29 2 2010.

JIEGOU HUAXUE Chinese J. Struct. Chem.

Vol. 29, No. 2 270~274

Synthesis, Structure and Luminescence of a 1-D Chain of Copper(I) Cyanide Decorated by Triphenylphosphine
QIN Li WANG Fei ZHAO Zhen-Guo ZHANG Qi-Sheng LU Can-Zhong
(State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences, Fuzhou, Fujian 350002, China) ABSTRACT A new wave-like infinite chain coordination polymer [Cu3(CN)3(PPh3)4]n (1, PPh3

= triphenylphosphine) has been synthesized by solution reaction and characterized by X-ray single-crystal structure diffraction analysis. The complex crystallizes in space group P 1 with a = 13.343(6), b = 13.429(7), c = 20.694(10) , = 103.163(4), = 96.704(5), = 101.981(6), V = 3479(3) 3, Z = 2, C75H60Cu3N3P4, Mr = 1317.76, Dc = 1.258 g/cm3, F(000) = 1356, = 1.043 mm-1, the final R = 0.0680 and wR = 0.1305 for 9232 observed reflections with I > 2(I). The infinite chain is linked by CH H bonding interactions to form a 2-D supramolecular network. Luminescent study reveals that the complex has green-light emission. Keywords: copper(I) cyanide, CH hydrogen bonds, crystal structure, luminescence

1 INTRODUCTION
In recent years, the copper(I) cyanide system has been a prevalent topic to coordination chemists in the design and synthesis of molecular functional materials
[13]

interrelated results[9

11]

It is well known that the employment of ancillary ligands plays an important role in supramolecular framework construction. Apart from the steric properties of the ligands, some subtle interactions derived from it, such as H-bond, CH interaction[12, 13] and - stacking[14], may also exert an influence on controlling the supramolecular architecture. In this paper, we report the synthesis, crystal structure and luminescent property of a new infinite chain coordination polymer [Cu3(CN)3(PPh3)4]n. The 1-D chain is linked by CH H-bonding interactions to form a 2-D supramolecular network.

. It is of interest that the cyano-bridged

transition-metal coordination polymers may increase the structural diversity and be applied in many yields . This is because the cyano group is a versatile ligand that could act as not only a monodentate ligand but also a bridging ligand adopting end-on or end-end modes, which can generate various complexes with different properties . In addition, with the closed-shell d , the Cu(I) has been demonstrated to be an effective way to impart intriguing photoluminescent characteristics via metal-ligand tal-metal interactions
[7, 8] [6] 10 [5] [4]

2
2. 1

EXPERIMENTAL
Materials and measurements

and meAll starting materials and reagents were of AR gra-

. With regards to the system,

Pikes group have reported a series of excellent

Received 6 March 2009; accepted 20 March 2009

This work was supported by the National Natural Science Foundation of China (20873150, 20821061, and 50772113), the Natural Science Foundation of Fujian Province (2007F3116, 2007HZ0001-1) and the Chinese Academy of Sciences (KJCX2-YW-M05) Corresponding author. E-mail: czlu@ms.fjirsm.ac.cn

2010

Vol. 29

JIEGOU HUAXUEChinese J.

Struct.

Chem.

271

de and used as received without further purification. Elemental analyses for C, H and N were performed on a Vario EL III elemental analyzer. Photoluminescent analyses were performed on a HORIBA JobinYvon FluoroMax-4 spectrometer. 2. 2 Synthesis of [Cu3(CN)3(PPh3)4]n A mixture of CuCN (0.090 g, 1.0 mmol) and equimolar amount PPh3 (0.262 g, 1.0 mmol) in methylene chloride (10 mL) was stirred for 30 min at room temperature to give a colorless solution. This solution was concentrated to give product in powder which was recrystallized from methylene chloride/ether to afford colorless crystals. Yield: 0.204 g, 62%. Anal. Calcd. (%) for C75H60Cu3N3P4: C, 68.36; H, 4.59; N, 3.19. Found (%): C, 68.59; H, 4.49; N, 3.17. 2. 3 Structure determination Crystallographic data were collected on a Rigaku Mercury-CCD diffractometer equipped with a graTable 1.
Bond Cu(1)N(1) Cu(1)X(1) Cu(1)P(1) Cu(1)P(2) Angle N(1)Cu(1)X(1) P(1)Cu(1)P(2) P(1)Cu(1)X(1) N(1)Cu(1)P(2) N(1)Cu(1)P(1) Dist. 2.006(4) 1.954(3) 2.2613(14) 2.2657(16) () 99.10(16) 119.13(5) 107.99(12) 114.26(11) 106.49(12)

