Phosphorescent Acentric Cuprous Halide ... - ACS Publications

Jun 7, 2008 - Three phosphorescent acentric cuprous halide coordination polymers, namely, [Cu2(pyt)Cl] (1), [Cu2(pyt)Br] (2), and [Cu5(pytH)3Cl5] (3) ...
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Phosphorescent Acentric Cuprous Halide Coordination Polymers for Nolinear Optical Materials Zheng-Ming Hao and Xian-Ming Zhang* School of Chemistry & Material Science, Shanxi Normal UniVersity, Linfen 041004, P. R. China

CRYSTAL GROWTH & DESIGN 2008 VOL. 8, NO. 7 2359–2363

ReceiVed December 9, 2007; ReVised Manuscript ReceiVed April 15, 2008

ABSTRACT: Three phosphorescent acentric cuprous halide coordination polymers, namely, [Cu2(pyt)Cl] (1), [Cu2(pyt)Br] (2), and [Cu5(pytH)3Cl5] (3) have been synthesized through the treatment of copper halides with achiral ligand pyridine-4-thiol (pyHt) by the hydro(solvo)thermal method. Complexes 1 and 2 are isostructural and exhibit three-dimensional (3-D) pillar-layered structures constructed by [Cu2SCl]∞/[Cu2SBr]∞ layers and pyridine pillars. The [Cu2SCl]∞ layer can be viewed as a fusion of zigzag [CuS]∞ and [CuCl]∞ chains. Alternately, the [Cu2SCl]∞ layers can be viewed as a fusion of six-membered Cu3S2Cl and Cu3Cl2S rings. Complex 3 shows a [Cu5S3Cl]∞ chain decorated by terminal chlorides and pyridine rings, in which the six Cu(I) atoms are linked by three µ3-S atoms and one µ3-Cl into a Cu6S3Cl cage, and a fusion of Cu6S3Cl cages via sharing Cu sites results in a onedimensional [Cu5S3Cl]∞ chain. At ambient temperature, 1, 2, and 3 show a strong yellow or red emission assigned from ligandto-metal charge transfer (LMCT) and/or metal-to-ligand charge-transfer (MLCT) character and a weak higher energy blue emission band assigned from halide to pyridine π* charge transfer. Their noncentrosymmetric structures are confirmed by measurement of second harmonic generation efficiency. Introduction 10

Luminescent polymeric and polynuclear d metal complexes, especially those containing metal-metal interactions, have been developed rapidly since the observation of phosphorescence of a variety of phosphine, arsine, and pyridine complexes of d10 metal centers in the 1970s.1–3 Theoretically, in the absence of (n +1)s and (n+1)p functions, interactions between the closedshell d10 centers are repulsive in nature.4–7 However, configuration mixing of the filled nd-orbitals with the empty orbitals derived from higher energy (n +1)s and (n +1)p orbitals has established some weak metal · · · metal interactions that often play an important role in the photophysical and photochemical properties of polymeric and polynuclear d10 metal complexes.4–9 For lighter d10 metal complexes, cuprous halides are the dominant species because of the diversity of structural types and stoichiometries.10–16 Generally, the aromatic nitrogen-donor ligands such as pyridine- and bipyridine-like ligands have been incorporated to improve photoluminescent properties of copper(I) halides.17–21 For example, at ambient temperature, cubanelike [CuI(pip)]4 (pip ) piperidine) displays a low energy luminescence band originating from an excited-state of mixed halide-to-metal charge transfer (XMCT) and copper-centered d f s,p character [termed as “cluster centered” (CC*) while replacement of saturated pip with aromatic pyridine generated analogous complex [CuI(py)]4 (py ) pyridine) that exhibits a higher energy emission band attributed to iodide to pyridineπ* charge transfer state as well as the low energy CC* band.22 The pyridine-4-thione (Hpyt) contains chemically tautomeric [-N(H)-C()S)- T -NdC(-SH)-] groups and possesses structural and binding properties of both thiolate and N-heterocycle.23,24 Thiolates and N-heterocycles are also good ligands for luminescent d10 metal complexes.6 Thus one may expect that the interesting photoluminescent properties will possibly be revealed upon incorporation of N-heterocyclic thiolates on cuprous halides. 25–30 In addition to fundamental studies in coordination chemistry, crystal structure, and luminescence, our interest in d10 ions * To whom correspondence should be addressed. Fax: Int. code +86 357 2051402; e-mail: [email protected].

