Zinc Pyromellitate Coordination Polymers with Bis(pyridylmethyl

ARTICLE pubs.acs.org/crystal

Zinc Pyromellitate Coordination Polymers with Bis(pyridylmethyl)piperazine Tethers: A Rare Binodal Network and a New Simple Self-Penetrated Topology Karyn M. Blake, Jacqueline S. Lucas, and Robert L. LaDuca* Lyman Briggs College and Department of Chemistry, Michigan State University, E-30 Holmes Hall, East Lansing, Michigan 48825, United States

bS Supporting Information ABSTRACT: Hydrothermal reaction of zinc nitrate, pyromellitic acid (H4pyro), and isomeric bis(pyridylmethyl)piperazines has afforded a pair of three-dimensional (3D) coordination polymers with intriguing 3D topologies. {[Zn2(Hpyro)2(H2O)2(H23-bpmp)] 3 H2O}n [1, 3-bpmp=bis(3-pyridylmethyl)piperazine] exhibits octahedral coordination at zinc and possesses a rare 4,5connected binodal net with (4462)(4466) tcs topology. {[Zn2(Hpyro)2(H2-4-bpmp)] 3 4H2O}n [2, 4-bpmp = bis(4-pyridylmethyl)piperazine] has tetrahedral coordination at zinc and an unprecedented yet very simple 3,4-connected binodal (4.82)(4.82 103) self-penetrated topology. Pyridyl nitrogen donor disposition and coordination geometry preference play a large role in structure-direction in this system. Complexes 1 and 2 undergo blueviolet light emission on excitation with ultraviolet light.

’ INTRODUCTION Recent years have seen an explosion of interest in coordination polymer solids, as this class of crystalline materials has important industrial uses such as gas storage,1 molecular separations,2 ion exchange,3 catalysis,4 and nonlinear optics.5 Basic research in this field is stimulated by the discovery of aesthetic molecular networks,6 many of which have not yet been predicted by theoretical investigations of connectivity and topology. Aromatic dicarboxylates have been to date the most popular choice of connecting ligands for the construction of divalent metal coordination polymers,7-10 wherein coordination geometry preferences along with numerous accessible carboxylate binding modes play a crucial dual role in structure direction. These structure-directing factors are even more complicated in coordination polymers containing pyromellitate ligands (pyro4-, 1,2,4,5-benzenetetracarboxylate, Scheme 1), whose eight potential oxygen donor atoms proffer myriad possible binding and bridging modes; the pyro ligand has been seen to bridge anywhere from two to ten metal centers.11 Additionally, alteration of pH levels during self-assembly can afford pyro4-,11 Hpyro3-,12 H2pyro2-,13 and H3pyro- anions,14 sometimes requiring adjustment of the metal:ligand ratio or the inclusion of interstitial alkali metal15 or organoammonium cations16 for the formation of neutral crystalline solids. The structural diversity and functional utility of coordination polymers containing r 2011 American Chemical Society

pyromellitate ligands have been further enhanced by the inclusion of neutral nitrogen base capping or tethering ligands.17 For example, [Cu(H2pyro)(2,20 -bipyridine)]n can catalyze the oxidation of cyclohexene,17a while {[Ni2(pyro)(4,40 -bipyridine)3] 3 3DMF}n retains its three-dimensional (3D) microporous framework after desolvation and adsorbs nitrogen gas.17b Recently, our group has been investigating the structural effects of the inclusion of bis(3-pyridylmethyl)piperazine (3bpmp) and bis(4-pyridylmethyl)piperazine (4-bpmp) ligands (Scheme 1) on divalent metal dicarboxylate coordination polymer topology.18,19 These ligands exhibit a modicum of conformational flexibility and can provide structure-directing hydrogen-bonding points of contact or protonation sites at their piperazinyl nitrogen atoms. Both have proven useful in accessing diverse metal-organic framework topologies, with 4-bpmp resulting in novel self-penetrated networks in several cases. For example, {Cu2(glutarate)2(4bpmp)] 3 4H2O}n has a six-connected uninodal 446108 mab selfpenetrated 3D net,19a [Co3(oxybisbenzoate)3(4-bpmp)2]n possesses a unique eight-connected uninodal 4451767 self-penetrated topology,19b and {[Zn3(tricarballylate)2(4-bpmp)(H-4-bpmp)2](ClO4)2 3 5H2O}n manifests self-penetrated two-dimensional (2D) layers Received: November 12, 2010 Revised: February 7, 2011 Published: March 03, 2011 1287

