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Self-assembly of looped triple-stranded helicatesw

Vicente,*a Juan Gil-Rubio,*a Natalia Barquero,a Vero nica Ca maraa and Jose b Norberto Masciocchi
Received (in Cambridge, UK) 13th October 2009, Accepted 23rd December 2009 First published as an Advance Article on the web 13th January 2010 DOI: 10.1039/b921279e The reaction of the organogold metallaligand [(AuCRCbpyl)2(l-Ph2P(CH2)4PPh2)] (bpyl = 2,2 0 -bipyridin-5-yl) with Fe2+ or Zn2+ ions gave helicates where the three ligand strands adopt a unique looped geometry. Metal-directed self-assembly of helicates has opened a new route to articial helical molecules with fascinating structures1 and potential applications in medicinal chemistry,2 catalysis3 and as advanced functional materials.4 Triple-stranded helicates are generally M2L3-type complexes of octahedrallycoordinated metals with ligands possessing two bidentate coordination sites. The spacer connecting these sites should be rigid enough to mechanically couple the chirality (D or L) of both chelates, ensuring that they adopt the same conguration.5 In almost all helicates reported these spacers are organic covalent chains, except for a few cases containing coordinative6 or hydrogen7 bonds. We have recently reported the synthesis and characterization of the luminescent organogold complexes [(AuCRCbpyl)2(m-Ph2P(CH2)nPPh2)] (bpyl = 2,2 0 -bipyridin-5-yl, n = 1, 2, 4, 10).8 Metallaligands of this type are potential building blocks for the assembly of nanometre-sized complexes with unique structures and properties.9 Herein we report the reactions of [(AuCRCbpyl)2(m-Ph2P(CH2)4PPh2)] (L, Scheme 1) with metal ions, primarily Fe2+, and the isolation of an octanuclear Au6Fe2 complex with a new type of helical topology. The reaction of L with hydrated Fe(II) perchlorate (MeCN, 2 : 3 Fe/L molar ratio) led to a red solution, whose 1H and 31 1 P{ H} NMR spectra were rather simple and displayed sharp signals, indicating the formation of a highly symmetrical discrete species. In contrast, the NMR spectra of the analogous reaction of L with hydrated Zn(II) perchlorate (pale-yellow solution) showed a similar set of signals accompanied by less intense broad signals, which were assigned to ill-dened oligomers.z Liquid diusion of Et2O into a MeCN solution of the iron complex gave rise to single crystals which were used for X-ray diraction analysis.y The crystal structure contains octametallic complexes, built by three molecules of L connecting two Fe2+ cations, therefore corresponding to the salt [Fe2L3](ClO4)4 (Fig. 1). The chain of each metallaligand is folded, forming an unprecedented triple-looped triple-helical arrangement of D3 symmetry. This symmetry is maintained both in the crystal (c Wycko position of 3.2 site symmetry) and in solution (see below). The three-fold symmetry axis is dened by the positions of the Fe atoms, while three perpendicular two-fold axes pass through the midpoints of the central methylene carbons of the diphosphines and bisect the Au. . .Au vectors of weakly interacting gold atoms. The conguration of both Fe(bpyl)32+ chelates within the complex is the same (D,D or L,L) giving rise to P or M helicates. A racemic mixture of both enantiomers is present in the single crystal. The structure of the tetrapositive cation is quite compact, likely favored by the three stabilising ). aurophilic interactions (Au. . .Au = 3.2144(5) A 1 13 1 The room temperature H and C{ H} NMR spectra of the Fe and Zn complexes agree with the D3 symmetry of the Fe complex in the solid state. Thus, they show only one set of signals corresponding to one half of the ligand and both the methylene and phenyl protons appear diastereotopic. In the 13C{1H} NMR spectra, the AuCaRCbCg carbons appear as doublets, due to coupling with phosphorus (JPC = 140.9 and 141.0 (a), 26.5 and 26.5 (b) and 2.8 and 3.0 Hz (g) for M = Fe and Zn, respectively). This indicates that the AuP bonds do not dissociate signicantly on the NMR time scale. The 31P{1H} NMR spectra displayed only

lica, Departamento de Qumica Grupo de Qumica Organometa nica, Facultad de Qumica, Universidad de Murcia, Inorga E-30071 Murcia, Spain. E-mail: jvs1@um.es; Web: http://www.um.es/gqo/; Fax: +34 868 887785; Tel: +34 868 884143 b Dipartimento di Scienze Chimiche e Ambientali, Universita` dellInsubria, I-22100 Como, Italy. E-mail: norberto.masciocchi@uninsubria.it; Fax: +39 031 2386630; Tel: +39 031 2386627 w Electronic supplementary information (ESI) available: Detailed syntheses and characterization data. NMR spectra of the reaction mixtures at dierent L : M2+ proportions. Plots of the Fe-complex structure (space-lling) and the crystal packing. Crystallographic data. CCDC 749572. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/b921279e

Scheme 1 Synthesis of triple stranded helicates. Dotted lines highlight the weak Au. . .Au contacts observed in the crystals of the Fe species.

