Cuprous Halide Complexes of a Variable Length Ligand: Helices, Cluster Chains, and Nets Containing Large Solvated Channels

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Article

Cuprous Halide Complexes of a Variable Length Ligand: Helices,Cluster Chains and Nets Containing Large Solvated Channels

William J. Gee, and Stuart Robert BattenCryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/cg3018858 • Publication Date (Web): 09 May 2013

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Cuprous Halide Complexes of a Variable Length

Ligand: Helices, Cluster Chains and Nets Containing

Large Solvated Channels

William J. Gee and Stuart R. Batten*

School of Chemistry, Monash University, Clayton, Victoria, 3800, Australia

Supporting Information Placeholder

ABSTRACT: The variable-length azacrown ether bridging ligand N,N'-bis(3-pyridyl-methyl)diaza-18-

crown-6 (b3pmdc) has been reacted with cuprous iodide to give a range of new discrete and polymeric

coordination compounds. Six structurally diverse CuI(b3pmdc) architectures were isolated as well as a

single oxidized CuII(b3pmdc) species. These include the helical 1D chain

[H4b3pmdc][Cu10I14]·CHCl3·2H2O (1), the luminescent linear cluster chain [Cu4I6(H2b3pmdc)] (2), the

guest water containing network [Cu4I4(Hb3pmdc)2](1.5ClO4)(0.5I3)·3.5H2O·2.5MeOH (3), the

luminescent cubane cluster chain [Cu4I4(b3pmdc)2] (4), the 3D net [Cu9I12(Kb3pmdc)3(H2O)4]·9MeOH

(5), the dinuclear mixed halide [Cu2Cl3.4I2.6(H4b3pmdc)] (6) and the cupric 1D chain

[CuCl2(H2b3pmdc)(MeOH)2]·2Cl·2MeCN (7). Manipulation of the ligand conformation was achieved

by the addition of the alkali metal salt potassium and by varying the pH of the solution with a range of

acids (HCl, HClO4). In the case of 2 and 4 green and yellow luminescent emission was observed, as a

result of the varied metal environment.

New molecular tools are needed to foster new developments in the growing field of crystal

engineering, with the goal of accelerating the development of materials with advantageous properties.1

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An emerging tool for the crystal engineer is the variable length ligand, which offers the ability to

manipulate the length and geometry of an organic linker in a predicable manner in response to chemical

stimuli. Proof of principle was recently demonstrated using a para-pyridyl substituted azacrown ether

ligand that exhibited variation in length ranging from ca. 7.7 Å to 16.6 Å as a result of coordination of

alkali, alkaline earth and transition metals.2 That same ligand was recently shown to manipulate spin

crossover properties in FeII compounds as a result of varying the guest molecule which, in turn, afforded

differing packing arrangements.3 Previously, related diazamacrocyclic ligands have shown promise as

molecular tectons, however targeted manipulation of ligand length was not reported.4

This work focuses on a meta-pyridyl variant of the dipyridyl azacrown ether family, namely N,N'-

bis(3-pyridyl-methyl)diaza-18-crown-6 (b3pmdc), reacted in cuprous iodide solution. Cuprous iodide

has been demonstrated to stabilize a diverse array of inorganic architectures, including 1D chains of

cubane clusters linked by organic spacers,5 polymeric CuxIy chains of varying ratios,5a,6 dinuclear

species,5e-g,7 discrete clusters,5c,6b,8 calixarene complexes,9 mixed valence clusters,10 CuI slabs11 and

nanosized wheels.12 These cuprous iodide species have unique properties including

photoluminescence5a-c,5e,5g,6c,13 and electrical conductivity,6a,11 allowing their potential application in

organic light-emitting diodes (OLEDs)5e and hybrid materials with second-order nonlinear optical

(NLO) responses.11

The rich diversity of chemical motif and application has drawn inorganic chemists seeking to put

ligands through a gamut of varying coordination modes and architectures,5f,7b,8a thereby demonstrating

their utility, as we aim to achieve here. Thus we report the synthesis and characterization of six

structurally-diverse CuI(b3pmdc) architectures, as well as a single oxidized CuII(b3pmdc) species.

These include the helical 1D chain [H4b3pmdc][Cu10I14]·CHCl3·2H2O (1), the luminescent linear cluster

chain [Cu4I6(H2b3pmdc)] (2), the guest water containing network

[Cu4I4(Hb3pmdc)2](1.5ClO4)(0.5I3)·3.5H2O·2.5MeOH (3), the luminescent cubane cluster chain

[Cu4I4(b3pmdc)2] (4) and the 3D net [Cu9I12(Kb3pmdc)3(H2O)4]·9MeOH (5). The use of hydrochloric

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acid yielded a dinuclear mixed halide [Cu2Cl3.4I2.6(H4b3pmdc)] (6) and a cupric 1D chain

[CuCl2(H2b3pmdc)(MeOH)2]·2Cl·2MeCN (7). Each of these species has been characterized using

single-crystal X-ray crystallography, supported by infrared spectroscopy, thermogravimetric analysis

and, in the case of 2 and 4, fluorescence spectrometry.