dx.doi.org/10.1021/cg1015109 | Cryst. Growth Des. 2011, 11, 1287–1293

Crystal Growth & Design Scheme 1. Ligands Used in This Study

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Table 1. Crystal and Structure Refinement Data for 1 and 2 data

with threaded-loop pseudo-rotaxane linkages.19c We have therefore sought to extend these efforts into the synthesis of 3-bpmp- or 4-bpmp-containing divalent metal pyromellitate coordination polymers. Herein, we report the synthesis and structural characterization of two 3D zinc pyromellitate coordination polymers containing isomeric bis(pyridylmethyl)piperazine ligands: {[Zn2(Hpyro)2(H2O)2(H23-bpmp)] 3 H2O}n (1) and {[Zn2(Hpyro)2(H2-4-bpmp)] 3 4H2O}n (2). In these materials, the pyridyl nitrogen donor disposition and coordination preference at zinc both have a significant cooperative effect on the final coordination polymer topology. Compound 1 manifests a rarely seen 3D binodal network, while compound 2 possesses a new, very simple self-penetrated topology. The luminescent behavior of these materials is also discussed.

Preparation of {[Zn2(Hpyro)2(H2O)2(H2-3-bpmp)] 3 H2O}n (1). Zinc nitrate hexahydrate (72 mg, 0.24 mmol), pyromellitic acid (79

mg, 0.32 mmol), 3-bpmp (101 mg, 0.38 mmol), and 8 mL of deionized water were placed into a 23 mL Teflon-lined acid digestion bomb. The bomb was sealed and heated in an oven at 120 C for 65 h and then cooled slowly to 25 C. Colorless blocks of 1 (97 mg, 84% yield based on Zn) were isolated after washing with distilled water and acetone and drying in air. Anal. calcd for C36H34N4O19Zn2 (1): C, 45.16; H, 3.58; N, 5.85%. Found: C, 45.44; H, 3.31; N, 6.06%. IR (cm-1): 3478 (w), 3022 (w), 2774 (w), 2456 (w), 2156 (w), 2086 (w), 1979 (w), 1709 (m), 1643 (w), 1567 (m), 1489 (m), 1458 (m), 1416 (m), 1335 (s), 1297 (m), 1229 (s), 1137 (s), 1114 (s), 1034 (m), 966 (m), 956 (m), 934 (s), 852 (vs), 840 (vs), 807 (vs), 778 (m), 755 (s), 731 (s).

Preparation of {[Zn2(Hpyro)2(H2-4-bpmp)] 3 4H2O}n (2).

Zinc nitrate hexahydrate (76 mg, 0.26 mmol), pyromellitic acid (76 mg, 0.30 mmol), 4-bpmp (109 mg, 0.41 mmol), and 8 mL of deionized water were placed into a 23 mL Teflon-lined acid digestion bomb. The bomb was sealed and heated in an oven at 120 C for 65 h and then cooled slowly to 25 C. Colorless blocks of 2 (110 mg, 87% yield based on Zn) were isolated after washing with distilled water and acetone and drying in air. Anal. calcd for C36H36N4O20Zn2 (2): C, 44.33; H, 3.72; N, 5.74%. Found: C, 44.86; H, 3.39; N, 6.02%. IR (cm-1): 3427 (w), 3000 (w), 2413 (w), 1688 (w), 1539 (s), 1482 (s), 1455 (s), 1441 (s), 1340 (vs), 1237 (m), 1188 (m), 1135 (m), 1061 (m), 1036 (m), 983 (m), 955 (m), 941 (m), 923 (m), 909 (m), 861 (m), 834 (m), 802 (m), 775 (m), 708 (s), 672 (m), 654 (m).

2 C36H36N4O20Zn2

empirical formula

C36H34N4O19Zn2

formula weight

957.41

975.42

crystal system

triclinic

monoclinic

space group

P1

P21/n

a (Å)

7.7354(6)

9.9681(6)

b (Å)

11.3208(9)

13.4652(8)

c (Å)

11.4353(9)

14.4896(9)

R () β ()

69.001(1) 89.672(1)

90 97.655(1) 90

γ ()

72.844(1)

V (Å3)

887.67(12)

1927.5(2)

Z

1

2

Dcalcd (g cm-3)

1.791

1.681

μ (mm-1)

1.448

1.337

min/max trans.