phite-monochromatic MoK radiation ( = 0.71073 ) at 293(2) K. Absorption corrections were applied using the SADABS program[15]. The structure was solved by direct methods and refined on F2 by fullmatrix least-squares procedures using the SHELX97 program package[16, 17]. All non-hydrogen atoms were refined anisotropically. The positions of hydrogen atoms attached to carbon atoms were fixed at their ideal positions. A total of 27262 reflections (2.0327.48) were collected with 15734 unique ones (Rint = 0.0475), of which 9232 with I > 2(I) were observed and used for structural elucidation. At convergence, the final R = 0.0680, wR = 0.1305 (w = 1/[2(Fo2) + (0.0506P)2 + 0.9326P], where P = (Fo2 + 2Fc2)/3), goodness-of-fit = 1.069, ()max = 0.344 and ()min = 0.333 e/3. Selected bond lengths and bond angles are listed in Table 1.

Selected Bond Lengths () and Bond Angles ()

Bond Cu(2)C(1) Cu(2)C(3) Cu(3)N(3) Cu(3)X(2) Angle X(1)Cu(1)P(2) C(1)Cu(2)C(3) N(1)C(1)Cu(2) N(3)C(3)Cu(2) N(3)Cu(3)X(2) Dist. 1.815(5) 1.792(4) 2.006(5) 1.952(3) () 107.88(12) 174.5(2) 178.0(5) 167.5(5) 110.93(19) Bond Cu(3)P(3) Cu(3)P(4) N(1)C(1) N(3)C(3) Angle P(3)Cu(3)P(4) N(3)Cu(3)P(3) X(2)Cu(3)P(4) X(2)Cu(3)P(3) N(3)Cu(3)P(4) Dist. 2.2929(16) 2.2909(17) 1.142(5) 1.143(6) () 112.42(5) 109.43(13) 106.75(13) 109.24(13) 108.05(13)

3 RESULTS AND DISCUSSION

3. 1 Structure description

two P atoms (P(3) and P(4)) from two triphenylphosphine ligands, one N atom from a cyanide ion N(3) in an end-end mode and one end atom X(2) in a disordered cyanide ion with the occupancy factors of 0.5 for N and 0.5 for C. However, the middle Cu(2) is coordinated by two C atoms from two end-end mode cyanides, resulting in a trinuclear (CuCN)3 asymmetric unit. The CuN, CuC and CuP distances are respectively in the ranges of 2.0062.007, 1.7921.816 and 2.2612.293 , similar to those reported[8]. As shown in Fig. 2, the adjacent trinuclear (CuCN)3 units are linked by the disordered cyanides to form a zigzag -[(CuCN)3]n- chain. There are C

The crystallographic analysis reveals that complex 1 has an infinite chain polymeric structure containing a trinuclear (CuCN)3 asymmetric unit. As shown in Fig. 1, the terminal Cu(1) is located in a distorted tetrahedral geometry surrounded by two P atoms (P(1) and P(2)) from two triphenylphosphine ligands, one N atom from a cyanide ion N(1) in an end-end mode and one end atom X(1) in a disordered cyanide ion with the occupancy factors of half N and half C
[18, 19]

. Another terminal Cu(3) has a

similar distorted tetrahedral geometry to Cu(1) with

272

QIN L. et al.: Synthesis, Structure and Luminescence of a 1-D Chain of Copper(I) Cyanide Decorated by Triphenylphosphine

No. 2

H-bonds

between

adjacent

chains,

as

adjacent chain offer the matched orientation and distances, leading to CH interactions with H distances of 2.841 and 2.891 , respectively. Thus, the individual 1-D chains are linked by CH H-bonding interactions to generate a 2-D supramolecular network (Fig. 3).

elaborated in Fig. 4. Two phenyl rings of the two crystallographic-independent triphenylphosphine ligands afford the unoccupied * orbitals, and two hydrogen atoms from two phenyl rings of the two symmetric triphenylphosphine ligands in the

Fig. 1.