Experimental Section

General Remarks. CAUTION: Metal perchlorates are potentially explosive! Only a small amount of

material should be prepared and handled with great care. The ligand b3pmdc was synthesized

according to a literature procedure14 using chemicals purchased from Sigma-Aldrich. A stock solution

of cuprous perchlorate was created by refluxing cupric perchlorate hydrate with an excess of copper

powder in acetonitrile for two hours. The resultant clear solution was filtered and stored under nitrogen.

Metal salts were purchased from Alfa Aesar. All yields shown are relative to Cu(ClO4)2�6H2O which in

each case is limiting.

Physical Measurements. Solid-state IR spectra were recorded using a Perkin Elmer 1600 series FTIR

or a Bruker Equinox 55 Infrared Spectrometer fitted with a Specac Diamond ATR source. Infrared band

frequencies are reported in wavenumbers (cm-1) and intensities are reported as strong (s), medium (m)

or weak (w). Thermogravimetric analysis was performed using a Mettler Toledo TGA/DSC 1 STARe

System and Software. Elemental analyses were performed by Campbell Microanalytical Laboratory,

Department of Chemistry, University of Otago, Dunedin, New Zealand. Solid-state photoluminescence

measurements were undertaken for single crystals of 2 and 4 using a fibre optic probe coupled to a

Varian Cary Eclipse fluorescence spectrophotometer. Sample emissions were passed through a

monochromator (CVI, dk480) and focused onto a fast response avalanche photodiode detector (APD,

Id-Quantique, Id-100).

Synthesis. [H4b3pmdc][Cu10I14]�CHCl3�2H2O (1). Compound 1 was obtained by slow diffusion of

solutions of cuprous perchlorate (0.06 mmol in 1 mL CH3CN) and b3pmdc (50 mg, 0.11 mmol) in

CHCl3 (1 mL) containing perchloric acid (0.23 mmol) into a buffer layer (1:1 CHCl3:MeOH, 1 mL)

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containing tetraethylammonium iodide (40 mg, 0.15 mmol). A crop of yellow crystals suitable for X-ray

analysis grew in the metal-rich layer after 24 h. The crystals were isolated by decanting the mother

liquor, washing with CH3CN followed by filtration. Yield: 4 mg, 23%. Anal. Calcd for

C25H41Cl3Cu10I14N4O6: C, 9.97; H, 1.37; N, 1.86. Found: C, 10.21; H, 1.50; N, 1.76. IR (ATR): υmax

3156w, 3111w, 3062w, 3014w, 2950w, 2736w, 1628w, 1599w, 1540m, 1462m, 1429w, 1400w, 1349w,

1311w, 1273w, 1251m, 1075s, 990m, 968m, 937m, 914m, 788m, 752m, 672m, 622m.

[Cu4I6(H2b3pmdc)] (2). Crystals were obtained from the same reaction as 1. Crystals grew in the

ligand-rich and buffer regions. Yield: 12 mg, 55%. Anal. Calcd for C12H19Cu2I3N2O2: C, 19.71; H, 2.62;

N, 3.83. Found: C, 19.82; H, 2.64; N, 3.90. IR (ATR): υmax 3158w, 3093w, 3047m, 2993w, 2952w,

2892m, 2631m, 1638w, 1609w, 1545m, 1466m, 1354m, 1258m, 1086s, 1024m, 991w, 970w, 902w,

803m, 678m, 622m.

[Cu4I4(Hb3pmdc)2](1.5ClO4)(0.5I3)·3.5H2O·2.5MeOH (3). Compound 3 was obtained by slow

diffusion of solutions of cuprous perchlorate (0.06 mmol in 1 mL CH3CN) and b3pmdc (50 mg, 0.11

mmol) in CHCl3 (1 mL) containing perchloric acid (0.11 mmol) into a buffer layer (1:1 CHCl3:MeOH, 1

mL) containing tetraethylammonium iodide (40 mg, 0.15 mmol). A small number of red crystals were

manually separated from a large quantity of yellow amorphous material after a period of two weeks.

Yield: 3 mg, 3%. The low yield precluded elemental analysis. υmax 3429w, 2871w, 1601w, 1478w,

1431m, 1353w, 1271w, 1192w, 1074s, 931m, 817w, 781w, 707m, 648w, 622m.

[Cu4I4(b3pmdc)2] (4). Obtained by slow diffusion of solutions of cuprous perchlorate (0.06 mmol in

1 mL CH3CN) and b3pmdc (50 mg, 0.11 mmol) in CHCl3 (1 mL) into a buffer layer (1:1

CHCl3:CH3CN, 1 mL) containing tetraethylammonium iodide (40 mg, 0.15 mmol). Colorless crystals

were observed after several days. Yield: 15 mg, 61%. Anal. Calcd for C48H72Cu4I4N8O8: C, 34.92; H,

4.40; N, 6.79. Found: C, 34.85; H, 4.37; N, 6.59. IR (ATR): υmax 2850m, 1597m, 1474m, 1426s, 1352m,

1299m, 1254m, 1192m, 1119s, 1040s, 992s, 947m, 909m, 836m, 795m, 701s, 649m.

