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N-allyl imidazole coordination polymers
Journal of Molecular Structure 796 (2006) 210–215 www.elsevier.com/locate/molstruc
Solvothermal preparation, X-ray structural characterization and properties of two novel 3D copper(I) halide/N-allyl imidazole coordination polymers Yu-Mei Song b, Jie Pang b, Kun Qian a, Xi-Sen Wang a,b,*, Xiao-Nian Li a, Ren-Gen Xiong b,* a
State Key Lab Breeding Base of Green Chemistry Synthetic Technology, College of Chemical Engineering and Material Science, Zhejiang University of Technology, Hangzhou 310032, People’s Republic of China b The State Key Laboratory of Coordination Chemistry, Coordination Chemistry Institute, Nanjing University, Nanjing 210093, People’s Republic of China Received 25 January 2006; received in revised form 14 February 2006; accepted 18 February 2006 Available online 25 April 2006
Abstract The solvothermal reactions of N-allyl imidazole with CuIX (XZCl, Br) afford two unprecedented 3D copper(I)–olefin coordination polymer Cu2X2(N-allyl imidazole) (XZCl for 1; Br for 2). This is the first 3D copper(I)–olefin coordination polymer synthesized in directed method, compared to most of olefin–Cu(I) coordination polymers prepared by electrochemical method. Of practical interest is that both of them contain 1D zigzag ladder chain composed of basic Cu2X2 dimer unit. Photoluminescent measurements show that 1 displays blue fluorescent emission while 2 has red fluorescent emission at room temperature. q 2006 Elsevier B.V. All rights reserved. Keywords: Solvothermal synthesis; Copper(I) halide organometallic; N-allyl imidazole copper(I) complex; Coordination polymer; Fluorescence; Solid state structure
1. Introduction Copper-catalyzed addition of carbanions to a,b-unsaturated carbonyls and copper-catalyzed cyclopropanation of alkenes by R-carbonyl diazoalkanes involve copper(I)–olefin complexes as catalytically active species or resting state [1]. Copper(I)–ethylene complexes may also participate in a variety of stress responses and developmental processes, as in the smallest plant hormone, an ethylene group binds tightly to the copper receptor site ETR [2]. Recently, The rational design and self-assembly of olefin–copper(I) coordination polymers with highly thermal stability and physical functions have been of intensive interest [3]. These polymers not only display general characters of metal–organic coordination polymer, but also still remain Cu–olefin complex features, such as Cu–p coordinating bond labile [4]. Due to these properties, the Cu(I)–olefin complexes have found a wide
* Corresponding authors. Address: The State Key Laboratory of Coordination Chemistry, Coordination Chemistry Institute, Nanjing University, 22 Han Kou Lu, Nanjing 210093, People’s Republic of China. Tel: C86 25 83594724; fax: C86 25 83314502. E-mail address: [email protected] (R.-G. Xiong).
0022-2860/$ - see front matter q 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.molstruc.2006.02.050
range of applications in fluorescent sensor [3], olefin separation [4] and chiral enantioseparation [5]. To the best of our knowledge, the presence of 3D olefin– copper(I) coordination polymer used olefin ligand and CuX synthesized in direct method is unknown, however, there are very rare 3D olefin–copper(I) coordination polymers reported [6]. The successful generation of 3D networks incorporating olefin coordination to a copper by directed method represents an exciting challenge in modern supramolecular and organometallic chemistry. With this in mind, we have studied the reactions of N-allyl imidazole with CuIX at different temperatures. Herein we report the synthesis, solid-state structures, and some optical-chemical properties of two olefin–copper(I) coordination polymers generated from such reactions. To our knowledge, both 1 and 2 represent the first example of 3D Cu(I)–olefin coordination polymers synthesized by direct-method, compared to most of olefin–Cu(I) coordinated polymers prepared by electrochemical method. 2. Experimental 2.1. Synthesis of the title coordination polymers Coordination polymer Cu2Cl2(N-allyl imidazole): CuCl (1.0 mmol) and N-allyl imidazole (1.0 mmol) were placed in a thick pyrex tube (ca. 20 cm in length). After addition of 2 mL