Asymmetry of complex 1

Fig. 2.

Zigzag backbone of complex 1

Fig 3. 2-D Supramolecular network of complex 1 with CH H-bonding interactions. Some aromatic rings were omitted for clarity

2010

Vol. 29

JIEGOU HUAXUE Chinese

J.

Struct. Chem.

273

Fig. 4.

CH H-bonding interactions in complex 1

3. 2

Luminescent property

CuCN itself[9

11]

. The origins of fluorescence of

The luminescent property of 1 in solid state has been investigated. Complex 1 exhibits a strong and broad fluorescent emission band centered at 480 nm when excited by UV light with max = 350 nm at room temperature (Fig. 5). Generally, the photophysical behavior of the coordination polymers formed by CuCN appears to be closely related to that of

complex 1 may be ascribed to the coupling of metalto-ligand charge transfer (MLCT) where the electron is transferred from the copper(I) center to unoccupied * orbital of cyanide ligand and metal-centered transitions (MC) of 3d103d94s and 3d103d94p on copper(I) centers[20
22]

Intensity (a.u)

400

500

600

700

Wavelength (nm)

Fig. 5.

Emission spectra of complex 1 in solid state at room temperature

REFERENCES
(1) (a) Ouahab, L. Chem. Mater. 1997, 9, 19091926; (b) Ohba, M.; Oh kawa, H. Coord. Chem. Rev. 2000, 198, 313328; (c) Moulton, B.; Zaworotko, M. J. Chem. Rev. 2001, 101, 16291658; (d) Niel, V.; Muoz, M. C.; Gaspar, A. B.; Galet, A.; Levchenko, G.; Real, J. A. Chem.-Eur. J. 2002, 8, 24462453. (2) (a) Soma, T.; Yuge, H.; Iwamoto, T. Angew. Chem., Int. Ed. Engl. 1994, 33, 16651666; (b) Soma, T.; Iwamoto, T. Inorg. Chem. 1996, 35, 18491856; (c) ernk, J.; Abboud, K. A.; Chomi, J.; Meisel, M. W.; Orend, M.; Orendov, A.; Feher, A. Inorg. Chim. Acta 2000, 311, 126132; (d) Dasna, I.; Golhen, S.; Ouahab, L.; Daro, N.; Sutter, J. P. Polyhedron 2001, 20, 13711374; (e) ernk, J.; Chomi, J.; Massa, W. Acta Crystallogr., Sect. C 2002, 58, m490m493; (f) Dong, W.; Wang, Q. L.; Si, S. F.; Liao, D. Z.; Jiang, Z. H.; Yan, S. P.; Cheng, P. Inorg. Chem. Commun. 2003, 6, 873876; (g) Potok, I.; Triikov, L.; Wagner, C. Acta Crystallogr., Sect. C 2003, 59, m249m251. (3) (a) Leznoff, D. B.; Xue, B. Y.; Batchelor, R. J.; Einstein, F. W. B.; Patrick, B. O. Inorg. Chem. 2001, 40, 60266034; (b) Shorrock, C. J.; Xue, B. Y.; Kim, P. B.; Batchelor, R. J.; Patrick, B. O.; Leznoff, D. B. Inorg. Chem. 2002, 41, 67436753; (c) White-Morris, R. L.; Stender, M.; Tinti, D. S.; Balch, A. L.; Rios, D.; Attar, S. Inorg. Chem. 2003, 42, 32373244.

274
(4)

QIN L. et al.: Synthesis, Structure and Luminescence of a 1-D Chain of Copper(I) Cyanide Decorated by Triphenylphosphine

No. 2

(a) Muller, U.; Schubert, M.; Teich, F.; Puetter, H.; Schierle-Arndt, K.; Pastr, J. J. Mater. Chem. 2006, 16, 626; (b) Dinc, M.; Yu, A. F.; Long, J. R. J. Am. Chem. Soc. 2006, 128, 8904; (c) Rowsell, J. L. C.; Yaghi, O. M. J. Am. Chem. Soc. 2006, 128, 1304; (d) Forster, P. M.; Cheetham, A. K. Top. Catal. 2003, 24, 79; (e) Kesanli, B.; Lin, W. Coord. Chem. Rev. 2003, 246, 305.