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[Cu9I12(Kb3pmdc)3(H2O)6]�9MeOH (5). Obtained by slow diffusion of solutions of cupric

perchlorate hydrate (43 mg, 0.12 mmol) in CH3OH (1 mL) and b3pmdc (50 mg, 0.11 mmol) in CHCl3

(1 mL) into a buffer layer (1:1 CHCl3:CH3OH, 1 mL) containing potassium iodide (25 mg, 0.15 mmol).

Red crystals were observed after a number of days. Yield: 21 mg, 77%. Anal. Calcd for

C27H32Cu3I4KN4O8 (1 - 5MeOH): C, 25.44; H, 3.66; N, 4.24; I, 38.40. Found: C, 25.31; H, 3.69; N,

4.27; I, 38.67. IR (ATR): υmax 2962w, 2869m, 1598w, 1476w, 1429m, 1350w, 1259m, 1090s, 932m,

797s, 706m, 645w, 622m.

[Cu2Cl3.4I2.6(H4b3pmdc)] (6). Obtained by slow diffusion of solutions of cuprous perchlorate

(0.06 mmol in 1 mL CH3CN) and b3pmdc (50 mg, 0.11 mmol) in CHCl3 (1 mL) containing

hydrochloric acid (0.45 mmol) into a buffer layer (1:1 CHCl3:MeOH, 1 mL) containing

tetraethylammonium iodide (40 mg, 0.15 mmol). Yellow crystals suitable for X-ray analysis grew after

several days. The crystals were isolated by decanting the mother liquor, washing with CH3OH followed

by filtration. Yield: 14 mg, 40%. Anal. Calcd for C24H40Cl3.4Cu2I2.6N4O4: C, 28.09; H, 3.93; N, 5.46; Cl

& I, 43.90. Found: C, 27.87; H, 3.90; N, 5.42; Cl & I, 44.34. IR (ATR): υmax 3047w, 2892w, 2632w,

2346w, 1639w, 1610w, 1545m, 1467m, 1354m, 1316w, 1258w, 1086s, 1024m, 991m, 970m, 925m,

903m, 886m, 840m, 826m, 803s, 762m, 677s.

[CuCl2(H2b3pmdc)(MeOH)2]�2Cl�2MeCN (7). Blue crystals of 7 grew a week after exposing the

mother liquor of 6 to air. The crystals were washed with CH3OH and isolated by filtration. Yield: 11

mg, 40%. Anal. Calcd for C30H52Cl4CuN6O6: C, 45.15; H, 6.57; N, 10.53. Found: C, 45.19; H, 6.57; N,

10.60. IR (ATR): υmax 3399s, 2963m, 2916m, 2631m, 1611m, 1484w, 1432m, 1360m, 1257w, 1197w,

1114s, 1077s, 997w, 966w, 937w, 912w, 851w, 810w, 700w, 657w.

X-ray Studies. Diffraction data for 3, 4 and 7 were collected at 123 K on a Bruker X8 Apex equipped

with a KAPPA CCD detector using Mo Kα radiation (λ = 0.71073 Å). Diffraction data for 1,2,5 and 6

were collected at 123 K at either the MX1 or MX2 beamlines at the Australian Synchrotron using

synchrotron radiation (λ = 0.710698 Å). Adsorption corrections based on multiscan methods were

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applied to 2 and 7.15 Apex structures were solved by direct methods in SHELX-9716 and refined by the

full-matrix method based on F2 with the program SHELXL-97 using the X-SEED software package.17

Data collection and integration for the synchrotron structures were performed within Blu-Ice18 and

XDS19 software programs. All hydrogen atoms attached to carbon were included in the model at

idealized positions and refined using the riding model. A summary of the crystallographic data for

compounds 1-7 is shown in Table 1.

Hydrogen atoms could not be modeled on methanol molecules within the pores of 5 and were omitted

from the model. Similarly, it was found that the methanol molecules within the pores could not sustain

anisotropic refinement, hence they were modeled as isotropic.

Tables of interatomic distances for structures 1-7 are included as Supporting Information.

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Table 1: Crystal data and structure refinement for compounds 1-7.