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Table 1 ˚ ] and angles [8] for 1 Bond lengths [A Cu(1)–N(1) Cu(1)–C(4)#1 Cu(1)–Cu(2)#2 Cu(2)–Cl(4) Cu(2)–Cl(3)#2 Cu(2)–Cu(2)#3 Cl(4)–Cu(2)#3 N(1)–C(7) N(2)–C(5) C(5)–C(7) C(4)–C(6) C(6)–Cu(1)#4 N(1)–Cu(1)–C(4)#1 N(1)–Cu(1)–Cl(3) C(4)#1–Cu(1)–Cl(3) C(6)#1–Cu(1)–Cu(2)#2 Cl(3)–Cu(1)–Cu(2)#2 Cl(4)#3–Cu(2)–Cl(3) Cl(4)#3–Cu(2)–Cl(3)#2 Cl(3)–Cu(2)–Cl(3)#2 Cl(4)–Cu(2)–Cu(1)#2 Cl(3)#2–Cu(2)–Cu(1)#2 Cl(4)–Cu(2)–Cu(2)#3 Cl(3)#2–Cu(2)–Cu(2)#3 Cu(1)–Cl(3)–Cu(2) Cu(2)–Cl(3)–Cu(2)#2 C(6)–C(4)–C(8) C(8)–C(4)–Cu(1)#4
1.953(3) 2.076(4) 3.0068(9) 2.3503(12) 2.4572(13) 3.0167(13) 2.3247(12) 1.379(5) 1.380(5) 1.345(6) 1.374(6) 2.028(4) 115.15(15) 105.84(10) 132.66(12) 99.02(13) 52.78(3) 120.59(4) 116.82(4) 93.35(4) 62.21(4) 50.19(3) 49.44(3) 129.68(5) 125.39(5) 86.65(4) 121.5(4) 113.0(3)
Cu(1)–C(6)#1 Cu(1)–Cl(3) Cu(2)–Cl(4)#3 Cu(2)–Cl(3) Cu(2)–Cu(1)#2 Cl(3)–Cu(2)#2 N(1)–C(3) N(2)–C(3) N(2)–C(8) C(8)–C(4) C(4)–Cu(1)#4 N(1)–Cu(1)–C(6)#1 C(6)#1–Cu(1)–C(4)#1 C(6)#1–Cu(1)–Cl(3) N(1)–Cu(1)–Cu(2)#2 C(4)#1–Cu(1)–Cu(2)#2 Cl(4)#3–Cu(2)–Cl(4) Cl(4)–Cu(2)–Cl(3) Cl(4)–Cu(2)–Cl(3)#2 Cl(4)#3–Cu(2)–Cu(1)#2 Cl(3)–Cu(2)–Cu(1)#2 Cl(4)#3–Cu(2)–Cu(2)#3 Cl(3)–Cu(2)–Cu(2)#3 Cu(1)#2–Cu(2)–Cu(2)#3 Cu(1)–Cl(3)–Cu(2)#2 Cu(2)#3–Cl(4)–Cu(2) C(6)–C(4)–Cu(1)#4 C(4)–C(6)–Cu(1)#4
2.028(4) 2.3703(11) 2.3247(12) 2.3763(13) 3.0068(9) 2.4572(13) 1.328(5) 1.344(5) 1.463(5) 1.499(6) 2.076(4) 153.36(16) 39.11(17) 95.78(12) 106.37(10) 128.77(12) 99.63(4) 115.42(4) 111.91(4) 118.22(4) 120.29(3) 50.19(3) 136.60(5) 90.07(3) 77.03(4) 80.37(4) 68.5(2) 72.3(2)
Symmetry transformations used to generate equivalent atoms: #1 xK1, KyC3/2, zK1/2; #2 KxC1, KyC1, KzC2; #3 KxC2, KyC1, KzC2; #4 xC1, KyC3/2, zC1/2. Table 2 ˚ ] and angles [8] for 2 Bond lengths [A Br(1)–Cu(2) Br(1)–Cu(1) Br(2)–Cu(1)#2 Cu(2)–N(1) Cu(2)–C(2)#3 Cu(2)–Cu(1) Cu(1)–Br(1)#1 C(2)–C(1) C(1)–Cu(2)#4 Cu(2)–Br(1)–Cu(1) Cu(1)–Br(2)–Cu(1)#2 Cu(1)–Br(2)–Cu(2)#2 N(1)–Cu(2)–C(2)#3 N(1)–Cu(2)–Br(1) C(2)#3–Cu(2)–Br(1) C(1)#3–Cu(2)–Br(2)#2 Br(1)–Cu(2)–Br(2)#2 C(1)#3–Cu(2)–Cu(1) Br(1)–Cu(2)–Cu(1) Br(2)–Cu(1)–Br(2)#2 Br(2)#2–Cu(1)–Br(1)#1 Br(2)#2–Cu(1)–Br(1) Br(2)–Cu(1)–Cu(2) Br(1)#1–Cu(1)–Cu(2) C(6)–N(2)–C(5) C(5)–N(2)–C(3) C(6)–N(1)–Cu(2) N(1)–C(6)–N(2) C(5)–C(4)–N(1) C(1)–C(2)–C(3) C(3)–C(2)–Cu(2)#4
2.4896(17) 2.524(2) 2.439(2) 1.960(8) 2.087(11) 3.0578(19) 2.503(2) 1.372(13) 2.060(11) 75.16(6) 80.18(7) 112.69(6) 113.5(4) 107.2(3) 131.6(3) 103.5(4) 101.11(5) 102.0(3) 52.93(5) 99.82(7) 113.56(7) 113.88(7) 120.01(7) 123.06(7) 107.0(8) 125.1(7) 126.7(6) 111.8(8) 110.7(9) 122.2(11) 112.9(6)
Br(1)–Cu(1)#1 Br(2)–Cu(1) Br(2)–Cu(2)#2 Cu(2)–C(1)#3 Cu(2)–Br(2)#2 Cu(1)–Br(2)#2 N(2)–C(6) C(2)–Cu(2)#4 Cu(2)–Br(1)–Cu(1)#1 Cu(1)#1–Br(1)–Cu(1) Cu(1)#2–Br(2)–Cu(2)#2 N(1)–Cu(2)–C(1)#3 C(1)#3–Cu(2)–C(2)#3 C(1)#3–Cu(2)–Br(1) N(1)–Cu(2)–Br(2)#2 C(2)#3–Cu(2)–Br(2)#2 N(1)–Cu(2)–Cu(1) C(2)#3–Cu(2)–Cu(1) Br(2)#2–Cu(2)–Cu(1) Br(2)–Cu(1)–Br(1)#1 Br(2)–Cu(1)–Br(1) Br(1)#1–Cu(1)–Br(1) Br(2)#2–Cu(1)–Cu(2) Br(1)–Cu(1)–Cu(2) C(6)–N(2)–C(3) C(6)–N(1)–C(4) C(4)–N(1)–Cu(2) C(4)–C(5)–N(2) N(2)–C(3)–C(2) C(1)–C(2)–Cu(2)#4 C(2)–C(1)–Cu(2)#4
2.503(2) 2.428(2) 2.887(2) 2.060(11) 2.887(2) 2.439(2) 1.330(11) 2.087(11) 121.37(6) 81.52(7) 69.50(6) 151.0(4) 38.6(4) 95.5(3) 89.9(2) 104.0(3) 106.1(2) 131.6(3) 48.33(4) 116.62(7) 115.35(7) 98.48(7) 62.17(5) 51.91(5) 127.9(8) 104.6(8) 128.4(7) 105.9(8) 110.2(7) 69.6(7) 71.7(6)
Symmetry transformations used to generate equivalent atoms: #1 KxC1, KyC1, Kz; #2 KxC2, KyC1, Kz; #3 xC1, KyC1/2, zC1/2; #4 xK1, KyC1/2, zK1/2.