coordination polymers of Hpyt has been primarily concerned with the development of noncentrosymmetric solids for possible applications in second order nonlinear optics (NLO). As noted, a noncentrosymmetric space group is the basic requirement for NLO materials because bulk second-order NLO susceptibility is a third-rank tensor and will vanish in a centrosymmetric environment.31 Because of the difficulty in controlling all the molecular forces that determine intermolecular arrangements within a unit cell, chemists have found that noncentrosymmetry in a crystal can be best ensured by introducing chirality in the individual molecules.32 According to the idea, the simplest method for noncentrosymmetric solids is using a chiral ligand. However, the best method for noncentrosymmetric solids is spontaneous resolution upon crystallization without any chiral sources, by which some d10 Zn(II) and Cd(II) complexes with acentric structure have been synthesized and reported.33,34 For d10 Cu(I) complexes, only a few noncentrosymmetric structures are known. Our previous work was mainly concentrated on Cu(I) complexes with intriguing centric structures and special properties such as CuI-CuI interaction;26,35 herein we report three phosphorescent acentirc cuprous complexes containing CuI-CuI interaction, namely, [Cu2(pyt)Cl] (1), [Cu2(pyt)Br] (2), and [Cu5(pytH)3Cl5] (3). Experimental Section Materials and Methods. All the starting materials were purchased commercially reagent grade. Elemental analyses were performed on a Perkin-Elmer 240 elemental analyzer. Infrared spectra were obtained in KBr Pellets on a Perkin-Elmer Spectrum BX FT-IR spectrometer in the range 400-4000 cm-1. XRPD data were recorded in a Bruker D8 ADVANCE diffractometer. Photoluminescence was performed on an Edinburgh FLS920 luminescence spectrometer. Thermal analyses (TG) were carried out in a nitrogen stream using SETARAM LABSYS equipment with a heating rate of 10 °C/min. Approximate estimation of second-order NLO intensity was obtained by a comparison of the results from a powdered sample with those obtained for urea.36 A pulsed Nd:YAG laser at a wavelength of 1064 nm was used to generate the SHG signal. The backward scattered SHG light was collected using a spherical concave mirror and passed through a filter that transmits only 532-nm radiation.

10.1021/cg701208g CCC: $40.75  2008 American Chemical Society Published on Web 06/07/2008

2360 Crystal Growth & Design, Vol. 8, No. 7, 2008

Hao and Zhang Table 2. Selected Bond Lengths (Å) and Angles (°) for 1-3

Table 1. Crystal Data and Structure Refinement Parameters for Compounds 1-3 empirical formula fw temp (K) λ (Å) crystal system space group a (Å) b (Å) c (Å) R (°) β (°) γ (°) V (Å3) Z Fcalc (g cm-3) µ (mm-1) F (000) cryst size (mm) θ (deg) reflcn indep reflcn Tmax/Tmin data/restrain/ param S Rla wR2b ∆Fmax/∆Fmin (e Å-3) a

C5H4ClCu2NS

C5H4BrCu2NS

C15H15Cl5Cu5N3S3

272.68 298(2) 0.71073 monoclinic Pc 3.9160(6) 7.8372(12) 11.4705(18) 90 93.215(3) 90 351.48(9) 2 2.577 6.629 264 0.14 × 0.10 × 0.03 2.60 to 28.59 1840 1294 0.8259/ 0.4571 1294/2/91

317.4 298(2) 0.71073 monoclinic Pc 3.9759(8) 7.8580(15) 11.773(2) 90 93.912(4) 90 366.97(12) 2 2.870 11.430 300 0.30 × 0.05 × 0.03 2.59 to 28.49 1562 1153 0.7255/ 0.1308 1153/2/91

828.43 298(2) 0.71073 monoclinic Cm 10.894(6) 20.828(12) 5.325(3) 90 104.344(10) 90 1170.4(12) 2 2.351 5.319 808 0.06 × 0.05 × 0.03 3.51 to 27.00 2938 2057 0.8567/ 0.7408 2057/2/148

1.083 0.0391 0.0800 0.680/-0.498

1.127 0.0297 0.0782 0.652/-0.639

0.977 0.0509 0.1015 0.822/-0.691

R1 ) ∑|Fo| - |Fc|/∑|Fo|. b wR2 ) [∑[w(Fo2 - Fc2)2]/∑[w(Fo2)2]]1/2.