Complex 1 2 3 4 5 6 7

Chemical formula

C25H41Cl3Cu10I1

4N4O6 C12H19Cu2I3N2

O2 C101H156Cl3Cu8I11

N16O40 C48H72Cu4I4N8

O8 C81H132Cu9I12K3N14O22

C24H40Cu2Cl3.4I2.6

N4O4 C30H52CuCl4N6O6

Formula Mass 3011.97 731.07 4244.99 1650.90 3837.95 1026.15 1068.84

Crystal system Triclinic Triclinic Triclinic Triclinic Trigonal Monoclinic Triclinic

Space group P1� P1� P1� P1� P-3 P21/n P1�

a/Å 10.642(2) 8.4710(17) 13.4834(13) 11.3584(13) 19.275(3) 10.9151(2) 9.1665(6)

b/Å 13.927(3) 8.8950(18) 16.9513(10) 14.054(2) 19.275(3) 11.4972(2) 10.0157(7)

c/Å 22.032(4) 12.919(3) 19.4949(12) 19.535(3) 13.123(3) 13.0904(3) 10.8275(7)

α/° 100.20(3) 107.31(3) 68.035(2) 107.967(8) 90 90 78.835(2)

β/° 90.27(3) 91.80(3) 73.558(2) 97.502(7) 90 91.945(1) 77.128(2)

γ/° 109.39(3) 96.29(3) 71.645(2) 98.108(7) 120 90 75.841(2)

Unit cell volume/Å3

3024.3(10) 921.6(3) 3852.4(4) 2886.0(7) 4222.6(12) 1625.9(2) 929.40(11)

Z 2 2 1 2 3 2 1

Temperature/K 123 123 123 123 123 123 123

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µ/mm-1 10.756 7.336 3.410 3.649 3.422 4.053 1.426

Reflections measured

51915 16250 62624 26701 88031 17255 7871

Independent reflections (Rint)

13743 (0.0350) 4581 (0.0548) 13733 (0.0470) 12328 (0.0705) 8639 (0.0776) 3767 (0.0240) 4203 (0.0127)

Obs. reflections

(I > 2σ(I))

12550 4357 10844 8549 7089 3414 3976

Final R1 (obs., all)

0.0451, 0.05183 0.0322, 0.0343 0.0671, 0.0909 0.0488, 0.0845 0.0720, 0.0813 0.0362, 0.0447 0.0236, 0.0279

Final wR2 (obs., all)

0.1235, 0.1560 0.0796, 0.0810 0.1832, 0.2119 0.1161, 0.1653 0.2372, 0.2487 0.1004, 0.1028 0.0822, 0.1035

GOF on F2 1.063 1.067 1.112 1.024 1.060 1.140 1.212

largest dif. peak/hole/e Å3

2.062/-4.057 1.012/-2.280 2.430/-3.080 1.207/-1.931 2.289/-2.175 1.784/-1.134 0.528/-0.856

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Results and Discussion

Synthesis of CuI and Cu

II Species. Two variables were initially targeted by this study to effect

changes in the ligand geometry of b3pmdc: the inclusion of a potassium cation and the lowering of pH,

each of which will influence the structure and rigidity of the azacrown group (Figure 1). The

incorporation of alkali (i.e. Figure 1a), alkaline earth and selected transition metals were recently

highlighted using a closely related ligand.2 Similarly, the basicity of the azacrown ligand in aqueous

solvent systems was found to facilitate inclusion of a water molecule upon protonation (Figure 1, (b)),

reproducibly giving an 'S' ligand geometry.20 In this work, we sought to control the degree of

protonation of b3pmdc through manipulation of solvent system and acidity. Cuprous iodide species

were generated by slow in situ diffusion of a copper source, typically [CuI(MeCN)4](ClO4), a source of

iodide (KI, NEt4I) and the ligand, b3pmdc. The diffusion gradient typically proceeded from metallic

acetonitrile or methanol, through a buffer layer (1:1 CHCl3:MeOH) containing the iodide source, to a

chloroform solution of b3pmdc. During instances where acid was added, acidification of b3pmdc was

undertaken in the chloroform layer followed by addition of the minimum quantity of methanol required

to resolve turbidity of the resultant mixture. Crystalline material suitable for single crystal X-ray

diffraction studies were found to deposit after several days in the buffer region. The yellow crystals of

1D polymer 1 were found to slowly return to solution as part of an equilibrium favoring eventual

formation of tetranuclear cluster 2. Blue crystals of cupric species 7 grew in the hours subsequent to

exposing the solution of 6 to air.

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Figure 1. Common ligand geometries observed for the azacrown ether group and relevant to b3pmdc.

Hydrogen and coordinative bonds are represented as dashed lines. Examples a, b and c are known from

prior work.2,20

Solid state structures of 1-7. Ten CuI centers were observed within the asymmetric unit of

[H4b3pmdc][Cu10I14]·CHCl3·2H2O (1) linked by fourteen iodides in a spiral conformation. Tetra-

protonated H4b3pmdc balances the charge, with the azacrown ammonium groups hydrogen bonding to

water molecules located above and below the crown ring (N-O distances of 2.827(10) Å and 2.835(11)

Å). The two water molecules are 3.104(12) Å apart and, although the hydrogen atom locations could not

be determined from the electron density map, hydrogen bonding interactions are highly probable

between the water molecules and the crown oxygens. A molecule of chloroform completes the

asymmetric unit (Figure 2). H4b3pmdc sits within the helical ridges of two polymeric [Cu10I14]∞ chains