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Fig. 2 Aromatic region of the 1H NMR spectra of isolated [Fe2L3](ClO4)4 (top), [Zn2L3](ClO4)4 (middle) and L (bottom).

Fig. 1 Molecular structure of the [Fe2L3]4+ cation viewed down a C2 (top) and the C3 symmetry axis. The three chemically equivalent L ligands are plotted in dierent colors; hydrogen atoms are omitted for clarity.

one sharp singlet at d values which are very similar to that of L, corresponding to the six magnetically equivalent P nuclei of the molecule. Remarkably, the 1H NMR signals of H3 0 and H4 0 (Scheme 1) are considerably shifted with respect to those of H3 and H4, respectively (Fig. 2). According to the crystal structure (Fig. 1), the magnetic shielding of H3 0 and H4 0 could be attributed to ring current eects of the nearby Ph rings. In addition, NOE contacts between phenylic and pyridinic protons are observed in the NOESY spectrum of the Fe complex at 40 1C (Fig. S8w).z These observations suggest that in solution the average disposition of the diphosphine chains is folded as in the crystal structure. Diusion NMR measurements10 gave very similar values for the diusion coecients of the Fe and the Zn complexes (5.83 1010 and 5.64 1010 m2 s1, respectively), pointing to a similar size of both in solution. A spherical hydrodynamic radius of was estimated for [Fe2L3]4+ using the StokesEinstein 11.0 A equation.10,11 This value agrees reasonably well with the molecular dimensions derived from the crystal structure of the complex (Fig. S9w). The reactions between L and Fe2+ or Zn2+ were also studied by 1H and 31P{1H} NMR spectroscopy at dierent L : M2+ molar ratios (Fig. S10w). The variations observed agree with a 3 : 2 stoichiometry of the complexes. Thus, the spectra of the reaction between Fe2+ and more than 1.5 equivalents of L displayed only the signals of free L and [Fe2L3]4+ but, when a L : Fe2+ ratio of 3 : 2 was used, only the signals of [Fe2L3]4+ were observed. When an excess of Fe2+ was used (1 : 1 molar ratio), [Fe2L3]4+ was still the main
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species. In contrast, the analogous experiments with Zn2+ displayed broad signals in addition to those of free L and [Zn2L3]4+. A mixture of unidentied species containing only a minor amount of [Zn2L3]4+ was formed when the L : Zn2+ ratio was 1 : 1. ESI-MS spectra were also measured for both reaction mixtures, showing peaks corresponding to the [M2L3]4+ cations, as well as to associations of the {[M2L3](ClO4)n}(4n)+ (n = 1 or 2) type, with the expected exact masses and isotopic distributions (Fig. S7w). These peaks were intense for the Fe complex but weak in the spectrum of the Zn complex. In both cases, no higher nuclearity species were detected. In conclusion, we have shown that metallaligand [(AuCRCbpyl)2(m-Ph2P(CH2)4PPh2)] (L) forms [M2L3]4+ complexes in the presence of Fe2+ or Zn2+ by a self-assembly process which was unexpected for such a long and exible ligand. The [Fe2L3]4+ cation presents a unique triple-helical structure containing three loops, which is stabilized by three Au. . .Au interactions and can be described as a triple-stranded triple-looped helicate. The reported octanuclear complexes are unprecedented examples of helicates with organogold strands. We are currently investigating the inuence of the diphosphine geometry and length in the self-assembly process; our preliminary results using diphosphines with markedly dierent spacers/ bridges show that the helicate structure of the [Fe2(Ln)3] core is maintained. n General de Investigacio n/FEDER We thank Direccio n (Grant CTQ2007-60808/BQU, C-Consolider) and Fundacio neca (Ayudas a los Grupos y Unidades de Excelencia Se n de Murcia 2007-2010, Grant Cient ca de la Regio 02992/PI/05) for nancial support. We also thank Dr A. Pastor for helpful discussions.

