Polyhedron 30 (2011) 465469

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Polyhedron
journal homepage: www.elsevier.com/locate/poly

N-heterocyclic carbenesilver complexes: Potential conductive materials for silver pastes in electronic applications
Won Jin Park a, Jaehoon Choe b, Sang Mi Lee c, Hye Jin Lee a, Jaeyoung Lee d, Kwang Ho Song c,, Hyosun Lee a,
a

Department of Chemistry, Kyungpook National University, 1370 Sankyuk-dong, Buk-gu, Daegu-city 702-701, Republic of Korea LG Chem. Ltd./Research Park, Munji-dong, Yuseong-gu, Deajeon-city 305-380, Republic of Korea c Department of Chemical and Biological Engineering, Korea University, Anam-dong, Seongbuk-gu, Seoul 136-713, Republic of Korea d Electrochemical Reaction and Technology Laboratory (ERTL), Department of Environmental Science and Engineering, Gwangju Institute of Science and Technology (GIST), Gwangju 500-712, Republic of Korea
b

a r t i c l e

i n f o

a b s t r a c t
New organosilver complexes, silver(I) tetraalkylbis(benzimidazolidene) halide [1a3a] and silver(I) dimethyl-N,N0 -hexyl(imidazolyl) bromide [4a], were synthesized and incorporated into electroconductive silver pastes. Complex 3a had a 15-fold higher conductivity than conventional silver salt pastes, specically silver(I) hexanoate, and exhibited a smooth, homogeneous surface after reductive heattreatment of the silver paste. While the conductivity of silver(I) hexanoate can be increased by up to 33% by the addition of a supporting silver source, such as Ag2O, the conductivity of 3a was markedly decreased by Ag2O treatment. Thus, 3a can be used in silver pastes with moderate conductivity and can reduce the amount of conventional silver supporting materials without loss of electroconductivity. 2010 Elsevier Ltd. All rights reserved.

Article history: Received 22 May 2010 Accepted 9 November 2010 Available online 25 November 2010 Keywords: N-heterocyclic carbenes (NHCs) Ag(I)NHC complex Silver(I) hexanoate Silver paste Electroconductivity

1. Introduction N-heterocyclic carbenes (NHCs) [1,2] have been used as ligands in the preparation of transition metal complexes since Arduengos report on the isolation of carbenes made stable by coordination with metal atoms through the nitrogen or carbon atoms of the NHC [37]. Specically, many recently prepared transition metal carbene complexes have been useful in synthetic organic chemistry [811], catalysis [1215] and in the fabrication of novel chemical materials [1618]. However, the linear geometry of silver (I) results in mostly mononuclear or binuclear silverNHC complexes [15,1925] or sometimes two- or three-dimensional multinuclear oligomers [2631], depending on the structure of the NHC ligands. For example, bidentate bibenzimidazole-based ligands make up the main chain in organometallic polymers with Pd and Pt [32]. There are many applications of silverNHC complexes as certain materials, however the use of silver(I)NHC complexes in conductive silver pastes is not common. Because silver(I) salts and elemental silver are effective electroconductive materials used in commercial printed circuit boards (PCBs) [3336], one might expect that a silver(I)NHC complex would boast identical or improved chemical and physical properties. Silver pastes composed
Corresponding authors. Tel.: +82 53 950 5337.
E-mail addresses: khsong@korea.ac.kr (K.H. Song), hyosunlee@knu.ac.kr (H. Lee). 0277-5387/$ - see front matter 2010 Elsevier Ltd. All rights reserved. doi:10.1016/j.poly.2010.11.021