(Figure 3). The pyridyl proton interacts very weakly with two iodide atoms in a bifurcated manner, with

observed (N)H…I distances of 3.069 Å and 2.999 Å. The majority of Cu-Cu distances within the

[Cu10I14]∞ chain range from 2.780 Å to 3.037 Å, however two contacts, Cu(1)-Cu(2): 2.5598(19) Å and

Cu(6)-Cu(7): 2.5456(19) Å, are extremely close to that of metallic copper (2.56 Å).6a The former range

relates well to other reports of cuprous chains6a and although unusual, Cu-Cu contacts of less than twice

the van der Waals radius of CuI (1.4 Å) have been observed previously in polymeric cuprous iodide

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chains.6b,c Each copper center possesses a tetrahedral CuI4 coordination environment. A helical chain of

this type, formed by face-sharing tetrahedra, has previously been termed a 'tetrahelix'.21 Two iodides

bridge in a µ4 fashion, with six each bridging in µ3 and µ2 manners completing the helical segment. The

chiral 'handedness' of the [Cu10I14]∞ chains alternates along the crystallographic c-axis, yielding an

overall racemic packing arrangement. The closest contact between the chains is an interiodide distance

(I(5)-I(5')) of ca. 4.0 Å. The addition of two equivalents of perchloric acid was essential to ensure 1

exists as the fully protonated species. Increasing the ratio of acid was found to improve the yield of 1

relative to a diprotonated species 2 (vide infra).

Figure 2. Structure of 1 showing the [Cu10I14]∞ chain, H4b3pmdc, chloroform and hydrogen bonded

water molecules. All non-acidic hydrogen atoms have been removed for clarity. Thermal ellipsoids are

shown at 50% probability.

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Figure 3. Positioning of H4b3pmdc between two [Cu10I14]∞ helical chains in 1. All non-acidic hydrogen

atoms, chloroform and water molecules have been removed for clarity.

Helix 1 was found to crystallize only in a high concentration of cuprous iodide, hence the crystals

were later found to dissolve as the metal concentration decreased due to diffusion of the Cu mixture

throughout the mixture. As a result, crystallization of a second yellow cuprous iodide species was later

observed. The structure of [Cu4I6(H2b3pmdc)] 2 is a 1D chain motif, however lack of protonation at the

pyridyl groups allows for H2b3pmdc to participate in coordination to the copper fragments, yielding a

coordination polymer (Figure 4). The [Cu4I6]2- cluster core can be viewed as the fusion of two [Cu2I3]

-

units, with the opposing half generated through an inversion center. Each copper atom retains the

tetrahedral coordination mode seen for 1, with Cu-Cu distances of 2.4574(9) Å (Cu(1)-Cu(2)) and

2.8848(14) Å (Cu(2)-Cu(2')) observed. Pyridyl groups coordinate to the cluster termini (Cu(1)-N(1):

1.988(3) Å) with four µ2 and two µ3 bridging iodides completing the cluster. The ligand adopts an 'S'

conformation with the ammonium protons oriented into the crown (Figure 1, (c)). Minimization of ionic

repulsion appears to largely govern the ligand geometry in this case. The ligand length, measured from

the pyridyl nitrogen donors, was found to be ca. 10.6 Å

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Figure 4. Coordination polymer 2 comprising alternating H2b3pmdc and [Cu4I6] units. Thermal

ellipsoids are shown at 50% probability.

Decreasing the ratio of acid to ligand resulted in monoprotonation the ligand in

[Cu4I4(Hb3pmdc)2](1.5ClO4)(0.5I3)·3.5H2O·2.5MeOH (3), which in combination with Cu4I4 cubane

nodes is incorporated into a ladder-like network. The asymmetric unit, shown in Figure 5, contains an

entire Cu4I4 cubane unit, with each copper atom exhibiting a tetrahedral coordination geometry

completed by pyridyl coordination from Hb3pmdc. Two unique Hb3pmdc ligands are present, each

protonated at a single tertiary amine within the crown and hydrogen bonding to a water molecule. The

charge on the cationic ligands is offset by a perchlorate molecule that is disordered over two positions,

and a molecule of triiodide and a second perchlorate molecule which each possess half occupancy. The

remaining void space is filled by two water molecules, one with full occupancy, one with half

occupancy, and four methanol molecules, one with full occupancy, three with half occupancy.

The overall structure resembles a 1D ladder-like net, with the sides of the ladders defined by Cu4I4

clusters bridged by one type of Hb3pmdc ligand, and the rungs provided by the second type of

Hb3pmdc ligand, which bridges the clusters in pairs to form loops (Figure 6). The Cu4I4 nodes have

Cu-Cu distances varying from 2.6129(19) Å (Cu(1)-Cu(2)) to 2.7113(19) Å (Cu(2)-Cu(3)), with an

average Cu-Cu distance of 2.65 Å. The hydrogen bonded water molecules within the azacrown impart a

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bent ligand geometry that has been observed in prior studies.2 Indeed the bridging lengths were found to

be ca. 9.2 and 10.2 Å, both of which are within the typical range for monoprotonated water-hosting

ligands of 8.9 to 10.2 Å.20 The ammonium hydrogen bond lengths were determined to be closest at

2.734(14) Å (N(2)-O(9)) and 2.689(11) Å (N(4)-O(10)), with the remaining distances observed to be

2.94(2) Å (O(9)-O(3)), 2.841(13) Å (O(9)-O(6)), 2.864(10) Å (O(10)-O(7)) and 2.822(10) Å (O(10)-

O(8)). The triiodide anion possesses a near linear geometry (175.00(14)° I(5)-I(6)-I(7)) and near

equivalent diiodide distances of 2.821(4) Å (I(5)-I(6)) and 2.873(4) Å (I(6)-I(7)).