0.7055/0.8341

0.6486/0.8046

hkl ranges

-9 e h e 9, -13 e k e 13,

-11 e h e 12, -16 e k e 16,

total reflections

12973

13798

unique reflections

3 234

3 538

R(int)

0.0609

0.0512

parameters/restraints

292/5

298/8

R1 (all data)

0.0432

0.0415

R1 [I > 2σ(I)] wR2 (all data)

0.0407 0.1111

0.0394 0.1128 0.1109

-13 e l e 13

’ EXPERIMENTAL SECTION General Considerations. Zinc nitrate and pyromellitic acid were purchased commercially. Bis(pyridylmethyl)piperazine isomers were prepared using a published procedure.20 Water was deionized above 3 MΩ cm in-house. IR spectra were recorded on powdered samples using a Perkin-Elmer Spectrum One instrument. The luminescence spectra were obtained with a Hitachi F-4500 Fluorescence Spectrometer on solid crystalline samples anchored to quartz microscope slides with Rexon Corporation RX-22P ultraviolet-transparent epoxy adhesive.

1

-17 e l e 17

wR2 [I > 2σ(I)]

0.1085

max/min residual (e-/Å3)

0.666/-0.681

0.547/-0.437

GOF

1.037

1.143

X-ray Crystallography. Single-crystal X-ray diffraction was performed on single crystals of 1 and 2 with a Bruker-AXS ApexII CCD instrument at 173 K. Reflection data were acquired using graphite-monochromated Mo KR radiation (λ = 0.71073 Å). The data were integrated via SAINT. 21 Lorentz and polarization effect and empirical absorption corrections were applied with SADABS.22 The structures were solved using direct methods and refined on F2 using SHELXTL.23 All nonhydrogen atoms were refined anisotropically. Hydrogen atoms bound to carbon atoms were placed in calculated positions and refined isotropically with a riding model. The hydrogen atoms bound to the piperazinyl nitrogen atom(s) of the bpmp ligands in 1 and 2 were found via Fourier difference maps and then restrained at fixed positions and refined isotropically. Relevant crystallographic data for 1 and 2 are listed in Table 1.

’ RESULTS AND DISCUSSION Synthesis and Spectral Characterization. The compounds in this study were prepared cleanly as crystalline products by hydrothermal reaction of zinc nitrate, pyromellitic acid, and the relevant bpmp isomer. The infrared spectra for 1 and 2 were consistent with their structural characteristics as determined by single-crystal X-ray diffraction (Figures S1 and S2, Supporting Information). Puckering modes of the pyridyl and phenyl rings are evident in the region between 820 and 600 cm-1. Asymmetric and symmetric C-O stretching modes of the deprotonated carboxylate groups of the Hpyro ligands correspond to the intense, broadened features at 1567 and 1335 cm-1 (for 1) and 1539 and 1340 cm-1 (for 2). Features ascribed to the protonated Hpyro carboxylate group are seen at 1709 (for 1) and 1688 cm-1 1288

dx.doi.org/10.1021/cg1015109 |Cryst. Growth Des. 2011, 11, 1287–1293

Crystal Growth & Design

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Figure 1. Coordination environment of 1. A complete H2-3-bpmp ligand is shown.

Scheme 2. Binding Modes of the Hpyro Ligands in 1 and 2

n-

Figure 2. (a) [Zn(Hpyro)(H2O)]n coordination polymer layer in 1. (b) Representation of the (4,4) grid in this layer with Zn and Hpyro nodes shown in gray and black, respectively.

(for 2). Broad yet weak bands in the region of ∼3400 to ∼3500 cm-1 in the spectra arise from water molecule and protonated carboxylate O-H bonds, along with N-H bonds

Figure 3. (a) {[Zn2(Hpyro)2(H2O)2(H2-3-bpmp)]n 3D coordination polymer lattice in 1, with [Zn(Hpyro)(H2O)]nnlayers drawn in red. (b) Representation of the rare (4462)(4466) tcs binodal network, with five-connected Zn and four-connected Hpyro nodes shown in gray and black, respectively. The H2-3-bpmp ligands are drawn as blue rods.

within the protonated piperazinyl rings of the bpmp ligands. The broadness of these higher energy spectral features is caused by hydrogen bonding (see below). 1289



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Figure 4. Coordination environment of 2. A complete H2-4-bpmp ligand is shown.

