-handed helix) in 10 with the ΛΛ-Ni2 and the ΔΔ-Ni2 binuclear complexes in the backbone of the helix, respectively. (b) Polyhedral view of a 3-D supramolecular network of 1 showing intra- (black dashed lines) and interhelix (red dashed lines) hydrogen bonds. Purple octahedron, (NiN6); green tetrahedron, (GeS4).

Figure 3. View of the way the binuclear Ni complex transfers the chirality in 1.

helical water chains formed by water molecules via hydrogen bonds,14 and water-mediated supramolecular helical structures with the water molecules being intervened between two consecutive organic molecules, have been reported.13,15 However, the helix described here, in which the water molecules are intervened between the inorganic chalcogenidometalate cluster and the binuclear TM organic ligand complex showing a hybrid characteristic, is quite different from them and has never been reported. Meanwhile, it should be point out that the binuclear Ni complexes in 1 and 10 transfer the chirality in a way that may not be performed by a mononuclear complex. The Ni2 part of the binuclear complex forms the intrahelix hydrogen bonds with

water molecules and T2 clusters that lead to a supramolecular helix, while the Ni1 part forms the interhelix N
H 3 3 3 S hydrogen bonds that help to preserve the chirality to a higher dimensionality (Figure 3). In 10 , the molecule structure, hybrid helix, and 3-D supramolecular structure all show opposite chiralities to those of 1 (Figure 2a and Figures S1 and S2 of the Supporting Information). In 1, besides the presence of a binuclear metal complex as a structure director, which is rarely reported in chalcogenidometalates,6 the other interesting observation is that the binuclear TM aliphatic-chelating-amine complex directs the formation of a chalcogenidometalate (Ge4S10)4
T2 cluster. Generally, the (Ge4Q10)4
clusters reported in the literature were directed by alkylammonium cations,11 alkali,16 alkalineearth,17 or main-group (e.g., Tl+)18 metal cations, or mononuclear TM complex cations.19 To the best of our knowledge, this is the first observation that the (Ge4Q10)4
cluster was formed under the direction of a binuclear TM complex. Enantiomerically pure crystals of 1 and 10 were obtained in the same crystallization, which indicates that the spontaneous resolution occurs during the course of the crystallization and the bulk sample tends to be a conglomerate. Although the chiral [TM2(teta)3]4+ complex can also be found in several compounds,12,20 however, all of them crystallize in an achiral space group or are racemic twinning except for the most related compound, [Ni2(teta)3](BPDS)2 3 4H2O,12a in which the Λ(δδλδ) Λ(δδλδ)-Ni2 binuclear complex similar to that in 1 and the Δ(λλδλ)Δ(λλδλ)-Ni2 binuclear complex similar to that in 10 coexisted, indicating it crystallizes as a kryptoracemate,12a,21 not a true conglomerate. Therefore, enantiomers 1 and 10 are the first 3320

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Figure 4. (a) Solid-state photoluminescence spectra of [Ni2(teta)3](Ge4S10) 3 H2O and H4tetaCl4 (λex = 350 nm) measured at room temperature. (b) Optical diffuse reflectance spectrum for [Ni2(teta)3](Ge4S10) 3 H2O at room temperature.

examples of [TM2(teta)3]4+ complex cation-containing compounds showing spontaneous chiral resolution. Because all starting materials are achiral, the bulk product is expected to be a 50:50 mixture of the two enantiomers. Generally, the absolute homohelicity can be induced by two types of driving forces:2c one is the internal induction (the chirality of the molecular building block forms an inherent part of the backbone of the helix); the other is the external induction (the chiral component is not part of the backbone of the helix). In this case, the chiral binuclear Ni complexes take part in the construction of the water-mediated hybrid helix, serving as an internal chiral driving force. It is worthwhile to mention that the correlation between molecular chirality and absolute helicity can be clearly observed in the entantiomers 1 and 10 , where chiral Ni binuclear complexes lead to the formation of homohelicity: the ΛΛ-Ni2 binuclear complex leads to a left-handed helix in 1, while the ΔΔ-Ni2 complex leads to a right-handed helix in 10 (Figure 2a), which is similar to the D-sugars leading to a righthanded helix in DNA. Enantiomers 1 and 10 exhibit luminescent properties, with an emission maximum occurring around 437 nm (λex = 350 nm) (Figure 4a). The emission is consistent with our previous investigation on the solid state luminescence of other similar compounds and is probably originated from the aliphatic chelating amine, because similar emission is also observed for the amine hydrochloride.22 The optical diffuse-reflection spectrum of the enantiomers is shown in Figure 4b, with the optical absorption edge estimated as 3.59 eV. Considering 1 and 10 crystallizing in an acentric space group, second harmonic generation (SHG) measurement was carried out on their powdery sample, which was irradiated by 1064 or 1905 nm laser light; however, no SHG response was observed, which is ascribed to their absorption near the SHG wavelength (532 and 953 nm, Figure S5).

’ CONCLUSION In summary, we report here the first homochiral binuclear metal complex cation-containing hybrid chalcogenidometalates exhibiting spontaneous chiral resolution, where a clear relationship between molecular chirality and absolute helicity, and a unique water-mediated supramolecular hybrid helix can be observed. Interestingly, the binuclear Ni complexes in 1 and 10 transfer the chirality via a method that may not be performed by a mononuclear one. These results demonstrate that novel inorganic
organic hybrid compounds with unique structures and chiral

characteristics can be expected by using a chiral binuclear metal complex as a structure director.

’ ASSOCIATED CONTENT

bS

Supporting Information. Crystallographic data (CIFs; CCDC 823074 for 1 and 823075 for 10 ), additional structural figures, PXRD patterns, IR and UV absorption spectra, and tables of bond distances and angles. This material is available free of charge via the Internet at http://pubs.acs.org.

’ AUTHOR INFORMATION Corresponding Author

*E-mail: [email protected]. Telephone: +86 591 591 83705882. Fax: +86 591 83714946.

’ ACKNOWLEDGMENT We gratefully acknowledge financial support by the NSF of China (90922035, 21003126), the 973 program (2011CBA00505), a Key Project from CAS (KJCX2.YW.M10), and the NSF of Fujian Province (2008I0026, 2008F3115). We are also grateful to Prof. Jian Zhang for helpful discussions. ’ REFERENCES (1) (a) Mason, S. F. Molecular Optical Activity and the Chiral Discriminations; Cambridge University Press: Cambridge, 1982. (b) Bonner, W. A. Origins Life Evol. Biospheres 1994, 24, 63. (c) Zhang, J.; Chen, S.; Zingiryan, A.; Bu, X. J. Am. Chem. Soc. 2008, 130, 17246. (2) (a) MacDermott, A. J., Cline, D. B., Ed. American Institute of Physics: Woodbury, NY, 1996. (b) Avalos, M.; Babiano, R.; Cintas, P.; Jimenez, J. L.; Palacios, J. C. Chem. Commun. 2000, 887. (c) Zhang, J.; Bu, X. Chem. Commun. 2009, 206. (3) (a) Collins, A. N., Sheldrake, G. N., Crosby, J., Eds. Chiral in Industry II; Wiley: New York, 1998. (b) Okamoto, Y.; Nakano, T. Chem. Rev. 1994, 94, 349. (c) Nolte, R. J. M. Chem. Soc. Rev. 1994, 23, 11. (d) Lin, W. MRS Bull. 2007, 32, 544. (e) Kesanli, B.; Lin, W. B. Coord. Chem. Rev. 2003, 246, 305. (f) F
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