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of 2-butanol, the tube was frozen with liquid N2, evacuated under vacuum, and sealed with a torch. The tube was then placed into oven at 70 8C for 5 days to give pale-yellow block crystals. Yield: ca. 40% on the basis of N-allyl imidazole. IR (KBr, cmK1) for 1: 3448(br w), 3148(w), 3111(w), 2925(w), 1626(w), 1517(s), 1443(w), 1397(m), 1278(w), 1233(s), 1112(m), 1086(s), 1025(w), 934(w), 837(s), 754 (s), 655(m), 630(m), 559(w), 476 (w). Coordination polymer Cu2Br2(N-allyl imidazole): CuBr (1.0 mmol) and N-allyl imidazole (1.0 mmol) were placed in a thick pyrex tube (ca. 20 cm in length). After addition of 2 mL of 2-butanol, the tube was frozen with liquid N2, evacuated under vacuum, and sealed with a torch. The tube was then placed into oven at 70 8 for 5 days to give pale-yellow block crystals. Yield: ca. 45% on the basis of N-allyl imidazole. IR (KBr, cmK1) for 2: 3442(br, w), 3144(m), 3118(s), 1739(w), 1670(w), 1623(w), 1515(s), 1442(m), 1396(s), 1279(m), 1253(w), 1231(s), 1113(s), 1088(s), 1024(m), 988(w), 950(w), 939(m), 908(w), 874(w), 835(s), 775(w), 756(s), 705(w), 657(s), 629 (s), 471(m), 430(w). In comparison to that of metal-free N-allyl imidazole with a peak at 1649 cmK1 which is the stretching vibration of metalfree CaC bond, there is a weak peak at 1626 cmK1 for 1 and at 1623 cmK1 for 2 in their IR spectra, indicating that CaC bond moiety groups directly link to Cu(I). 2.2. Single crystal structure determination X-ray diffraction data for compounds 1 and 2 were collected at ambient temperature on Bruker Smart Aepex-II CCD area ˚ ). The structures detector (Mo Ka X-radiation, lZ0.71069 A were solved with direct methods using the program SHELXTL (Sheldrick, 1997). All the non-hydrogen atoms were located from the trial structure and then refined anisotropically with SHELXTL using full-matrix least-squares procedure. The hydrogen atom positions were fixed geometrically at calculated distances and allowed to ride on the parent carbon atoms. The final difference Fourier map was found to be featureless. Crystallographic data (excluding structure factors) for the complexes have been deposited with the Cambridge Crystallographic Data Center as supplementary publication no. CCDC 602565 and 602566. The crystal data for 1: C6H8Cl2Cu2N2, MrZ306.12, Monoclinic, space group, P2(1)/c, aZ6.3234(13) ˚ , bZ16.440(3) A ˚ , cZ8.7390(17) A ˚ , aZgZ908, bZ A ˚ 3, ZZ4, TZ293(2)K, D cZ 96.49(3)8, VZ902.7(3) A 2.253 g cmK3, mZ5.242 mmK1, R1Z0.0359, wR2Z0.1208, GOFZ0.980. 2: C6H8Br2Cu2N2, MrZ395.04, Monoclinic, ˚ , bZ17.333(4) A ˚ , cZ space group, P2(1)/c, aZ6.4149(11) A ˚ , aZgZ908, bZ98.170(18)8, VZ9 950.4(3) A ˚ 3, 8.6356(17) A K3 K1 ZZ4, TZ293(2)K, DcZ2.761 g cm , mZ12.825 mm , R1Z0.0480, wR2 Z0.1394, GOFZ1.131. The bond distances and angles of coordination polymers 1 and 2 are listed in Tables 1 and 2, respectively.
N
N
+ CuCl
2-butanol
N
N
Cu2Cl2
N
N
Cu2Br2
70°C
N
N
+ CuBr
2-butanol 70°C
Scheme 1.
conditions. The coordination polymers, Cu2Cl2(N-allyl imidazole) (1) and Cu2Br2(N-allyl imidazole) (2), were isolated from these reaction mixtures (Scheme 1). EPR spectra of single crystal samples of 1 and 2 are silent, indicating that the statuses of Cu atoms in these two coordination polymers is C1. The X-ray crystal structure analysis of complex 1 illustrated there are one unique ligand and two different coordination environmental copper atoms in compound 1, as depicted in Fig. 1. Cu1 possesses a tetrahedral coordination geometry composed of two halide atoms, a N atom and a CaC bond moiety in different N-allyl imidazole. The Cu2 centers are coordinated by four halide atoms while each Cl anion acts as m3-linker to bridge three Cu atoms to result in the formation of a four-coordinated metal center with a tetrahedral coordination geometry. Thus, the ligand allylimidazole acts as a bidentate spacer to link two Cu(I) ions by using one N atom and one olefin moiety to give rise to a 3D olefin–copper(I) network, as shown in Fig. 2. As Table 1 ˚) indicates, the CaC double bond distance (1.374(2) A is slightly longer than those found in [Cu(HB(3,5-Me2PZ)3(C2H4))](3,5-Me2PZZhydrotris(3,5-dimethyl-1-pyrazolylbo˚ ) [7a], [Cu2 (COT)(hfacac)2] (COTZ1,3,5,7rate) (1.329(9) A cyclododecatriene, hfacacZhexafluroacetylacetone) (1.31(1)– ˚ ) [7b], [Cu2Cl2(C5H8)] (C5H8Z2-methylbutadiene) 1.33(1) A ˚ ) [7c] and [CuCl(C4H6O2)] (C4H6O2Zmethylpro(1.358(7) A ˚ ) [7d], but slightly shorter than penoate) (1.370(8) A those found in [CuCl-(C5H8O)](C5H8OZ1-penten-3-one)
3. Results and discussion In this present investigation, we have reacted N-allyl imidazole with either CuCl or CuBr under solvothermal
Fig. 1. Part of the structure of 1 showing the four-coordinated copper center bound to two ligands in which ligand attached to two copper(I) centers (H atoms are omitted for clarity).