of organosilver complexes, such as Ag(I)NHCs, have electronic properties comparable to commercial Ag(I)carboxylates and can be used in electronic devices instead of metallic nanoparticles [37]. Silver ink and silver pastes are commonly used in inkjet [3739] and roll printing [34] processes to fabricate conductive patterns on substrates such as PCBs, and can be applied to PDP electrodes, FPCB circuits, RFID antennas, EMI screens, solar cells, and exible displays [4042]. The current study focused on the synthesis and characterization of silver(I)NHC complexes having the ligands bis-benzimidazolium and bis-imidazolium, and their application as electroconductive materials. Since the use of bidentate ligands requires two equivalents of silver for complexation, this study demonstrates a means of reducing the cost of synthetic silver pastes without sacricing the desired electrical properties. 2. Experimental 2.1. General consideration
1 H NMR (400 and 600 MHz) and 13C NMR (75.46 and 150.83 MHz, respectively) were recorded using Bruker Advance Digital 400 and 600 NMR spectrometers. Infrared (IR) spectra were recorded by a Bruker FT/IR-Alpha (neat) spectrometer, and the data are reported in cm1. Elemental analyses and ICP (Inductively

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Coupled Plasma) were performed on a Fison-EA1108 and Thermo IRIS XDL duo, respectively. Absorption and emission spectra were obtained on a Jasco V-530 UV/Vis spectrophotometer and Jasco FP-6500 spectrouorometer, respectively. The surface morphology and crystal structure of the prepared Ag complex electrode were analyzed using eld-emission scanning electron microscopy (FE-SEM; Hitachi S-570) and X-ray diffraction (XRD; Rigaku, D/max Uitima III) using Cu Ka radiation, respectively. The electrical resistance was measured by IVIUN technology, Compactstate Electrochemical Interface B07508. 2.2. Synthesis of the ligands and silver complexes 2.2.1. Tetraallylbis(benzimidazolium) bromide, L3 Tetraallyl bis(benzimidazolium) bromide (L3) was prepared by slightly modifying a method previously described in the literature [32,43]. A mixture of 3,30 -bibenzimidazole (2.00 g, 8.54 mmol) [44] and sodium hydride (55 wt.