1a Cu(1)-S(1) Cu(1)-S(1a) Cu(1)-Cl(1) Cu(2)-N(1b) S(1)-Cu(1)-S(1a) S(1)-Cu(1)-Cl(1) S(1a)-Cu(1)-Cl(1) N(1b)-Cu(2)-S(1) N(1b)-Cu(2)-Cl(1c)

2.2134(19) 2.2277(19) 2.255(2) 2.003(6) 123.71(9) 121.39(7) 114.40(7) 118.3(2) 109.4(2)

Cu(2)-S(1) Cu(2)-Cl(1c) Cu(2)-Cl(1d)

2.242(2) 2.398(2) 2.579(2)

S(1)-Cu(2)-Cl(1c) N(1b)-Cu(2)-Cl(1d) S(1)-Cu(2)-Cl(1d) Cl(1c)-Cu(2)-Cl(1d)

116.76(7) 104.5(2) 102.01(7) 103.74(8)

2b Cu(1)-S(1) Cu(1)-S(1a) Cu(1)-Br(1)

2.207(2) Cu(2)-S(1c) 2.249(2) Cu(2)-Br(1) 2.3907(13) Cu(2)-Br(1a) Cu(2)-N(1b) S(1)-Cu(1)-S(1a) 126.31(10) S(1c)-Cu(2)-Br(1) S(1)-Cu(1)-Br(1) 121.44(7) N(1b)-Cu(2)-Br(1a) S(1a)-Cu(1)-Br(1) 111.87(6) S(1c)-Cu(2)-Br(1a) N(1b)-Cu(2)-S(1c) 119.7(3) Br(1)-Cu(2)-Br(1a) N(1b)-Cu(2)-Br(1) 108.7(2)

2.246(2) 2.5329(14) 2.6077(15) 2.003(7) 116.26(7) 104.6(2) 103.78(6) 101.31(5)

3c Cu(1)-S(1a) Cu(1)-S(1) Cu(1)-S(2) Cu(1)-Cl(1) Cu(3)-S(1) S(1a)-Cu(1)-S(1) S(1)-Cu(1)-S(2) S(1a)-Cu(1)-Cl(1) S(1)-Cu(1)-Cl(1) S(2)-Cu(1)-Cl(1) Cl(3)-Cu(3)-Cl(1b)

2.334(3) 2.334(3) 2.402(4) 2.426(4) 2.245(3) 110.05(14) 105.83(9) 114.22(9) 114.22(9) 105.88(13) 120.58(14)

Cu(2)-Cl(2) Cu(2)-S(2b) Cu(2)-S(1) Cu(3)-Cl(3) Cu(3)-Cl(1b) S(1a)-Cu(1)-S(2) Cl(2)-Cu(2)-S(2b) Cl(2)-Cu(2)-S(1) S(2b)-Cu(2)-S(1) Cl(3)-Cu(3)-S(1) S(1)-Cu(3)-Cl(1b)

2.221(3) 2.238(2) 2.248(3) 2.187(3) 2.354(3) 105.83(9) 126.81(13) 122.25(12) 110.94(12) 129.13(12) 109.10(12)

Symmetry codes: (a) x + 1, y, z; (b) x, y - 1, z; (c) x - 1, -y + 1, z + 1/2; (d) x, -y + 1, z + 1/2. b Symmetry codes: (a) x + 1, y, z; (b) x + q, -y + 2, z - 1/2; (c) x + 1, -y + 1, z - 1/2. c Symmetry codes: (a) x, -y + 2, z; (b) x, y, z + 1. a

