The new complexes [Ru(NO)(PPh3)](2)(eta(2)-C-m)(m=60 1 or 70 2) have been prepared by heating a solution of C-60(or C-70) with [Ru(NO)(2)(PPh3)(2)] in toluene. They have been characterized by elemental analysis, IR, UV/VIS, XPS, C-13 and P-31 NMR spectroscopy. The photovaltaic effect for the new compounds has been studied

Cheng, DD

Dong, ZR

Lin, YS

Wu, ZY

Yang, SG

Zhan, MX

詹梦熊

Chinese Chemical Letters

Xiamen University Institutional Repository

Chinese Chemical Letters Vol. 13, No. 12, pp 1209 – 1212, 2002 http://www.imm.ac.cn/journal/ccl.html  1209New Ruthenium Complexes of Fullerene C60&C70 Da Dian CHENG, Zhen Rong DONG, Zhen Yi WU, Yong Sheng LIN, Sen Gen YANG Meng Xiong ZHAN*  Department of Chemistry, Xiamen University, Xiamen 361005   Abstract: The new complexes [Ru(NO)(PPh3)]2(η2-Cm)(m=60 1 or 70 2) have been prepared by heating a solution of C60(or C70) with [Ru(NO)2(PPh3)2] in toluene.  They have been characterized by elemental analysis, IR, UV/VIS, XPS, 13C and 31P NMR spectroscopy.  The photovaltaic effect for the new compounds has been studied.  Keywords: Fullerene, ruthenium complex, photovaltaic effect.   Since subsequent development of the large-scale synthesis of fullerenes1, the fullerene coordination chemistry has played an important role. In the previous studies2, a number of metallo-C60 derivatives have been synthesized, but it was unsuccessful for A. N. Chernega et al. to attach some fragments to C60, after heating a solution containing equimolar amounts of either [RuH(Cl)(PPh3)3] or [RhCl(PPh3)3] and C60 in toluene at 50°C for 1 week, they found no reaction occurred; they also found C60 was unreactive towards [RuH2(CO)(PPh3)3] and [Ru(NO)2(PPh3)2], the electron richness of the fragments was considered as a reason of the lack of reactivity. Recently we found that above mentioned fragments could react with fullerenes in reflux toluene. This paper describes the preparation and characterization of new ruthenium complexes of fullerene C60&C70, which were synthesized via the reactions of [Ru(NO)2(PPh3)2] with the fullerene C60&C70.   Experimental  All manipulations were performed under nitrogen atmosphere.  The complex [Ru(NO)2 (PPh3)2] was prepared according to the literature3. Elemental analysis was recorded on a Carlo Erba-1110 elemental analyzer.  Infrared spectra were recorded on a Nicolet AVATAR FT-IR360 spectrometer using KBr pellets.  The UV/VIS electronic spectra were recorded on a UVIKON UV-240 spectrometer.  X-ray photoelectron spectroscopy (XPS) were recorded on a VGESCAB  MK II spectrometer, 13C and 31P NMR spectra were obtained on a Varian UNITY                                                    *E-mail: kanzhu@xmu.edu.cn Da Dian CHENG et al. 1210plus-500 spectrometer in solution. General procedure for synthesis  A solution of Cm (m=60 or 70) in toluene (20 mL) was added to a solution of [Ru(NO)2(PPh3)2] in toluene (5 mL).  The mixture was refluxed with stirring for 18 h, then kept at ~90°C and stirred for another 6 h.  Volume of the reaction mixture was reduced to 5 mL by evaporation and the product precipitated by addition of n-hexane (50 mL).  The solid was filtrated and washed with n-hexane (3 × 10 mL), dried in vacuo. [Ru(NO)(PPh3)]2(η2-C60) 1. Yield 32 mg, 67%. (Found: C, 76.89; H, 1.45; N, 1.86. Calcd. for [Ru(NO)(PPh3)]2(η2-C60): C, 76.49; H, 1.99; N, 1.86%); IR (cm-1): 1828s, 1721vs, 1690vs (νNO); 1182m，574m，522s [ν(C60)]. UV/VIS (toluene): λmax/nm 435, 599, 650. XPS (Ru): EB/eV 280.6. 31P NMR (solvent CDCl3, δppm): 29.8 (s PPh3).  13C NMR (solvent CDCl3+CS2, δppm): 146.2, 144.7, 144.4, 143.9, 142.9, 142.3(s, C60), 133.5(d, PPh3), 131.9, 131.6, 131.0, 128.9, 128.8(s, PPh3), 128.2(d, PPh3). [Ru(NO)(PPh3)]2(η2-C70) 2. Yield 31 mg, 56%. (Found: C, 78.58; H, 1.37; N, 1.69. Calcd. for [Ru(NO)(PPh3)]2(η2-C70): C, 78.24; H, 1.85; N, 1.72%); IR (cm-1): 1831m, 1723vs, 1691vs (νNO); 1430s, 794m, 641m, 575m ， 536s [ν(C70)]; 419w [ν (Ru-(η2-C=C))]. XPS (Ru): EB/eV 281.0. 13C NMR (solvent CS2+CDCl3, δppm): 150.2, 147.7, 147.0, 145.0, 130.5(C70); 131.9, 131.8, 131.6, 128.8, 128.2, 128.1, 128.0, 125.1 (PPh3); 115.0(sp3C, C70).   Results and Discussion  The synthesis reaction can be expressed as follows:   Cm+Ru(NO)2(PPh3)2[Ru(NO)(PPh3)]2(η2-Cm)(m=60 1 or 70 2)  The IR spectrum of the compound 1 showed the bands of C60 at 522, 574 and 1182 cm-1, the spectrum of the compound 2 showed the bands of C70 at 536, 575, 641, 794 and 1430 cm-1. ν(NO) at 1690, 1721 cm-1 and 1691, 1723 cm-1 respectively, typical absorption for the linear MNO system.  