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Fig. 2. Zigzag double chain of Cu2X2 dimers linked by ligands. (H atoms are omitted for clarity). Fig. 4. Part of the structure of 2 showing the slightly distorted tetrahedral coordination geometry around copper centers.
˚ ) [7e]. It is interesting to note that the CaC bond (1.383(8) A lengths of the coordinated olefin in the two copper(I) ˚ ) and Cu4Br4L (1.34(2) A ˚) p-complexes Cu4Cl4L (1.33(2) A (LZC7H8, 1,4-pentadiene) containing a Cu4X4 cubane core are slightly shorter than those of 1 [7f] and in the copper(I) ˚ ) (LZtrially-1,3,5p-complex Cu4Br4L (1.346(2)–1.442 A triazine-2,4,6-(1H,3H,5H)-trione) are slightly longer than those of 1 [7f]. Finally, the lengthening of the CaC double bond may be typical of ethylene ligands that are h2-bonded to low valiant electron-rich transition metals [8]. The complicate structure of the network can be best understood by considering zigzag double chains of Cu2Cl2 dimers centers that extend in the a-direction. The ligands lie either side of the zigzag chain and each ligand links two metal centers within this chain, as can be seen in Fig. 2. The described double chain links to four equivalent parallel chains through bridging N-allyl imidazole groups. The N atoms in N-allyl imidazole directs upward in Fig. 2 to link to one parallel chain while the CaC bond moiety groups direct downward to link to another.
Fig. 3. Perspective view along the a-axis of the extended structure of 1 with the chains extending in the direction of the a-axis. Each blue chain connects to four red chains, and each red chain connects to four blue chains.
The full structure is represented in Fig. 3 that shows the view down along the a-axis. To aid in the identification of the chains, individual chains are represented by either blue spheres or red spheres. Inspection of Fig. 3 reveals that each blue chain connects to four red chains and each red chain connects to four blue chains. To the best of our knowledge, 1 is the first structurally characterized 3D olefin–copper(I) coordination polymer which was synthesized by reaction olefin ligand with Cu(I) in directed method. Interestingly, compound 2, formulated as Cu2Br2(N-allyl imidazole) is essentially isostructural to 1. Part of the 3D structure of 2 is represented in Fig. 4. A minor difference between compounds 1 and 2 is the zigzag double chains of
Fig. 5. Perspective views of the extended structure of 1 (a) along the b-axis; (b) along the c-axis.
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Fig. 6. Perspective views of the extended structure of 1 (a) along the a-axis; (b) along the b-axis; (c) along the c-axis.
Cu2X2 dimers centers extend in the a-direction for 1, while those extend in the bc plane for 2. This results in the different topological structure between compounds 1 and 2 (Figs. 5 and 6). Finally the bond distances of Cu–C, C–C, C–N and Cu–Br (Table 2) are unexceptional and in normal ranges found in the corresponding CuBr(olefin) coordination polymers. The diffuse-reflectance UV–vis spectrum of 1 and 2 shows only a low-energy band at ca. 404 and 406 nm, which can be assigned to the metal-to-ligand charge transfer (MLCT) band [9]. The yellow emission spectrum of 1 in the solid state at room temperature is shown in Fig. 7, with
a maximum at ca. 580 nm (lexcZ363 nm). While the red emission spectrum of 2 in the solid state at room temperature show a maximum at ca. 620 nm (lexcZ 363 nm), a clearly bathochromic shift occurs in 2 relative to [Cu4I4(py)] (lemaxZ580 nm) and [Cu(3,4-bpyBr) (lemaxZ 580 nm) [11], which is probably due to p-back-donation from the filled metal dp orbital to the vacant antibonding p* orbital of the coordinated olefin [10]. In conclusion, the solvothermal synthesis technique provides a powerful synthetic method to give organometallic compounds with unique properties those are not readily accessible in solution method.
Y.-M. Song et al. / Journal of Molecular Structure 796 (2006) 210–215 (a) 1.5
Relative Intensity
1.4
[2]
1.3 1.2
[3]
1.1 1.0 0.9 0.8 540
560
580
600
620
640
Wavelength (nm) (b) 1.3
Relative Intensity
1.2 1.1 1.0
[4] 0.9 0.8
[5] 0.7 600
610
620
630 640 650 Wavelength (nm)
660
670
680
[6]
Fig. 7. Fluorescent emission spectra of 1 (a) and 2(b) in the solid state at room temperature (lZ363 nm). [7]
Acknowledgements This work was supported by The Major State Basic Research Development Program (Grant no. G2000077500), Distinguished Young Scholar Fund to R.-G. Xiong (no. 20225103) and the Natural Science Foundation of China and the 20030284001(SRFDP) as well as Zhejiang Province Key Discipline Funding for Industrial Catalysis.