%, 0.730 g, 16.8 mmol) in toluene (30 mL) was heated to 110 C for 1 h, and then allowed to cool to ambient temperature. Allyl bromide (4.40 mL, 51.5 mmol) was added via syringe to the reaction solution, which was then stirred at 110 C for 1 h. Dried DMF (30 mL) was added to dissolve the precipitate, followed by stirring at 110 C for 6 h and then at 60 C for 4 h. Upon completion, the suspension was cooled and then diluted with toluene (50 mL), producing a tan-colored precipitate that was collected by vacuum ltration. The precipitate was then successively rinsed with THF (10 mL 2) and dried in vacuo to give a dark beige-colored solid (4.07 g, 85.7%). 1H NMR (400 MHz, DMSO-d6): d 9.96 (s, 2H), 8.64 (s, 2H), 8.17 (s, 2H), 6.24 (m, 4H), 5.58 (d, J = 2.0 Hz, 4H), 5.52 (d, J = 3.5 Hz, 4H), 5.49 (d, J = 4.5 Hz, 4H), 5.37 (d, J = 1.3 Hz, 4H). 13C NMR (600 MHz, DMSO-d6): d 49.34 (4C), 113.23 (2C), 114.96 (2C), 120.85 (2C), 121.11 (2C), 126.59 (2C), 131.42 (4C), 132.25 (4C), 137.88 (2C), 136.49 (4C), 143.59 (2C). IR (solid neat, cm1): 3415(s), 3120(w), 2959(s), 1818(w), 1618(s), 1562(s), 1490(m), 1435(s), 1383(w), 1335(w), 1267(w), 1214(m), 1159(w), 1034(w), 1002(s), 936(s), 856(w), 812(s), 731(w), 606(m), 478(w), 414(w). 2.2.2. Dimethyl-N,N0 -hexyl(imidazolium) chloride, L4 A mixture of 1,6-dichlorohexane (5.00 mL, 34.4 mmol) and N-methylimidazole (5.54 mL, 68.8 mmol) in hexane (30 mL) was heated at 55 C for 2 days, and the resulting residue was dried in vacuo. Addition of methylene chloride (30 mL) produced a white solid that was collected by vacuum ltration, washed with pentane (20 mL 2), and dried in vacuo (5.04 g, 45.8%). 1 H NMR (400 MHz, CDCl3): d 10.77 (s, 2H), 7.78 (s, 2H), 7.27 (s, 2H), 4.43 (t, J = 4.2 Hz, 4H), 4.07 (s, 6H), 2.03 (dd, J = 3.7 Hz, 4H), 1.75 (dd, J = 3.8 Hz, 4H), 1.50 (dd, J = 3.5 Hz, 4H). 13C NMR (600 MHz, CDCl3): d 25.33 (2C), 31.19 (2C), 38.84 (2C), 51.31 (2C), 121.34 (2C), 122.29 (2C), 206.93 (2C). IR (solid state, cm1): 791(m), 679(w), 655(w), 635(m), 622(s), 600(w), 582(w), 567(s). Anal. Calc. for C14H24N4Cl2: C, 52.66; H, 7.58; N, 17.55. Found: 50.25; H, 8.17; N, 16.53%. 2.2.3. Silver (I) tetramethylbis(benzimidazolidene) iodide (1a) [45] Tetramethylbis(benzimidazolium) iodide (L1) [43] (0.200 g, 0.366 mmol) and silver oxide (0.0850 g, 0.366 mmol) were added to THF (30 mL) under argon atmosphere. The reaction ask was wrapped with aluminum foil to avoid light and was heated at 70 C for 3 days. The reaction solution was separated from any residue by ltration and then evaporated. The obtained solid was successively washed with water (20 mL 2) and pentane (20 mL 2) and dried in vacuo to give a pale grey solid (0.160 g, 57.5%). 1H NMR (300 MHz, DMSO-d6): d 7.48 (s, 2H), 7.41 (d, J = 3.9 Hz, 2H), 7.21 (d, J = 4.0 Hz, 2H), 3.40 (s, 6H), 3.25