Table 2. Selected Bond Distance (Å) and Angle () Data for 1 and 2 1 Zn1-O1

2.056(2)

N1-Zn1-O9

Zn1-O8a

2.063(2)

O1-Zn1-O3a

86.38(8)

Zn1-N1 Zn1-O9

2.105(3) 2.148(2)

O8a-Zn1-O3a N1-Zn1-O3a

175.24(8) 90.89(9)

Zn1-O3a

2.161(2)

O9-Zn1-O3a

86.05(8)

b

2.238(2)

O1-Zn1-O4b

171.34(7)

Zn1-O4

165.93(9)

O1-Zn1-O8a

97.53(8)

O8a-Zn1-O4b

90.60(8)

O1-Zn1-N1

102.07(9)

N1-Zn1-O4b

80.71(9)

O8a-Zn1-N1

90.94(9)

O9-Zn1-O4b

85.36(8)

O1-Zn1-O9

91.45(8)

O3a-Zn1-O4b

85.37(8)

O8a-Zn1-O9

91.12(8)

120.86(8)

2 Zn1-O6c

1.9267(18)

O6c-Zn1-O7d

Zn1-O1

1.9527(17)

O1-Zn1-O7d

98.14(8)

Zn1-O7d

1.9611(19)

O6c-Zn1-N1

100.72(8)

Zn1-N1 O6c-Zn1-O1

2.039(2) 128.20(8)

O1-Zn1-N1

100.02(8)

O7d-Zn1-N1

105.27(8)

Symmetry equivalent positions: -x þ 1, -y, -z. b Symmetry equivalent positions: x - 1, y, z. c Symmetry equivalent positions: x - 1/2, -y þ 3/2, z þ 1/2. d Symmetry equivalent positions: -x þ 1/2, y þ 1/2, -z þ 1/2. a

Structural Description of {[Zn2(Hpyro)2(H2O)2(H2-3-bpmp)] 3 H2O}n (1). The asymmetric unit of compound 1 contains a

divalent zinc cation, a singly protonated Hpyro trianion, an aqua ligand, one-half of a 3-bpmp molecule whose central piperazinyl ring is protonated at its piperazinyl nitrogen atoms, and a half-occupied water molecule of crystallization position (Figure 1). At zinc, the coordination environment is a distorted {ZnO5N} octahedron, with the equatorial positions taken up by carboxylate oxygen atom donors from four different Hpyro ligands. Axial positions are filled by an aqua ligand and a pyridyl nitrogen atom donor from a H2-3-bpmp ligand. Bond lengths and angles within the coordination environment of 1 are listed in Table 1.

Deprotonated carboxylate groups of the Hpyro ligands all bind to zinc, bridging a pair of zinc atoms at one terminus and acting as monodentate donors at the other two. The protonated carboxylate group does not bind to zinc. Thus, the Hpyro trianions serve as exotetradentate ligands with a μ4-κ4O:O0 : O00 :O000 bridging mode (Scheme 2), forming [Zn(Hpyro)(H2O)]nn- coordination polymer layers that are oriented along the ab crystal planes (Figure 2a). Embedded within the layer motif are anti-syn bridged {Zn2(OCO)2} eight-membered rings formed through the bridging carboxylate groups of two Hpyro ligands; the Zn 3 3 3 Zn through-space distance across these circuits measures 4.758 Å. Considering the Zn atoms and exotetradentate Hpyro ligands as four-connected nodes reveals a simple (4,4) grid topology within the [Zn(Hpyro)(H2O)]nnlayers (Figure 2b). Intralayer hydrogen-bonding donation from the aqua ligands or protonated carboxylate groups and ligated carboxylate groups provides some ancillary structural stabilization (Table 3). Adjacent [Zn(Hpyro)(H2O)]nnlayers are conjoined into a noninterpenetrated {[Zn2(Hpyro)2(H2O)2(H2-3-bpmp)]n 3D coordination polymer net (Figure 3a) by symmetry imposed anti-conformation H2-3-bpmp ligands that bridge pairs of Zn atoms with a Zn 3 3 3 Zn contact distance of 14.348 Å. Thus, the Zn atoms act as five-connected nodes. From this perspective, the underlying 3D topology of 1 can be construed as a 4,5-connected binodal net (Figure 3b). According to TOPOS,24 this net possesses a rare (4462)(4466) tcs topology (ThCr2Si2 prototype), which has only been reported in coordination polymer € chemistry twice previously (in Ohrstr€ om's barium oxalate phase [Ba(C2O4)(H2C2O4)(H2O)2]n25 and in our cadmium dicarboxylate complex {[Cd2(phthalate)2(bis(4-pyridylformyl)piperazine)(H2O)2]n26). The water molecules of crystallization occupy small incipient voids within the 3D net, comprising 5.4% of the unit cell volume according to PLATON.27 Protonated piperazinyl rings of the H2-3-bpmp ligands engage in hydrogen-bonding donation to unligated oxygen atoms of ligated Hpyro carboxylate groups (Table 3). Structural Description of {[Zn2(Hpyro)2(H2-4-bpmp)] 3 4 H2O}n (2). The asymmetric unit of compound 2 consists of a divalent zinc cation, a singly protonated Hpyro moiety, one-half 1290