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Solvothermal preparation, X-ray structural characterization and properties of two novel 3D copper(I) halide/N-allyl imidazole coordination polymers Yu-Mei Song b, Jie Pang b, Kun Qian a, Xi-Sen Wang a,b,*, Xiao-Nian Li a, Ren-Gen Xiong b,* a
State Key Lab Breeding Base of Green Chemistry Synthetic Technology, College of Chemical Engineering and Material Science, Zhejiang University of Technology, Hangzhou 310032, People’s Republic of China b The State Key Laboratory of Coordination Chemistry, Coordination Chemistry Institute, Nanjing University, Nanjing 210093, People’s Republic of China Received 25 January 2006; received in revised form 14 February 2006; accepted 18 February 2006 Available online 25 April 2006
Abstract The solvothermal reactions of N-allyl imidazole with CuIX (XZCl, Br) afford two unprecedented 3D copper(I)–olefin coordination polymer Cu2X2(N-allyl imidazole) (XZCl for 1; Br for 2). This is the first 3D copper(I)–olefin coordination polymer synthesized in directed method, compared to most of olefin–Cu(I) coordination polymers prepared by electrochemical method. Of practical interest is that both of them contain 1D zigzag ladder chain composed of basic Cu2X2 dimer unit. Photoluminescent measurements show that 1 displays blue fluorescent emission while 2 has red fluorescent emission at room temperature. q 2006 Elsevier B.V. All rights reserved. Keywords: Solvothermal synthesis; Copper(I) halide organometallic; N-allyl imidazole copper(I) complex; Coordination polymer; Fluorescence; Solid state structure
1. Introduction Copper-catalyzed addition of carbanions to a,b-unsaturated carbonyls and copper-catalyzed cyclopropanation of alkenes by R-carbonyl diazoalkanes involve copper(I)–olefin complexes as catalytically active species or resting state [1]. Copper(I)–ethylene complexes may also participate in a variety of stress responses and developmental processes, as in the smallest plant hormone, an ethylene group binds tightly to the copper receptor site ETR [2]. Recently, The rational design and self-assembly of olefin–copper(I) coordination polymers with highly thermal stability and physical functions have been of intensive interest [3]. These polymers not only display general characters of metal–organic coordination polymer, but also still remain Cu–olefin complex features, such as Cu–p coordinating bond labile [4]. Due to these properties, the Cu(I)–olefin complexes have found a wide
* Corresponding authors. Address: The State Key Laboratory of Coordination Chemistry, Coordination Chemistry Institute, Nanjing University, 22 Han Kou Lu, Nanjing 210093, People’s Republic of China. Tel: C86 25 83594724; fax: C86 25 83314502. E-mail address: [email protected] (R.-G. Xiong).
0022-2860/$ - see front matter q 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.molstruc.2006.02.050
range of applications in fluorescent sensor [3], olefin separation [4] and chiral enantioseparation [5]. To the best of our knowledge, the presence of 3D olefin– copper(I) coordination polymer used olefin ligand and CuX synthesized in direct method is unknown, however, there are very rare 3D olefin–copper(I) coordination polymers reported [6]. The successful generation of 3D networks incorporating olefin coordination to a copper by directed method represents an exciting challenge in modern supramolecular and organometallic chemistry. With this in mind, we have studied the reactions of N-allyl imidazole with CuIX at different temperatures. Herein we report the synthesis, solid-state structures, and some optical-chemical properties of two olefin–copper(I) coordination polymers generated from such reactions. To our knowledge, both 1 and 2 represent the first example of 3D Cu(I)–olefin coordination polymers synthesized by direct-method, compared to most of olefin–Cu(I) coordinated polymers prepared by electrochemical method. 2. Experimental 2.1. Synthesis of the title coordination polymers Coordination polymer Cu2Cl2(N-allyl imidazole): CuCl (1.0 mmol) and N-allyl imidazole (1.0 mmol) were placed in a thick pyrex tube (ca. 20 cm in length). After addition of 2 mL