Syntheses. [Cu2(pyt)Cl] (1). A mixture of CuCl2 · 2H2O (0.068 g, 0.4 mmol), pytH (0.022 g, 0.2 mmol), NaN3 (0.014 g, 0.2 mmol), CH3CN (3 mL), and water (2 mL) in a mole ratio of 2:1:1:288:555 was sealed in a 15 mL Teflon-lined stainless container, which was heated to 140 °C and held 96 h. After the sample was cooled to room temperature, yellow sheet-like crystals of 1 were obtained in the yield of 30% (based on pytH). Anal. Calcd. for 1, C5H4ClCu2NS: C, 22.02; H, 1.48; N, 5.14. Found: C, 21.91; H, 1.53; N, 5.12. IR (KBr, cm-1): 1629w, 1587m, 1477w, 1398s, 1104 w, 806w, 711w. [Cu2(pyt)Br] (2). The preparing procedure of 2 is similar to 1 except for CuBr2 instead of CuCl2. Yellow block crystals of 2 were obtained in the yield 40%. Anal. Calcd for C5H4BrCu2NS: C, 18.94; H, 1.27; N, 4.42. Found: C, 18.85; H, 1.32; N, 4.33. IR (KBr, cm-1): 1589m, 1479m, 1409m, 1106s, 814w, 713w. [Cu5(pytH)3Cl5] (3). A mixture of CuCl2 · 2H2O (0.068 g, 0.4 mmol), pytH (0.022 g, 0.2 mmol), NaN3 (0.014 g, 0.2 mmol), and CH3CN (5 mL) in a mole ratio of 2:1:1:480 was sealed in a 15 mL Teflon-lined stainless container, which is heated to 140 °C and held 96 h. Red block crystals of 3 were obtained in yield: 30% (based on pytH). Anal. Calcd for C15H15N3S3Cu5Cl5: C, 21.75; H, 1.82; N, 5.07. Found: C, 21.77; H, 1.80; N, 5.08. IR (KBr, cm-1): 3118w, 1616s, 1473s, 1201m, 1099m, 694m, 492m. Crystallographic Studies. X-ray single-crystal diffraction for complexes 1-3 were collected on a Bruker SMART APEX CCD diffractometer at 298(2) K using Mo KR radiation (λ ) 0.71073 Å). The program SAINT was used for integration of the diffraction profiles, and the program SADABS was used for absorption correction. All the structures were solved by direct methods using the SHELXS program of the SHELXTL package and refined by full-matrix least-squares methods with SHELXTL.37 All nonhydrogen atoms were refined with anisotropic thermal parameters. The hydrogen atoms of organic ligands were generated theoretically onto the specific carbon and nitrogen atoms, and refined isotropically with fixed thermal factors. Further details for structural analysis are summarized in Table 1. Selected bond lengths and bond angles are shown in Table 2.

Results and Discussion Description of Structures. Complexes 1 and 2 are isostructural, and only the structure of 1 is described herein. Compound 1 crystallizes in monoclinic noncentric space group Pc, and the asymmetric unit consists of two copper(I) ions, one chloride, and one pyt group as shown in Figure 1a. All the atoms localize on general positions. The Cu(1) shows a trigonal geometry, coordinated by two S atoms from two pyt groups and one chloride. The Cu(1)-S bond lengths are 2.2134(19) and 2.2277(19) Å, and the Cu(1)-Cl(1) bond length is 2.255(2) Å. The L-Cu(1)-L bond angles are in the range of 114.40(7)123.71(9)°. The Cu(2) shows a distorted tetrahedral geometry, coordinated by one N and one S from two pyt and two chlorides. The Cu(2)-S bond length is 2.242(2) Å; the Cu(2)-Cl bond lengths are 2.255(2) and 2.579(2) Å; the Cu(2)-N bond length is2.003(6)Å.TheL-Cu(2)-Lbondanglesare102.01(7)-118.3(2)°. Compound 1 exhibits a 3-D structure consisting of [Cu2SCl]∞ layers and pyridine rings. As is shown in Figure 1c, both Cl(1) and S(1) atoms in a µ3 mode link three adjacent Cu(I) atoms. Each Cu(1) is connected to two S(1) and one Cl(1) while each Cu(2) is connected to two Cl(1) and one S(1). The layered motif with formula [Cu2SCl]∞ is present as a result of such a linking fashion, which can be described as a fusion of zigzag [CuS]∞ and [CuCl]∞ chains via Cu-S and Cu-Cl contacts. The [Cu2SCl]∞ layers can also be viewed as alternating fusion of six-membered Cu3S2Cl and Cu3Cl2S rings. To the best of our knowledge, such a [Cu2SCl]∞ layer has not been documented in coordination polymers of cuprous chloride. The adjacent [Cu2SCl]∞ layers are further linked by pyridine rings via S-C

Phosphorescent Cu Halide Coordination Polymers

Crystal Growth & Design, Vol. 8, No. 7, 2008 2361

Figure 2. The coordination environments of copper sites (a), the [Cu5S3Cl]∞ chain-like motif (b) and one-dimensional structure (c) and 3-D supramolecular array (d) in 3.