In the absence of perchloric acid, neutral ligands were incorporated into a 1D coordination polymer of

b3pmdc, both linking and capping cubane [Cu4I4] clusters in the structure of [Cu4I4(b3pmdc)2]∞ (4,

Figure 7). One of the two b3pmdc ligands caps the cluster in an intramolecular fashion whereas the

second ligand serves to bridge between two [Cu4I4] units. The copper atoms are arrayed in a tetrahedron,

each coordinating to a single pyridyl group and three µ3 bridging iodides. The Cu-Cu distances vary

from 2.6035(15) Å (Cu(2)-Cu(3)) to 2.8101(15) Å (Cu(1)-Cu(2)) with an average distance of 2.69 Å.

The bond lengths between the pyridyl groups and copper centers range from 2.054(8) (Cu(4)-N(7)) to

2.021(7) (Cu(2)-N(4)) Å. The capping b3pmdc ligand sits over the cluster core in a fashion reminiscent

of a pair of earmuffs, culminating in a compact bridging length of ca. 6.2 Å. Despite the lack of a

templating force, be it metal inclusion, hydrogen bound water or charge repulsion, the second ligand

exhibits a bridging length of ca. 13.3 Å, more than double that of the capping ligand. This is largely a

result of the size of the [Cu4I4(b3pmdc)] moieties, necessitating the ligand being nearly fully extended

in order to bridge between these units (Figure 7, bottom).

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Figure 5. Structure of 3. The [Cu4I4] cubane unit with to two Hb3pmdc ligands coordinating. Only one

of the two possible disordered positions for the counter anions is shown. Hydrogen atoms and lattice

solvent molecules have been omitted for clarity.

Figure 6. Extended 1D ladder-like motif exhibited by 3. Hydrogen atoms, counter ions and lattice

solvent molecules have been omitted for clarity.

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Figure 7. 1D coordination polymer 4 comprising a bridging and capping b3pmdc ligand and [Cu4I4]

units. Thermal ellipsoids where shown are at 50% probability.

Replacement of tetrabutylammonium iodide with potassium iodide resulted in neutral ligands hosting

potassium cations. The resulting 3D coordination polymer contains both [Cu4I5] and [Cu5I6] cluster

units, with an overall composition of [Cu9I12(Kb3pmdc)3(H2O)4]·9MeOH (5) (Figure 8). The

asymmetric unit contains one third of the cluster core, with I(1), I(3) and Cu(1) each located on a

threefold rotation axis. Half of the b3pmdc ligand is present in the asymmetric unit, with the remainder

generated by an inversion center located at the potassium cation. The potassium cation coordinates to

both iodide and a water molecule, and three molecules of methanol were also located in the lattice. The

presence of an extra cuprous iodide, Cu(3) and I(4), constitutes the difference between the [Cu4I5] and

[Cu5I6] cluster units, and occurs such that the extra atoms show half the expected site occupancy. This

suggests a random arrangement of the two cluster types rather than an ordered arrangement which

would lead to the two clusters being crystallographically distinct. Cu(3) exhibits distorted trigonal

planar coordination with angles of 105.7(3)° (I(2)-Cu(3)-I(4)), 114.6(3)° (I(1)-Cu(3)-I(2)) and 138.4(3)°

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(I(1)-Cu(3)-I(4)) observed. In the absence of Cu(3) and I(4) the void is filled by a water molecule

coordinated to potassium.

Figure 8. Structure of 5. Only the pyridyl groups of two b3pmdc ligands coordinating to the [Cu4I5]

cluster are shown.

Each cluster is coordinated to three Kb3pmdc ligands, and each Kb3pmdc ligand in turn bridges two

clusters, leading to honeycomb-like 2D (6,3) networks (Figure 9) which possess large hexagonal

windows (diameter ca. 13 Å). The layers stack in an eclipsed fashion, leading to large channels. Each

channel is filled by solvent methanol. Two interactions fuse the layers into a 3D network: ionic

interactions between K(1) and the partially occupied I(4), and π-π interactions between the pyridyl

groups of stacked b3pmdc ligands, with an observed π-π distance of 3.88 Å (Figure 10).

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Figure 9. Packing of 5 along the crystallographic c-axis. All hydrogen atoms and methanol molecules

within the hexagonal pore have been removed for clarity.