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Table 1 ˚ ] and angles [8] for 1 Bond lengths [A Cu(1)–N(1) Cu(1)–C(4)#1 Cu(1)–Cu(2)#2 Cu(2)–Cl(4) Cu(2)–Cl(3)#2 Cu(2)–Cu(2)#3 Cl(4)–Cu(2)#3 N(1)–C(7) N(2)–C(5) C(5)–C(7) C(4)–C(6) C(6)–Cu(1)#4 N(1)–Cu(1)–C(4)#1 N(1)–Cu(1)–Cl(3) C(4)#1–Cu(1)–Cl(3) C(6)#1–Cu(1)–Cu(2)#2 Cl(3)–Cu(1)–Cu(2)#2 Cl(4)#3–Cu(2)–Cl(3) Cl(4)#3–Cu(2)–Cl(3)#2 Cl(3)–Cu(2)–Cl(3)#2 Cl(4)–Cu(2)–Cu(1)#2 Cl(3)#2–Cu(2)–Cu(1)#2 Cl(4)–Cu(2)–Cu(2)#3 Cl(3)#2–Cu(2)–Cu(2)#3 Cu(1)–Cl(3)–Cu(2) Cu(2)–Cl(3)–Cu(2)#2 C(6)–C(4)–C(8) C(8)–C(4)–Cu(1)#4
1.953(3) 2.076(4) 3.0068(9) 2.3503(12) 2.4572(13) 3.0167(13) 2.3247(12) 1.379(5) 1.380(5) 1.345(6) 1.374(6) 2.028(4) 115.15(15) 105.84(10) 132.66(12) 99.02(13) 52.78(3) 120.59(4) 116.82(4) 93.35(4) 62.21(4) 50.19(3) 49.44(3) 129.68(5) 125.39(5) 86.65(4) 121.5(4) 113.0(3)
Cu(1)–C(6)#1 Cu(1)–Cl(3) Cu(2)–Cl(4)#3 Cu(2)–Cl(3) Cu(2)–Cu(1)#2 Cl(3)–Cu(2)#2 N(1)–C(3) N(2)–C(3) N(2)–C(8) C(8)–C(4) C(4)–Cu(1)#4 N(1)–Cu(1)–C(6)#1 C(6)#1–Cu(1)–C(4)#1 C(6)#1–Cu(1)–Cl(3) N(1)–Cu(1)–Cu(2)#2 C(4)#1–Cu(1)–Cu(2)#2 Cl(4)#3–Cu(2)–Cl(4) Cl(4)–Cu(2)–Cl(3) Cl(4)–Cu(2)–Cl(3)#2 Cl(4)#3–Cu(2)–Cu(1)#2 Cl(3)–Cu(2)–Cu(1)#2 Cl(4)#3–Cu(2)–Cu(2)#3 Cl(3)–Cu(2)–Cu(2)#3 Cu(1)#2–Cu(2)–Cu(2)#3 Cu(1)–Cl(3)–Cu(2)#2 Cu(2)#3–Cl(4)–Cu(2) C(6)–C(4)–Cu(1)#4 C(4)–C(6)–Cu(1)#4
2.028(4) 2.3703(11) 2.3247(12) 2.3763(13) 3.0068(9) 2.4572(13) 1.328(5) 1.344(5) 1.463(5) 1.499(6) 2.076(4) 153.36(16) 39.11(17) 95.78(12) 106.37(10) 128.77(12) 99.63(4) 115.42(4) 111.91(4) 118.22(4) 120.29(3) 50.19(3) 136.60(5) 90.07(3) 77.03(4) 80.37(4) 68.5(2) 72.3(2)
Symmetry transformations used to generate equivalent atoms: #1 xK1, KyC3/2, zK1/2; #2 KxC1, KyC1, KzC2; #3 KxC2, KyC1, KzC2; #4 xC1, KyC3/2, zC1/2. Table 2 ˚ ] and angles [8] for 2 Bond lengths [A Br(1)–Cu(2) Br(1)–Cu(1) Br(2)–Cu(1)#2 Cu(2)–N(1) Cu(2)–C(2)#3 Cu(2)–Cu(1) Cu(1)–Br(1)#1 C(2)–C(1) C(1)–Cu(2)#4 Cu(2)–Br(1)–Cu(1) Cu(1)–Br(2)–Cu(1)#2 Cu(1)–Br(2)–Cu(2)#2 N(1)–Cu(2)–C(2)#3 N(1)–Cu(2)–Br(1) C(2)#3–Cu(2)–Br(1) C(1)#3–Cu(2)–Br(2)#2 Br(1)–Cu(2)–Br(2)#2 C(1)#3–Cu(2)–Cu(1) Br(1)–Cu(2)–Cu(1) Br(2)–Cu(1)–Br(2)#2 Br(2)#2–Cu(1)–Br(1)#1 Br(2)#2–Cu(1)–Br(1) Br(2)–Cu(1)–Cu(2) Br(1)#1–Cu(1)–Cu(2) C(6)–N(2)–C(5) C(5)–N(2)–C(3) C(6)–N(1)–Cu(2) N(1)–C(6)–N(2) C(5)–C(4)–N(1) C(1)–C(2)–C(3) C(3)–C(2)–Cu(2)#4
2.4896(17) 2.524(2) 2.439(2) 1.960(8) 2.087(11) 3.0578(19) 2.503(2) 1.372(13) 2.060(11) 75.16(6) 80.18(7) 112.69(6) 113.5(4) 107.2(3) 131.6(3) 103.5(4) 101.11(5) 102.0(3) 52.93(5) 99.82(7) 113.56(7) 113.88(7) 120.01(7) 123.06(7) 107.0(8) 125.1(7) 126.7(6) 111.8(8) 110.7(9) 122.2(11) 112.9(6)
Br(1)–Cu(1)#1 Br(2)–Cu(1) Br(2)–Cu(2)#2 Cu(2)–C(1)#3 Cu(2)–Br(2)#2 Cu(1)–Br(2)#2 N(2)–C(6) C(2)–Cu(2)#4 Cu(2)–Br(1)–Cu(1)#1 Cu(1)#1–Br(1)–Cu(1) Cu(1)#2–Br(2)–Cu(2)#2 N(1)–Cu(2)–C(1)#3 C(1)#3–Cu(2)–C(2)#3 C(1)#3–Cu(2)–Br(1) N(1)–Cu(2)–Br(2)#2 C(2)#3–Cu(2)–Br(2)#2 N(1)–Cu(2)–Cu(1) C(2)#3–Cu(2)–Cu(1) Br(2)#2–Cu(2)–Cu(1) Br(2)–Cu(1)–Br(1)#1 Br(2)–Cu(1)–Br(1) Br(1)#1–Cu(1)–Br(1) Br(2)#2–Cu(1)–Cu(2) Br(1)–Cu(1)–Cu(2) C(6)–N(2)–C(3) C(6)–N(1)–C(4) C(4)–N(1)–Cu(2) C(4)–C(5)–N(2) N(2)–C(3)–C(2) C(1)–C(2)–Cu(2)#4 C(2)–C(1)–Cu(2)#4
2.503(2) 2.428(2) 2.887(2) 2.060(11) 2.887(2) 2.439(2) 1.330(11) 2.087(11) 121.37(6) 81.52(7) 69.50(6) 151.0(4) 38.6(4) 95.5(3) 89.9(2) 104.0(3) 106.1(2) 131.6(3) 48.33(4) 116.62(7) 115.35(7) 98.48(7) 62.17(5) 51.91(5) 127.9(8) 104.6(8) 128.4(7) 105.9(8) 110.2(7) 69.6(7) 71.7(6)
Symmetry transformations used to generate equivalent atoms: #1 KxC1, KyC1, Kz; #2 KxC2, KyC1, Kz; #3 xC1, KyC1/2, zC1/2; #4 xK1, KyC1/2, zK1/2.