(s, 6H). 13C NMR (600 MHz, CDCl3): d 27.06 (2C), 54.49 (2C), 105.99 (2C), 107.81 (2C), 119.52 (2C), 128.91 (2C), 130.37 (2C), 134.11 (2C), 154.10 (2C). IR (solid state, cm1): 3416(m), 3057(m), 2918(m), 2850(m), 1665(w), 1569(s), 1491(s), 1443(s), 1384(s), 1264(m), 1155(w), 1093(w), 1031(w), 1009(w), 945(w), 843(m), 808(s), 792(s), 667(w), 594(w). Anal. Calc. for C18H18N4 Ag2I2: C, 28.45; H, 2.39; N, 7.37. Found: C, 28.37; H, 2.65; N, 7.35%. ICP (Ag): Calc.: 28.39, Found: 28.25%. 2.2.4. Silver (I) tetrabenzylbis(benzimidazolidene) bromide (2a) Tetrabenzylbis(benzimidazolium) bromide (L2) [32] (0.500 g, 0.661 mmol) and silver oxide (0.153 g, 0.661 mmol) were added to THF (30 mL) under an argon atmosphere. The reaction ask was wrapped with aluminum foil to avoid light and was heated at 70 C for 3 days. The reaction solution was separated from any residue by ltration and then evaporated. The obtained solid was successively washed with water (20 mL 2) and pentane (20 mL 2) and dried in vacuo to give a pale grey solid (0.380 g, 59.2%). 1H NMR (300 MHz, DMSO-d6): d 7.47 (s, 2H), 7.41 (d, J = 3.9 Hz, 2H), 7.21 (d, J = 4.0 Hz, 2H), 3.40 (s, 6H), 3.25 (s, 6H). 13 C NMR (600 MHz, DMSO-d6): d 30.97 (4C), 79.47 (2C), 113.87 (2C), 115.68 (2C), 127.69 (8C), 129.15 (8C), 131.14 (2C), 132.21 (2C), 134.53 (2C), 136.49 (4C), 136.55 (4C), 206.81 (2C). IR (solid state, cm1): 3415(s), 3029(w), 1617(m), 1496(s), 1483(s), 1454(s), 1396(s), 1351(m), 1182(w), 1022(w), 798(w), 701(s), 621(w). Anal. Calc. for C42H34N4Ag2Br2: C, 52.00; H, 3.53; N, 5.77. Found: C, 51.39; H, 4.17; N, 6.63%. ICP (Ag): Calc.: 22.23, Found: 22.97%. 2.2.5. Preparation of silver (I) tetraallylbis(benzimidazolidene) bromide (3a) Tetraallylbis(benzimidazolium) bromide (L3) (0.95 g, 1.71 mmol) and silver oxide (0.396 g, 1.71 mmol) were added to THF (30 mL) under argon atmosphere. The reaction ask was wrapped with aluminum foil to avoid light and was heated at 70 C for 3 days. The reaction solution was separated from any residue by ltration and then evaporated. The obtained solid was successively washed with water (20 mL 2) and pentane (20 mL 2) and dried in vacuo to give a pale grey solid (0.910 g, 69.1%). 1H NMR (300 MHz, DMSO-d6): d 8.11 (s, 2H), 7.86 (d, J = 2.0 Hz, 4H), 6.17 (m, 4H), 5.31 (s, 4H), 5.27 (s, 4H), 5.24 (d, J = 2.7, 4H), 5.19 (d, J = 2.7 Hz, 4H). 13C NMR (600 MHz, DMSO-d6): d 49.63 (4C), 113.16 (2C), 115.15 (2C), 121.19 (4C), 121.40 (2C), 131.42 (2C), 132.40 (4C), 138.19 (2C), 143.65 (2C), 137.91 (2C). IR (solid state, cm1): 3435(s), 2919(m), 1642(m), 1483(s), 1439(s), 1390(s), 1339(s), 1193(m), 991(s), 938(s), 804(s), 708(w), 538(w). Anal. Calc. for C26H26N4Ag2Br2: C, 40.55; H, 3.40; N, 7.28. Found: C, 39.11; H, 3.46; N, 7.01%. ICP (Ag): Calc.: 28.02, Found: 27.63%. 2.3. Electrical conductivity Electrical resistance was measured with a standard fourpoint probe apparatus at ambient pressure for complexes 1a to 4a and the reference silver complex 5b [46]. The samples were prepared as pastes; the rst group of samples consisted of individual Ag(I)NHC complexes 1a4a or the reference silver hexanoate 5b in 1 mL of ethylenediamine (EDA). The second group of samples consisted of a gradient mixture of 1a4a with Ag2O as an additional silver supply in EDA (1 mL) [47]. Each paste was mixed thoroughly into the EDA and hand-printed onto glass substrates with a roller. The printed substrates were sintered at 130 C for 30 min to reduce the silver paste to metallic silver [48]. The paste layer of each sample was assumed to be 1 mm thick, although SEM images showed relatively rough surfaces with a maximum thickness of 1 mm. The conductivity of each sample was measured at least three times