Substituting hydrochloric acid for the perchloric acid retained the acidic environment for protonation

of b3pmdc observed with 1 and 2, but imparted a new variable in the form of halide exchange. Aside

from the obvious differences in ionic radii, chloride is also more likely to engage in significant

hydrogen bonding interactions, which may then affect the coordination motifs in the cuprous halides

regions. These effects were realized with isolation of ionic pair [Cu2Cl3.4I2.6(H4b3pmdc)] (6), which

contains a tetra-protonated b3pmdc ligand and a mixed halide CuI dimer (Figure 11). The structure

crystallizes in the P1� space group, with the asymmetric unit consisting of half of both the CuI dimer and

H4b3pmdc. The bridging halide exhibits substitutional disorder, with site occupancy factors refined as

0.3 iodide and 0.7 chloride. Hydrogen bonding to the terminal chlorides of the copper dimer occurs

from both pyridinium and tertiary ammonium groups from separate H4b3pmdc molecules. These

interactions are displayed at either terminus of the copper dimer (Figure 12). In this manner, each

H4b3pmdc hydrogen bonds to four distinct copper dimers. As each cluster also interacts with four

crown molecules, a hydrogen bonded 3D cds net22 is formed with alternating H4b3pmdc and cluster

nodes. Hydrogen bond lengths range from 3.160(5) Å (N(1)-Cl(1)) to 3.179(4) Å (N(2)-Cl(1)), however

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the strength of the pyridyl derived N(1) hydrogen bond is likely less, owing to the more angled

directionality (ca. 138°) relative to the tertiary ammonium N(2) derivative (ca. 154°).

Figure 10. Inter-sheet interactions in 5. Only the pyridyl groups of two b3pmdc ligands coordinating to

the [Cu4I5] cluster are shown. Each pyridyl group undergoes offset π-π stacking with neighboring

b3pmdc ligands. Ionic interactions between K(1) and I(4) occur where copper is present.

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Figure 11. Solid-state structure of ionic pair 6 which comprises [H4b3pmdc][Cu2Cl2I2X2] (X = 0.3 I,

0.7 Cl). All non-acidic hydrogen atoms have been removed for clarity.

Figure 12. Hydrogen bonding network observed between a copper dimer of 6 and four separate

H4b3pmdc molecules, which, in turn, are hydrogen bonded to four copper dimers.

After isolation of 6, prolonged exposure of the filtrate to air resulted in dioxygen mediated oxidation

of the remaining CuI to CuII, generating blue crystals of [CuCl2(H2b3pmdc)(MeOH)2]·2Cl·2MeCN (7)

after only twelve hours. The cupric metal center is located on an inversion center and has an octahedral

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conformation, with two methanol molecules present in Jahn-Teller distorted axial positions and para

arrangement of the chloride and pyridyl groups in the equatorial positions (Figure 13). Both of the

coordinated methanol molecules hydrogen bond to a second chloride anion, with protonation of

H2b3pmdc providing an additional hydrogen bond interaction (Figure 13, bottom) and charge

balancing. Hydrogen bond distances of 3.1262(13) Å (O(3)-Cl(2)) and 3.1059(14) (N(2)-Cl(2)) were

observed, suggesting near equivalent interactions between both donor atoms. The three bond lengths

about the copper atom are 2.0167(13) Å (Cu(1)-N(1)), 2.3186(4) Å (Cu(1)-Cl(1)) and 2.5015(13) Å

(Cu(1)-O(3)), each duplicated by symmetry to give the six coordinate geometry. The overall length of

H2b3pmdc was found to be ca. 12.5 Å. The overall structure is 1D polymeric in nature, with H2b3pmdc

covalently linking cupric chloride units. Non-covalent hydrogen bond interactions between ammonium

chloride and coordinated methanol molecules strengthen the chain (Figure 13, bottom). Small lattice

voids are filled by molecules of acetonitrile.

Figure 13. 1D coordination polymer 7 comprises alternating H2b3pmdc and [CuCl2] units. Further

chlorides are hydrogen bonded by coordinated methanol and the tertiary ammonium proton. Thermal

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ellipsoids are shown at 50% probability. One molecule of acetonitrile is also present within the lattice

(not shown).

While attempts were made to oxidize the reaction mixtures containing compounds 1-5 in a similar

manner as yielded crystalline 7, ultimately these efforts proved unsuccessful. Typically precipitates with

low solubility in common organic solvents were isolated and not analyzed further.