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of 2-butanol, the tube was frozen with liquid N2, evacuated under vacuum, and sealed with a torch. The tube was then placed into oven at 70 8C for 5 days to give pale-yellow block crystals. Yield: ca. 40% on the basis of N-allyl imidazole. IR (KBr, cmK1) for 1: 3448(br w), 3148(w), 3111(w), 2925(w), 1626(w), 1517(s), 1443(w), 1397(m), 1278(w), 1233(s), 1112(m), 1086(s), 1025(w), 934(w), 837(s), 754 (s), 655(m), 630(m), 559(w), 476 (w). Coordination polymer Cu2Br2(N-allyl imidazole): CuBr (1.0 mmol) and N-allyl imidazole (1.0 mmol) were placed in a thick pyrex tube (ca. 20 cm in length). After addition of 2 mL of 2-butanol, the tube was frozen with liquid N2, evacuated under vacuum, and sealed with a torch. The tube was then placed into oven at 70 8 for 5 days to give pale-yellow block crystals. Yield: ca. 45% on the basis of N-allyl imidazole. IR (KBr, cmK1) for 2: 3442(br, w), 3144(m), 3118(s), 1739(w), 1670(w), 1623(w), 1515(s), 1442(m), 1396(s), 1279(m), 1253(w), 1231(s), 1113(s), 1088(s), 1024(m), 988(w), 950(w), 939(m), 908(w), 874(w), 835(s), 775(w), 756(s), 705(w), 657(s), 629 (s), 471(m), 430(w). In comparison to that of metal-free N-allyl imidazole with a peak at 1649 cmK1 which is the stretching vibration of metalfree CaC bond, there is a weak peak at 1626 cmK1 for 1 and at 1623 cmK1 for 2 in their IR spectra, indicating that CaC bond moiety groups directly link to Cu(I). 2.2. Single crystal structure determination X-ray diffraction data for compounds 1 and 2 were collected at ambient temperature on Bruker Smart Aepex-II CCD area ˚ ). The structures detector (Mo Ka X-radiation, lZ0.71069 A were solved with direct methods using the program SHELXTL (Sheldrick, 1997). All the non-hydrogen atoms were located from the trial structure and then refined anisotropically with SHELXTL using full-matrix least-squares procedure. The hydrogen atom positions were fixed geometrically at calculated distances and allowed to ride on the parent carbon atoms. The final difference Fourier map was found to be featureless. Crystallographic data (excluding structure factors) for the complexes have been deposited with the Cambridge Crystallographic Data Center as supplementary publication no. CCDC 602565 and 602566. The crystal data for 1: C6H8Cl2Cu2N2, MrZ306.12, Monoclinic, space group, P2(1)/c, aZ6.3234(13) ˚ , bZ16.440(3) A ˚ , cZ8.7390(17) A ˚ , aZgZ908, bZ A ˚ 3, ZZ4, TZ293(2)K, D cZ 96.49(3)8, VZ902.7(3) A 2.253 g cmK3, mZ5.242 mmK1, R1Z0.0359, wR2Z0.1208, GOFZ0.980. 2: C6H8Br2Cu2N2, MrZ395.04, Monoclinic, ˚ , bZ17.333(4) A ˚ , cZ space group, P2(1)/c, aZ6.4149(11) A ˚ , aZgZ908, bZ98.170(18)8, VZ9 950.4(3) A ˚ 3, 8.6356(17) A K3 K1 ZZ4, TZ293(2)K, DcZ2.761 g cm , mZ12.825 mm , R1Z0.0480, wR2 Z0.1394, GOFZ1.131. The bond distances and angles of coordination polymers 1 and 2 are listed in Tables 1 and 2, respectively.
N
N
+ CuCl
2-butanol
N
N
Cu2Cl2
N
N
Cu2Br2
70°C
N
N
+ CuBr
2-butanol 70°C
Scheme 1.
conditions. The coordination polymers, Cu2Cl2(N-allyl imidazole) (1) and Cu2Br2(N-allyl imidazole) (2), were isolated from these reaction mixtures (Scheme 1). EPR spectra of single crystal samples of 1 and 2 are silent, indicating that the statuses of Cu atoms in these two coordination polymers is C1. The X-ray crystal structure analysis of complex 1 illustrated there are one unique ligand and two different coordination environmental copper atoms in compound 1, as depicted in Fig. 1. Cu1 possesses a tetrahedral coordination geometry composed of two halide atoms, a N atom and a CaC bond moiety in different N-allyl imidazole. The Cu2 centers are coordinated by four halide atoms while each Cl anion acts as m3-linker to bridge three Cu atoms to result in the formation of a four-coordinated metal center with a tetrahedral coordination geometry. Thus, the ligand allylimidazole acts as a bidentate spacer to link two Cu(I) ions by using one N atom and one olefin moiety to give rise to a 3D olefin–copper(I) network, as shown in Fig. 2. As Table 1 ˚) indicates, the CaC double bond distance (1.374(2) A is slightly longer than those found in [Cu(HB(3,5-Me2PZ)3(C2H4))](3,5-Me2PZZhydrotris(3,5-dimethyl-1-pyrazolylbo˚ ) [7a], [Cu2 (COT)(hfacac)2] (COTZ1,3,5,7rate) (1.329(9) A cyclododecatriene, hfacacZhexafluroacetylacetone) (1.31(1)– ˚ ) [7b], [Cu2Cl2(C5H8)] (C5H8Z2-methylbutadiene) 1.33(1) A ˚ ) [7c] and [CuCl(C4H6O2)] (C4H6O2Zmethylpro(1.358(7) A ˚ ) [7d], but slightly shorter than penoate) (1.370(8) A those found in [CuCl-(C5H8O)](C5H8OZ1-penten-3-one)
3. Results and discussion In this present investigation, we have reacted N-allyl imidazole with either CuCl or CuBr under solvothermal
Fig. 1. Part of the structure of 1 showing the four-coordinated copper center bound to two ligands in which ligand attached to two copper(I) centers (H atoms are omitted for clarity).