W.J. Park et al. / Polyhedron 30 (2011) 465469 Table 1 Resistance and conductivity of the Ag(I)NHC complexes (1a4a) and the reference complex Ag(I) hexanoate, 5b. Complex 1a 2a 3a 4a 5b 1a 2a 3a 4a 5b 1a 2a 3a 4a 5b
a

467

3. Results and discussion 3.1. Synthesis and characterization of the ligands and the complexes The synthesis of ligands L1 and L2, as reported by Bielawski et al. [32,43], was achieved by cyclization of commercially available 3,30 -diaminobenzidine to 3,30 -bibenzimidazole in formic acid and then base, followed by the addition of four equivalents of methyl iodide and benzyl bromide, respectively. Ligand L3 was synthesized in a similar manner. For comparison, a non-conjugated bidentate NHC ligand, dimethyl-N,N0 -hexyl(imidazolium) chloride (L4), was also synthesized [49]. Silver-metallation was carried out with moderate yield by reducing Ag2O through the elimination of water in the absence of base (Scheme 1). Metallation was only achieved in hot THF. However, the ideal reaction solvent for complex 4a was methylene chloride. Compounds 1a3a exhibited, in general, very low solubility in organic solvents. Compounds 3a and 4a were moderately soluble in DMSO and CDCl3, respectively, while both 1a and 2a exhibited very poor solubility in DMSO. The synthesized compounds were characterized by 1H NMR, 13C NMR, UV/PL, IR, CHN and ICP analysis for Ag. The successful synthesis of these complexes was conrmed by the disappearance of the hydrogen on the carbon atom of L3, for example, which produced a shift at d 8.11 in the 1H NMR spectrum. Additionally, the ipso carbon atom of L3 at d 144.77 in the 13C NMR shifted to d 154.10, which is slightly downeld from the corresponding chemical shift of 3a. The electronic absorption spectra of L1 and 1a in DMSO exhibited intense absorption bands at kmax = 296 nm (e = 25800 M1 cm1) and kmax = 310 nm (e = 7500 M1 cm1), respectively, with a slight red shift [45]. The shapes and positions of the ligand bands were similar, indicating that substitution of the silver halide for the carbene hydrogen atom of NHC only slightly altered the

Complex/Ag2Oa 1/0 1/0 1/0 1/0 1/0 2/1 2/1 2/1 2/1 2/1 4/1 4/1 4/1 4/1 4/1

Resistance (105, X cm) 12.46 18.44 0.5963 271 9.073 25.73 1.950 22.97 21.60 4.090 16.33 14.19 18.44 38.60 17.86

Conductivity (106, X1 cm1) 8.025 5.422 167.9 0.369 11.02 33.89 51.28 4.353 4.630 24.45 6.124 7.047 5.423 2.590 5.599

Mixed as molar ratio.

at ten different positions to yield an average conductivity. These measurements resulted in an experimental error of less than 12% when performed as follows. The sintered substrates were placed between two copper electrodes, separated by 1 cm, and the electrical resistance between the electrodes was measured by applying a voltage from a constant DC source with a current range of 1 mA and a frequency range of 1000 Hz. The current through the sample was then measured with an electrometer. Measurements at each of the ten spots were performed in triplicate. Each resistance value in Table 1 is the average of ten measurements.

R N N X

NH N

RX Toluene/100 oC
R N N R

N H

N N R R N N Ag N R

Ag 2O Toluene/100 oC
X Ag

R = CH3, X = I (L1) R = CH2Ph, X = Br (L2) R = CH2CH=CH2, X = Br (L3)

R = CH3, X = I (1a) R = CH2Ph, X = Br (2a) R = CH2CH=CH2, X = Br (3a)

Cl Ag

Cl Ag

Me

Cl(CH2)6Cl C6H6
Me

Cl N N
6 N

Cl N Me

Ag 2 O MC/40 oC
N Me

6 N

Me

L4

4a

O H O

Ag2 O H 2O/60 oC 5b
O

O Ag

Scheme 1. Synthesis of the new Ag(I)NHC complexes (1a4a) and the reference complex Ag(I) hexanoate (5b).

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1.0 0.9 0.8 0.7

297

296

Inten sity (arb , un it)

296

intensity

0.6 0.5 0.4 0.3

309 304 303

[L1] [L2] [L3] [1a] [2a] [3a]

A g co m p le x (1 a ) A g co m p le x (2 a ) A g co m p le x (3 a )
A g (200)

A g (1 1 1 ) A g ( 0 0 6 ) A g (2 2 0 ) A g (2 2 2 )

A g (3 1 1 )

0.2 0.1 0.0 -0.1 260 280 300 320 340 360 380 400 420

20

40

60

80

2theta (deg.)
Fig. 3. XRD structure of the Ag(I)NHC complexes (1a3a).

wavelength (nm)
Fig. 1. UV absorption spectra of the NHC ligands (L1L3) and the Ag(I)NHC complexes (1a3a).

structure of the complex (Fig. 1). High-energy photoemission bands appeared at kmax = 352 nm for L1 and at kmax = 405 nm for 1a, indicating a red shift (Fig. 2) [50,51]. The same concentrations of the non-conjugated NHC ligand L4 and its silver complex 4a did not yield any noticeable absorption or emission band. Further structural characterization of the Ag complexes was provided by powder XRD data (Fig. 3). Their crystal structures show dominant small angle peaks, which are comparable to the characteristic peaks of N-alkylimidazolesilver complexes [52]. Other relatively big angle peaks are assigned to (1 1 1), (2 0 0), (3 1 1) and (2 2 0) reections in all the complexes. Specically, complex 3a shows additional peaks assigned to (0 0 6) and (2 2 2).