Figure 1. The coordination environments of copper sites with 35% thermal ellipsoid probability in 1 (a) and 2 (b), the [Cu2SCl]∞ layer (c) and (d) 3-D pillar-layered structure (c) in 1.

and Cu-N bonds to finish 3-D framework as shown in Figure 1d. The topology of 1 is a three- and four-connected net, in which the three-connected nodes are Cu(1) and Cl(1) and the four connected nodes are S(1) and Cu(2). The short Schla¨fli symbol is (63)Cu1(63)Cl1(65.8)S1(65.8)Cu2. Compound 3 crystallizes in monoclinic noncentric space group Cm and the asymmetric unit consists of three copper sites, three chlorides, and 1.5 pytH molecules as shown in Figure 2a. The crystallographic mirror plane passes through Cu(1), Cl(1), S(2), N(2), and C(6) atoms, which bisects the pytH consisting of S(2), C(6), C(7), C(8), N(2), C(7a), and C(8a). The pytH

groups exist in the form of pyridine-4-thione, and the N atoms of pytH are protonated. The Cl(1) in a µ3 mode is bonded to three Cu(I) ions, while Cl(2) and Cl(3) are terminal. The Cu-S and Cu-Cl distances are in the range of 2.238(2)-2.402(4) and 2.187(3)-2.426(4) Å, respectively. The Cu(1) adopts a distorted tetrahedral geometry, coordinated by one Cl(1) and three S atoms. The L-Cu(1)-L (S, Cl) angles are in the range of 105.83(9)-114.22(9)°. The Cu(2) site adopts a trigonal geometry, coordinated by one Cl(2) and two S atoms. The L-Cu(2)-L (S, Cl) angles are in the range of 110.94(12)-126.81(13)°. The Cu(3) also adopts a trigonal coordination geometry, coordinated by S(1), Cl(1), and Cl(3). The L-Cu(3)-L (S, Cl) angles are in the range of 109.10(12)-129.13(12)°. Both S(1) and S(2) atoms adopt µ3-coordination modes, while the Cl ions adopt µ3 and terminal two types of coordination modes. In 3, the six Cu(I) atoms are linked by three µ3-S atoms and one µ3-Cl into a Cu6S3Cl cage (Figure 2b). The Cu6S3Cl cage has a structure that is formed by replacement of one µ3-S with one µ3-Cl in

2362 Crystal Growth & Design, Vol. 8, No. 7, 2008

Hao and Zhang

Figure 3. TGA curves of 1 and 3 in nitrogen atmosphere and at the heating rate of 10 °C/min.

Figure 4. Photoluminescent emissions of 1-3.

Cu6S4 caged observed [Cu3(pyt)2(CN)].26 The sharing of Cu sites by adjacent Cu6S3Cl cages results in an unprecedented onedimensional [Cu5S3Cl]∞ chain. The [Cu5S3Cl]∞ chain is decorated by terminal chlorides and pyridine rings of pytH via Cu-Cl and S-C bonds to generate chain-like structure of 3 (Figure 2c). To be noted, the distance of H(1a) · · · Cl(3) (2.587 Å) is shorter than the sum of van der Waal radii of H and Cl (2.95 Å), which in combination with the 170.4° angle of N(1)-H(1a) · · · Cl(3) indicates the existence of N-H · · · Cl hydrogen.38 It should also be noted that all N-H · · · Cl hydrogen bonds in 3 point toward same direction, which will generate the force to strengthen the three-dimensional supramolecular framework (Figure 2d). Solvent Effect. Solvents played a important role in the hydro(solvo)thermal synthesis of the three complexes. For example, the reaction of CuCl2 · 2H2O and pytH in mixed solvents CH3CN/H2O resulted in 3-D pillar-layered complex 1, while the similar reaction in mixed solvents C2H5OH/H2O resulted in the 3-D diamond-like complex [Cu10Cl10(pytH)4].27 In contrast, when the sole solvent CH3CN was used, similar reaction resulted in chain-like complex 3. It should be mentioned that 1, 2, and 3 are also available in the absence of NaN3, but the addition of NaN3 in starting materials can improve yield and quality of single crystals. Similar solvent effect can be observed in linkage isomers [Cu(teeOMe)2Br2] (teeOMe ) 1-(2methoxyethyl)tetrazole),39 the zigzig CuZn chain structures of [Cu(en)2ZnCl4] · dmso and [Cu(en)2ZnCl4] · dmf, and isostructural [Cu(en)2CdBr4] · dmso and [Cu(en)2CdI4] · dmf.40 Thermal Analyses. Thermogravimetric analyses for 1 and 3 in nitrogen stream at the heating rate of 10 °C min-1 was performed on a polycrystalline samples. The TGA curves of 1 and 3 show that both are thermally stable up to 240 °C (Figure 3a). Compound 1 decomposes in the temperature range 240-390 °C to form an unstable intermediate that has empirical composition Cu2SCl (69.8%, calc. 71.3%). In the step, the weight loss of 30.2% indicates the removal of C, H, N atoms of pyt groups. The unstable intermediate slowly decomposes upon further heating, and the final residue of 58.2% at 880 °C is indicative of Cu2S (calc. 57.9%). The Cu2S residue is also confirmed by XRPD. Compound 3 decomposes in the temperature range 240-378 °C to an unstable intermediate with empirical composition Cu5S3Cl (55.1%, calc. 55.6%). This indicates the removal of C, H, N atoms of pyt groups and terminal Cl in the step, which is reasonable to consider the structure of 3. The intermediate further decomposes upon heating, and stable residue Cu2S (48.1%, calc. 47.9%) is formed at 950 °C. Photoluminescence. The room temperature emission spectra of pyt based complexes 1-3 (λex ) 320 nm) are shown in Figure