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Fig. 2. Zigzag double chain of Cu2X2 dimers linked by ligands. (H atoms are omitted for clarity). Fig. 4. Part of the structure of 2 showing the slightly distorted tetrahedral coordination geometry around copper centers.
˚ ) [7e]. It is interesting to note that the CaC bond (1.383(8) A lengths of the coordinated olefin in the two copper(I) ˚ ) and Cu4Br4L (1.34(2) A ˚) p-complexes Cu4Cl4L (1.33(2) A (LZC7H8, 1,4-pentadiene) containing a Cu4X4 cubane core are slightly shorter than those of 1 [7f] and in the copper(I) ˚ ) (LZtrially-1,3,5p-complex Cu4Br4L (1.346(2)–1.442 A triazine-2,4,6-(1H,3H,5H)-trione) are slightly longer than those of 1 [7f]. Finally, the lengthening of the CaC double bond may be typical of ethylene ligands that are h2-bonded to low valiant electron-rich transition metals [8]. The complicate structure of the network can be best understood by considering zigzag double chains of Cu2Cl2 dimers centers that extend in the a-direction. The ligands lie either side of the zigzag chain and each ligand links two metal centers within this chain, as can be seen in Fig. 2. The described double chain links to four equivalent parallel chains through bridging N-allyl imidazole groups. The N atoms in N-allyl imidazole directs upward in Fig. 2 to link to one parallel chain while the CaC bond moiety groups direct downward to link to another.
Fig. 3. Perspective view along the a-axis of the extended structure of 1 with the chains extending in the direction of the a-axis. Each blue chain connects to four red chains, and each red chain connects to four blue chains.
The full structure is represented in Fig. 3 that shows the view down along the a-axis. To aid in the identification of the chains, individual chains are represented by either blue spheres or red spheres. Inspection of Fig. 3 reveals that each blue chain connects to four red chains and each red chain connects to four blue chains. To the best of our knowledge, 1 is the first structurally characterized 3D olefin–copper(I) coordination polymer which was synthesized by reaction olefin ligand with Cu(I) in directed method. Interestingly, compound 2, formulated as Cu2Br2(N-allyl imidazole) is essentially isostructural to 1. Part of the 3D structure of 2 is represented in Fig. 4. A minor difference between compounds 1 and 2 is the zigzag double chains of
Fig. 5. Perspective views of the extended structure of 1 (a) along the b-axis; (b) along the c-axis.
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Fig. 6. Perspective views of the extended structure of 1 (a) along the a-axis; (b) along the b-axis; (c) along the c-axis.
Cu2X2 dimers centers extend in the a-direction for 1, while those extend in the bc plane for 2. This results in the different topological structure between compounds 1 and 2 (Figs. 5 and 6). Finally the bond distances of Cu–C, C–C, C–N and Cu–Br (Table 2) are unexceptional and in normal ranges found in the corresponding CuBr(olefin) coordination polymers. The diffuse-reflectance UV–vis spectrum of 1 and 2 shows only a low-energy band at ca. 404 and 406 nm, which can be assigned to the metal-to-ligand charge transfer (MLCT) band [9]. The yellow emission spectrum of 1 in the solid state at room temperature is shown in Fig. 7, with
a maximum at ca. 580 nm (lexcZ363 nm). While the red emission spectrum of 2 in the solid state at room temperature show a maximum at ca. 620 nm (lexcZ 363 nm), a clearly bathochromic shift occurs in 2 relative to [Cu4I4(py)] (lemaxZ580 nm) and [Cu(3,4-bpyBr) (lemaxZ 580 nm) [11], which is probably due to p-back-donation from the filled metal dp orbital to the vacant antibonding p* orbital of the coordinated olefin [10]. In conclusion, the solvothermal synthesis technique provides a powerful synthetic method to give organometallic compounds with unique properties those are not readily accessible in solution method.
Y.-M. Song et al. / Journal of Molecular Structure 796 (2006) 210–215 (a) 1.5
Relative Intensity
1.4
[2]
1.3 1.2
[3]
1.1 1.0 0.9 0.8 540
560
580
600
620
640
Wavelength (nm) (b) 1.3
Relative Intensity
1.2 1.1 1.0
[4] 0.9 0.8
[5] 0.7 600
610
620
630 640 650 Wavelength (nm)
660
670
680
[6]
Fig. 7. Fluorescent emission spectra of 1 (a) and 2(b) in the solid state at room temperature (lZ363 nm). [7]
Acknowledgements This work was supported by The Major State Basic Research Development Program (Grant no. G2000077500), Distinguished Young Scholar Fund to R.-G. Xiong (no. 20225103) and the Natural Science Foundation of China and the 20030284001(SRFDP) as well as Zhejiang Province Key Discipline Funding for Industrial Catalysis.
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