Figure 5. (a) [Zn(Hpyro)]nn- coordination polymer layer in 2. (b) Representation of the Archimedean 4.82 net in this layer with Zn and Hpyro nodes shown in gray and black, respectively.

of a 4-bpmp molecule doubly protonated at its central piperazinyl ring, and two water molecules of crystallization (Figure 4). In contrast to the octahedral environment at zinc in 1, that of 2 is a {ZnO3N} tetrahedron. The three oxygen donors belong to different Hpyro ligands, while the pyridyl nitrogen donor atom of a H2-4-bpmp rounds out the coordination sphere. Bond lengths and angles around zinc are listed in Table 2. As in 1, one of the carboxylate groups of each Hpyro ligand is protonated, and these ligands construct [Zn(Hpyro)]nn- coordination polymer layers (Figure 5a). However, the Hpyro ligands in 2 are exotridentate and not exotetradentate as in 1, with μ3κ3O:O0 :O00 bridging mode (Scheme 2). Thus, both the Zn atoms and the Hpyro ligands are three-connected nodes within the layer motif, which results in an Archimedean 4.82 topology consisting of four- and eight-membered circuits (Figure 5b). In turn, adjacent [Zn(Hpyro)]nnlayers are connected into a neutral 3D [Zn2(Hpyro)2(H2-4-bpmp)] coordination polymer net (Figure 6a) by tethering H2-4-bpmp ligands, which span a Zn 3 3 3 Zn contact distance of 15.898 Å. Notably, this distance is significantly longer than the closest interlayer Zn 3 3 3 Zn contact (9.968 Å). This results in the necessity of the H2-4-bpmp ligands to connect to Zn atoms in neighboring layers offset by þb or -b. The interlayer regions reveal a crossing pattern for the H2-4bpmp ligands, which optimizes piperazinyl ring hydrogen-bonding donation to unligated Hpyro carboxylate oxygen atoms in the [Zn(Hpyro)]nnlayers (Table 3). The underlying topology of 2 was investigated, treating the Hpyro ligands as three-connected nodes, the Zn atoms as four-connected nodes, and the crossing H2-4-bpmp ligands as linkers. A simple, self-penetrated, 3,4connected binodal network (Figure 6b) was uncovered using

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Figure 6. (a) {[Zn2(Hpyro)2(H2-4-bpmp)]n 3D coordination polymer framework in 2, with [Zn(Hpyro)]nnlayers drawn in red and crossed H2-4-bpmp drawn in green. (b) Representation of the unprecedented (4.82)(4.82103) self-penetrated binodal network, with four-connected Zn and three-connected Hpyro nodes shown in gray and black, respectively. The H2-4-bpmp ligands are drawn as green rods and can be seen crossing between [Zn(Hpyro)]nn- layer submotifs.

Figure 7. Close-up view of the self-penetration of 10-membered circuits in the network of 2.