4a. As can be seen, 1, 2, and 3 show strong yellow or red emission centered at 565 nm (τ ) 27.76 µs), 544 nm (τ ) 26.38 µs), and 624 nm (τ ) 9.15 µs), respectively. Besides, a weak higher energy emission band at 467 nm (τ ) 2.21 µs), 468 nm (τ ) 12.54 µs), and 467 nm (τ ) 2.29 µs) is observed in 1-3, respectively. In general, possible assignments for the excited states which are responsible for emission phenomena of Cu(I)complexes are ligand centerd π f π* transitions (LC), ligandto-ligand (LLCT), ligand-to-metal (LMCT), metal-to-ligand (MLCT) charge transfer transitions or metal centered d10 f d9s1 (MC) transitions.6 On the basis of microsecond-order decay lifetime, all these emissions in 1-3 can be determined to be phosphorescence, and the transitions from π f π* excited states of pyt and pymt can be eliminated. Complexes 1 and 2 contain layered [Cu2SCl]∞ and [Cu2SBr]∞ structural motif and 3 contains 1-D [Cu5S3Cl]∞ chain decorated by terminal Cl and pyridine rings. The shortest Cu-Cu distances are 3.16 Å in 1 and 3.06 Å in 3, respectively, which beyond twice van der Waals radii of Cu(I) (2.8 Å). However, there has been mounting evidence for CuI-CuI interactions from the short metal-metal distances (usually between 260 and 350 pm) in several crystal structures,41 and thus possibly there exists very weak CuI-CuI interactions in 1 and 3. According to the photoluminescent properties of other Cu(I)/halide/thiolate clusters, the weak higher energy blue emissions in 1-3 are tentatively assigned as originating from the halides to aromatic pyridine π* charge transfer. The low-energy yellow and red emissions in 1-3 are assigned as from ligand-to-metal charge transfer (LMCT) and/or metal-to-ligand charge-transfer (MLCT) characters.6,7,42 Second Harmonic Generation Efficiency. According to the principles proposed by Kurtz and Perry,36 the strength of second harmonic generation (SHG) efficiency of the compounds can be estimated by measuring powder samples. Compounds 1 and 2 show SHG intensities of 0.1 relative to that of urea, respectively, whereas 3 exhibits very weak SHG signal under same experimental condition. These observations confirm that 1, 2, and 3 crystallize in the chiral and acentric space group, consistent with the structural analyses. The SHG intensities of 1 and 2 are comparable with that of technologically important LiNbO3, which has a powder SHG intensity of 1.5 vs urea. Conclusions We have successfully obtained three acentric Cu(I) halide coordination polymers through spontaneous assembly of achiral ligand and copper halide under a solvothermal method. At ambient temperature, 1, 2, and 3 show interesting phosphorescent emissions: a strong yellow or red emission and a weak

Phosphorescent Cu Halide Coordination Polymers

higher energy blue emission band. The SHG measurement confirm that three complexes crystallize in acentric space group, indicating they may be suitable candidates for NLO materials. Acknowledgment. This work was financially supported by NSFC (20771069), FANEDD (200422), and NCET-05-0270. Supporting Information Available: Crystal structural data in CIF format and XPRD data for 1-3. This material is available free of charge via the Internet at http://pubs.acs.org.

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