Table 2 ICP/TGA data of Ag(I)NHC (1a4a) and the reference complex Ag(I) hexanoate, 5b. Complex ICP (% of Ag content) Calculation 1a 2a 3a 4a 5b
a

TGAa (decomposition temperature, C) 10% 347.32 368.43 433.74 339.47 258.51 20% 423.53 412.57 454.39 351.15 276.00 Char yield 61.26 46.32 60.57 46.66 73.78

Experiment 28.25 22.97 27.63 40.42 46.33

28.39 22.23 28.02 40.48 48.37

TGA data was acquired in an N2 atmosphere at 10 C/min.

3.2. Conductivity of the silver pastes The conductivity (r) was calculated according to the general equation r = (I/V)(d/a), where I is the current in amperes and V is the potential drop across the sample of cross-sectional area a and thickness d. The silver paste with the highest conductivity was fabricated from complex 3a in EDA, as indicated in Table 2. ICP analyses revealed that the silver content was almost two times lower in 1a3a compared with that of 4a and the reference silver complex 5b. Because the solubilities of these complexes in EDA are similar, the high conductivity of 3a appears to be an intrinsic quality of the

120

351

100
355

358

80

intensity

410 401

[L1] [L2] [L3] [1a] [2a] [3a]

complex. Compound 3a also exhibited the highest 20% decomposition temperature, indicating that silver was effectively reduced upon thermal treatment of the paste, despite its low concentration. Ag2O, which is used as an additional source of silver in standard commercial processes, was added to the complex mixtures in an effort to increase the conductivity of the resulting pastes. Optimal mixture ratios for the paste and ink media were also considered. Reduction of Ag2O to Ag occurs at 250300 C [53], indicating that the low sintering temperatures used with silver pastes and inks may not be effective in the system of the silver material mixture. The commercial silver hexanoate 5b paste, as well as compounds 2a and 4a, showed an increase in conductivity, with the incorporation of up to 33% silver oxide. Interestingly, the addition of Ag2O resulted in a signicant drop in conductivity for pastes composed of 3a or 1a. This decrease may be due to the immiscibility between the complexes and EDA, combined with the shrinkage of the silver oxide particles upon sintering [54]. Additionally, SEM micrographs of the silver pastes in Fig. 4 showed no correlation between heat treatment, surface smoothness and conductivity. Thus, the silver content of the paste, the degree of reducibility of the Ag complex, and the degree of homogeneity of the paste or ink are crucial factors in determining the electrical conductivity. 4. Conclusions New Ag(I)NHC complexes were synthesized for use in electrically conductive silver pastes. Although these new materials contained low concentrations of silver, relative to common commercial materials in silver pastes and inks, they each exhibited relatively high thermal stability and moderate conductivity. The conductivity of a conjugated bis-NHCAg complex was higher than that of a non-conjugated bidentate NHCAg complex or a commercial silver salt, thus demonstrating its potential in industrially relevant electrically conductive pastes.

60
406

40

20

0 200 300 400 500 600 700

wavelength (nm)
Fig. 2. Photoemission spectra of the NHC ligands (L1bL3) and the Ag(I)NHC complexes (1a3a).

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Fig. 4. SEM micrographs of silver pastes on glass substrates after sintering.

Acknowledgments The authors are grateful to the BK21 programs of Korea University and Kyungpook National University supported by LG Chem. Ltd. This work was supported by the Nuclear R&D Programs through the National Research Foundation of Korea (NRF) funded by Ministry of Education, Science and Technology (Grant No. 2010-0018535).

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