Notes and references

z [Fe2L3](ClO4)4: Anal. Calcd. for C156H126Au6Cl4Fe2N12O16P6: C, 46.31; H, 3.14; N, 4.15. Found: C, 46.34; H, 3.14; N, 4.14. 1H NMR (400.9 MHz, CD3CN): d 8.12 (d, 6 H, H3, 3JHH = 8.4 Hz), 8.01 (d, 6 H, H4, 3JHH = 8.4, 4JHH = 1.7 Hz), 7.70 (m, 30 H, Ph1), 7.51 (s, 6 H, H6),

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7.207.08 (m, 30 H, H3 0 , H6 0 , o-Ph2 and p-Ph2), 6.90 (m, 12 H, H4 0 and H5 0 ), 6.57 (m, 12 H, m-Ph2), 2.90 (m, 6 H, CH2CH2P), 2.162.02 (two m, 12 H, CH2CH2P and CH2CH2P), 1.84 (m, 6 H, CH2CH2P). 31P{1H} NMR (81.0 MHz, CD3CN): d 36.9 (s). ESI-MS (MeCN) m/z: 1923.2 ([Fe2L3](ClO4)22+), 1413.2, 1345.2, 1333.1 ([FeL](ClO4)+), 1279.1, 1249.1 ([Fe2L3](ClO4)3+), 1206.7, 999.1 ([Au2(CRCbpyl)(dppb)]+), 911.9 ([Fe2L3]4+), 855; exact m/z calcd. for [Fe2L3]4+: 911.6331, found: 911.6340, D = 1 ppm. [Zn2L3](ClO4)4: Anal. Calcd. for C156H126Au6Cl4N12O16P6Zn2 4H2O: C, 45.29; H, 3.26; N, 4.06. Found: C, 45.00; H, 2.98; N, 4.03. 1 H NMR (400.9 MHz, CD3CN): d 8.30 (d, 6 H, H3, 3JHH = 8.5 Hz), 7.99 (dd, 6 H, H4, 3JHH = 8.3, 4JHH = 1.7 Hz), 7.88 (d, 6 H, H6, 4 JHH = 1.5 Hz), 7.83 (ddd, 6 H, H6 0 , 3JHH = 5.1, 4JHH = 1.5, 5JHH = 0.6 Hz), 7.76 (d, 6 H, H3 0 , 3JHH = 7.9 Hz), 7.717.66 (m, 30 H, Ph1), 7.29 (m, 6 H, p-Ph2), 7.16 (m, 12 H, o-Ph2), 7.01 (ddd, 6 H, H5 0 , 3JHH = 5.2, 3JHH = 7.6, 4JHH = 1.0 Hz), 6.83 (m, 18 H, H4 0 and m-Ph2), 2.83 (m, 6 H, CH2CH2P), 2.28 (m, 6 H, CH2CH2P), 2.05 (m, 6 H, CH2CH2P), 1.81 (m, 6 H, CH2CH2P). 31P{1H} NMR (81.0 MHz, CD3CN): d 36.9 (s). ESI-MS (MeOHMeCN) m/z: 3965 ([Zn2L3](ClO4)3+), 2521 ([ZnL2](ClO4)+), 1933 ([Zn2L3](ClO4)22+), 1421 ([Zn{Au2(CRCbpyl)3(dppb)}]+), 1355, 1341 ([ZnL](ClO4)+), 1255 ([Zn2L3](ClO4)3+), 1211 ([ZnL2]2+), 999 ([Au2(CRCbpyl)(dppb)]+), 917 ([Zn2L3]4+), 855. exact m/z calcd. for [Zn2L3]4+: 915.6310, found: 915.6302, D = 0.9 ppm. y Crystal data. [Fe2L3](ClO4)412CH3CN5H2O, trigonal, P-31c, a = , V = 9134.9(5) A 3, Z = 2, rc = 19.4440(4), c = 27.9000(13) A , T = 100 K, 1.686 g cm3, m(Mo-Ka) = 5.134 mm1, l = 0.71073 A Rint = 0.0435, R1 = 0.040 and wR2 = 0.112 for 6251 observed reections with I > 2s(I) and 332 rened parameters. CCDC code 749572. The crystal packing of the organometallic cations generates large cavities (accounting for nearly 32% of the total crystal volume), in which disordered perchlorates are hosted, together with a number of solvent molecules. The formulation proposed above, even if not explaining all electron density residuals, represents the best compromise between the complexity of the guest solvent molecules and the simplicity of a stoichiometric formula, leading to appreciably low crystallographic disagreement factors. z The 1H NMR spectrum of [Zn2L3](ClO4)4 became very broad on lowering the temperature. No signicant NOEs between the protons of the Ph and bpyl groups were detected in the room temperature NOESY spectra. 1 M. Albrecht, Chem. Soc. Rev., 1998, 27, 281; M. Albrecht, Chem. Rev., 2001, 101, 3457; J. M. Lehn, A. Rigault, J. Siegel, J. Harroweld, B. Chevrier and D. Moras, Proc. Natl. Acad. Sci. U. S. A., 1987, 84, 2565; C. Piguet, G. Bernardinelli and G. Hopfgartner, Chem. Rev., 1997, 97, 2005; C. Piguet, M. Borkovec, J. Hamacek and K. Zeckert, Coord. Chem. Rev., 2005, 249, 705.

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