TOPOS, with a Schl€afli symbol of (4.82)(4.82103) and a long Vertex symbol of (4.8.8)(4.8.8.10.10.102). A topological analysis with TOPOS and SYSTRE output with an embedded net is given in the Supporting Information. The self-penetration mechanism involves intertwining and then linking of the 10-membered circuits involving the H2-4-bpmp ligands; a close-up of the selfcatenation is depicted in Figure 7. Water molecules of crystallization are anchored to the coordination polymer backbone via hydrogen-bonding donation from protonated Hpyro carboxylate 1291



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Table 3. Hydrogen Bonding Distance (Å) and Angle () Data for 1 and 2 symmetry transformation D-H 3 3 3 A

d(H 3 3 3 A)

— DHA

d(D 3 3 3 A)

for A

1 O9-H9A 3 3 3 O2 O9-H9B 3 3 3 O4

2.19(2)

154(3)

2.960(3)

x - 1, y, z

1.86(2)

153(4)

2.627(3)

-x þ 1, -y þ 1, -z

N2-H2N 3 3 3 O2 O5-H5A 3 3 3 O7

1.909(19)

171(3)

2.797(3)

-x þ 1, -y þ 1, -z

1.58(2)

166(4)

2.442(3)

1.832(18)

174(3)

2.713(3)

-x þ 1, -y þ 2, -z þ 1

2.00(2) 2.172(19)

153(4) 171(3)

2.750(3) 2.954(3)

-x þ 1, -y þ 2, -z

3 O2W

1.892(19)

173(3)

2.701(3)

-x þ 1/2, y þ 1/2, -z - 1/2

3 O8

2.25(3)

141(4)

2.921(3)

1.710(19)

176(3)

2.573(3)

2 N2-H2N 3 3 3 O8 O2W-H2WB 3 3 3 O5 O1W-H1WB 3 3 3 O1 O1W-H1WA 3 3 O2W-H2WA 3 3

O3-H3O 3 3 3 O1W

groups. These occupy 12.2% of the unit cell volume. The selfpenetration of the network of 2 minimizes solvent-accessible extra-framework space, if compared to the voids that would be present if a noninterpenetrated straight-pillared network was formed instead. Luminescence Spectra of 1 and 2. Irradiation of complexes 1 and 2 with ultraviolet light (λex = 300 nm) in the solid state resulted in modest blue-violet visible light emission with λmax values of ∼465 and ∼435 nm, respectively (Figure S3, Supporting Information). Thus, the emissive behavior property is ascribed to ligand-centered electronic transitions between π-π* or π-n molecular orbital manifolds within the aromatic pyridyl rings of H2-3-bpmp and H2-4-bpmp tethers.28 The difference in intensity between the emission of solid 1 and 2 is attributed to crystallite size effects as opposed to any molecular structurebased effects.

’ CONCLUSIONS Coordination geometry preference and pyridyl donor disposition appear to play a predominant role in instilling 3D topology in divalent zinc pyromellitate bis(pyridylmethyl)piperazine coordination polymers. Octahedral geometry at zinc in the 3-bpmp derivative 1 allows the binding of four Hpyro trianions at a single zinc center, resulting in the formation of [Zn(Hpyro)(H2O)]nnlayers with a standard (4,4) grid topology. A rare binodal tcs network is generated upon bridging by 3-bpmp tethers. In contrast, the tetrahedral geometry at zinc in the 4-bpmp analog 2 only permits binding of three Hpyro ligands, which affords three-connected [Zn(Hpyro)]nnlayers with an Archimedean topology consisting of four- and eight-membered circuits. The longer span between the pyridyl donors in the anti conformation 4-bpmp ligands does not permit the straight pillaring seen in 1, instead resulting in a novel crossed-ligand self-penetrated network. Bis(4-pyridylmethyl)piperazine continues to be a useful ligand for the construction of self-catenated coordination polymer topologies. ’ ASSOCIATED CONTENT

bS

Supporting Information. Infrared and emission spectra for 1 and 2 and topological analysis for 2. This material is available free of charge via the Internet at http://pubs.acs.org.

x - 1/2, -y þ 3/2, z - 1/2

Accession Codes

Crystallographic data (excluding structure factors) for 1 and 2 have been deposited with the Cambridge Crystallographic Data Centre with nos. 800369 and 800368, respectively. Copies of the data can be obtained free of charge via the Internet at http:// www.ccdc.cam.ac.uk/conts/retrieving.html or by mail at CCDC, 12 Union Road, Cambridge CB2 1EZ, United Kingdom. Fax: 441223336033. E-mail: [email protected].

’ AUTHOR INFORMATION Corresponding Author

*E-mail: [email protected].

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