(5) (6)

He, X.; Lu, C. Z.; Yuan, D. Q.; Chen, S. M.; Chen, J. T. Eur. J. Inorg. Chem. 2005, 21812188. (a) Chan, W. H.; Mak, T. C. W.; Che, C. M. J. Chem. Soc., Dalton Trans. 1998, 22752276; (b) Fu, W. F.; Chan, K. C.; Miskowski, V. M.; Che, C. M. Angew. Chem., Int. Ed. 1999, 38, 27832785; (c) Che, C. M.; Mao, Z.; Miskowski, V. M.; Tse, M. C.; Chan, C. K.; Cheung, K. K.; Phillips, D. L.; Leung, K. H. Angew. Chem., Int. Ed. 2000, 39, 40844088; (d) Fu, W. F.; Chan, K. C.; Cheung, K. K.; Che, C. M. Chem.Eur. J. 2001, 7, 46564664.

(7)

(a) Jansen, M. Angew. Chem., Int. Ed. Engl. 1987, 26, 10981110; (b) Ford, P. C.; Vogler, A. Acc. Chem. Res. 1993, 26, 220226; (c) Schmidbaur, H. Chem. Soc. Rev. 1995, 24, 391400; (d) Pyykk, P. Chem. Rev. 1997, 97, 597636; (e) Puddephatt, R. J. Chem. Commun. 1998, 10551062; (f) Patterson, H. H.; Kanan, S. M.; Omary, M. A. Coord. Chem. Rev. 2000, 208, 227241.

(8) (9) (10) (11)

Lin, Y. Y.; Lai, S. W.; Che, C. M.; Fu, W. F.; Zhou, Z. Y.; Zhu, N. Y. Inorg. Chem. 2005, 44, 15111524. Pike, R. D.; DeKrafft, K. E.; Ley, A. N.; Tronic, T. A. Chem. Commun. 2007, 37323734. Tronic, T. A.; DeKrafft, K. E.; Lim, M. J.; Ley, A. N.; Pike, R. D. Inorg. Chem. 2007, 46, 88978912. Lim, M. J.; Murray, C. A.; Tronic, T. A.; DeKrafft, K. E.; Ley, A. N.; DeButts, J. C.; Pike, R. D.; Lu, H. Y.; Patterson, H. H. Inorg. Chem. 2008, 47, 69316947.

(12) (13) (14) (15) (16) (17) (18) (19) (20) (21) (22)

Topics in Current Chemistry: Design of Organic Solids; Weber, E. Ed.; SpringerVerlag: Berlin 1998, 198. Brada, D.; Brammer, L.; Champness, N. R. CrystEngComm. 2005, 7, 119. Blake, A. J.; Champness, N. R.; Khlobystov, A. N.; Lemenovskii, D. A.; Li, W. S.; Schrder, M. Chem. Commun. 1997, 13391340. Sheldrick, G. M. SADABS: Program for Siemens Area Detector Absorption Corrections; University of Gttingen: Gttingen, Germany 1997. Sheldrick, G. M. SHELXS97: Program for the Crystal Structure Solution; University of Gttingen, Germany 1997. Sheldrick, G. M. SHELXL97: Program for the Crystal Structure Refinement; University of Gttingen, Germany 1997. Dyason, J. C.; Healy, P. C.; Engelhardt, L. M.; Pakawatchai, C.; Patrick, V. A.; White, A. H. J. Chem. Soc., Dalton Trans. 1985, 839844. Bowmaker, G. A.; Hartl, H.; Urban, V. Inorg. Chem. 2000, 39, 45484554. Liu, X.; Guo, G. C.; Fu, M. L.; Zou, J. P.; Zheng, F. K.; Huang, J. S. Inorg. Chim. Acta 2006, 359, 16431649. Bayse, C. A.; Brewster, T. P.; Pike, R. D. Inorg. Chem. 2009, 48, 174182. Wang, H.; Lia, M. X.; Shao, M.; Wang, Z. X. Journal of Molecular Structure 2008, 889, 154159.