Luminescence study of 2 and 4. Previous studies have shown that cuprous iodide species

coordinated by pyridyl groups may exhibit photoluminescence, emitting blue, green or orange light

depending on the motif.5e,23 Clusters 2 and 4 were investigated for photoluminescent behavior, with both

found to emit room temperature, solid-state photoluminescence (Figure 14). Both had comparable

excitation wavelength maxima (338 nm for 2, 342 nm for 4). A second less intense maximum was

observed at ca. 370 nm, which is consistent with previously reported double absorption profiles of other

tetrahedral CuI systems.5a,23 The emission profile of 2 displayed a maximum at λ = 502 nm, giving blue-

green photoluminescence. The emission was observed to tail to ca. 700 nm. By contrast, the emission

spectrum of 4 showed considerable red-shifting relative to 2, with a maximum at λ = 553 nm, imparting

a yellow-green hue. The emission profile also was found to terminate at 720 nm. The cause of

photoluminescent emission in cuprous iodide species is thought to be related to a triplet centered (3CC)

excited state as a result of halide to metal charge transfer and d-s transitions.5a No luminescence

behavior was evident for network 3.

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Figure 14. Photoluminescence profiles for 2 (dashed excitation, green emission traces) and 4 (solid

excitation, orange emission traces).

The replacement of the apical coordinating pyridyl group with an iodide in 5 results in the absence of

photo luminescent behavior, possibly due to the presence of potassium-coordinated water adjacent to the

cuprous clusters. Water derived O-H oscillators are renowned for their ability to quench metal-based

luminescent emission.24 This explanation also explains the lack of luminescent behavior observed for

network 3.

Gas adsorption and thermogravimetric analysis. The structure was analyzed for gas adsorption

characteristics which, disappointingly, were found to be lacking. This evaluation included trialing a

range of activation protocols, including use of supercritical CO2. Thermogravimetric analysis suggested

5 should exhibit thermal stability to a temperature of ca. 200 °C (see Supporting Information).

Consequently we postulate that the single ionic link (Cu(3)-I(4)-K(1)) per every two cluster units offers

insufficient stabilization to the open channel motif upon desolvation. Indeed instability of the cluster

core was evidenced by the observation of sublimed iodine in the experimental apparatus after heating

the sample at 80 °C.

Ligand conformational analysis. A comparison of the various coordination geometries observed for

b3pmdc within this study found that the tetra-protonated ligand adopts an 'S' confirmation within a

narrow range of distances (ca. 10.3 to 10.6 Å (1, 6)) between the pyridyl nitrogens across the ligand.

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Protonation of only the tertiary amine groups of b3pmdc left the pyridyl groups free to participate in

metal coordination, yet retention of the 'S' conformation was still seen. Comparable overall ligand

lengths resulted, provided the ammonium protons were directed into the aza-ring (2, ca. 10.6 Å).

Outward orientation (i.e. Figure 1, (d)) yielded a longer ligand length of ca. 12.5 Å, likely influenced by

the reorientations necessary for hydrogen bonding to chloride in 7. Singular protonation of the

azacrown, resulting in hydrogen bonding of a guest water molecule, yielded two ligand bridging lengths

in structure 3: ca. 9.2 and 10.2 Å. These lengths, as well as the observed bent ligand geometry, are

typical of ligands that exhibit this behaviour.20 The neutral ligands in 4 were found to have the

conformational freedom to adopt either short (6.2 Å) or long (13.3 Å) coordination lengths, as well as

both crescent and elongated trans-pyridyl conformations. The longest observed ligand length was

induced by potassium incorporation in 5 (ca. 14.6 Å) as a result of the alkali metal forcing the azacrown

functionality into a planar, trans-pyridyl conformation, consistent with previous studies.2

In conclusion, we have observed a range of conformations for the bridging b3pmdc ligand, induced

by incorporation of water molecules, potassium ions or variation of reaction pH. Both cuprous and

cupric halide architectures have been utilized as a means of promoting these variations in ligand

geometry. Six separate architectures containing b3pmdc were synthesized and isolated, including a 3D

network containing large solvent filled channels, a racemic mixture of chiral 1D cuprous iodide chains

and two photoluminescent 1D cuprous iodide cluster chains.

ASSOCIATED CONTENT

SUPPORTING INFORMATION

Crystallographic data in CIF format. Further crystallographic details are given in Tables S1 to S6.

Thermogravimetric analytical trace of 5 is given in Figure S1. This material is available free of charge

via the Internet at http://pubs.acs.org.

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AUTHOR INFORMATION

Corresponding Author

* Email: [email protected]

ACKNOWLEDGMENTS

The authors gratefully acknowledge the Australian Research Council, Monash University for financial

support. This research was, in part, undertaken on the macromolecular crystallography (MX1 and MX2)

beamlines at the Australian Synchrotron, Victoria, Australia. The authors acknowledge Dr. Matthew

Hill for determining the gas adsorption characteristics of compound 5.

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SYNOPSIS TOC

The conformational variability of a diaza-18-crown-6 ligand has been restricted by variations to

pH and guest molecules within the scope of cuprous halide chemistry.

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67x38mm (600 x 600 DPI)

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56x32mm (300 x 300 DPI)

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92x85mm (300 x 300 DPI)

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97x94mm (300 x 300 DPI)

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49x24mm (300 x 300 DPI)

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754x277mm (96 x 96 DPI)

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Documents

Cuprous Halide Complexes of a Variable Length Ligand: Helices, Cluster Chains, and Nets Containing Large Solvated Channels