These values of ν(NO) were higher than that of  [Ru(NO)2(PPh3)2] (1656 and 1614 cm-1).  It suggested that owing to the hypercon jugation of Cm-Ru-NO-P-Ph, the electronic consistency on the N=O bond increased, the values of ν(NO) turned higher, the electrons moved easily.  There is a new band at around 1830 cm-1 in both IR spectra of the two compounds.  The UV/VIS spectrum of compound 1 showed a band at 435 nm and two weak and broad bands at 599 and 650 nm exhibiting considerably less fine structure than for uncoordinated C60.  These data were typical for fullerene cage which has been modified by complexation4,5.  The XPS spectra of 1 and 2 showed the peak at 280.6 eV and 281.0 eV, respectively.  It is higher than that of [Ru(NO)2(PPh3)2](280.2 eV).  The result suggested that the d electrons of Ru flowed to fullerenes to form π bonds, as a result, the valence of Ru increased.  The 31P NMR spectrum of 1 contained a singlet resonance at δ 29.8, for comparison, the 31P NMR spectrum of [Ru(NO)2(PPh3)2] showed a singlet at δ 54.8.  It suggested that the electronic consistency around the P nuclear increased as a result of the hyperconjugation of the new compound.  The 13C NMR of compound 1 showed a further 6 peaks New Ruthenium Complexes of Fullerene C60&C70 1211assignable to the C60 moiety.  No more resonance of C60 was detected because of the low solubility of the compound.  The 13C NMR of compound 2 showed a 6 resonances due to C70, the resonance at δ 115.0 is lower than normal sp3 C, it suggested that the electrons of the sp3 C flowed to the metal Ru because of forming σ bond. The characterization data showed that electrons would transfer easier in the new molecule than in the reagents because of the hyperconjugation effect, so the good photovaltaic effect was expected.  The opening circuit voltage was recorded on a Pz-8 direct current voltage meter.  A FL-35 Xenon lamp was used to illuminate the samples.  The photovoltaic effect (PVE) of the new complexes was observed in a conventional three-electrode cell.  A complex film-GaAs disk was used as the working electrode; a Pt disk (1 cm2) was used as the subsidiary electrode and a saturated calomel electrode as the reference electrode.  The complex was deposited on the working electrode with the solvent method.  The illumination intensity was 0.050 w/cm2.  Under the dark and illuminated states, the PVE was measured, the photogenerated voltage (∆V) was obtained and listed in the Table 1. As expected, PVE of the complexes plated GaAs electrode was increased.  The effect became best when the thickness of the complex film was around 1 µm, then it decreased with increasing the thickness of the film.  The reason was that the electric resistance was increasing with the increasing of the thickness of the film.  The solution of I2/I3- was the best medium for the test of photovoltaic effect.  And the ∆V for the complex of C70 was higher than that of C60, because there were more hexahedron webs and more photo quantum effect for C70 than for C60.  Table 1  ∆V of the new compounds                             thickness of the complex film (µm) medium    0    0.5   1.0   2.0   3.0   4.0 O2/H2O (0.1 mol/L KCl) 310 354a 385b 358a 430b 341a 392b 302a 354b 283a 303b BQ/H2Q (0.01 mol/L) 265 280a 305b 285a 324b 306a 276b 293a 258b 257a 244b Fe(CN)63-/ Fe(CN)64-(0.1 mol/L) 347 402a 417b 408a 395b 413a 392b 397a 381b 366a 357b ∆V (mV) I2(0.001mol/L)/I3- (0.1m0l/L) 268 358a 385b 387a 401b 322a 414b 293a 387b 262a 312b  a ∆V of C60[Ru(NO)(PPh3)]2. b ∆V of C70[Ru(NO)(PPh3)]2.   Acknowledgments  We wish to express our gratitude for the financial support of this work by the Doctor program of Higher Education of China (No. 98038410), Natural Science Foundation of Fujian (No. E0110001) and Self-select program of Xiamen University.     Da Dian CHENG et al. 1212References  1. (a)H. W. Kroto, J. R. Heath, S. C. O’Brein, R. F. Curl, R. E. Smalley, Nature, 1985, 318, 162. (b)W. Krätschmer, L. D. Lamb, K. Fostiropoulos, D. R. Huffman, Nature, 1990, 347, 354.  (c) W. Krätschmer, K. Fostiropoulos, D. R. Huffman, Chem. Phys. Lett., 1990, 170, 167. 2.  (a)K. Tang, S. Zheng, X. Jin, H. Zeng, Z. Gu, X. Zhou, Y. Tang, J. Chem. Soc. Dalton Trans., 1997, 3585. (b) A. N. Chernega, M. L. H. Green, J. Haggitt, A. H. H. Stephens, J. Chem. Soc. Dalton Trans., 1998, 755. 3.  Parshall G.W., Translated by W Ma, P. S. Pan, Z. K. Xiong et al, Inorganic Synthesis, Beijing: Science Press, 1986, 52. 4.  J. P. Hare, H. W. Kroto, R. Taylor, Chem. Phys. Lett., 1991, 177, 394. 5.  T. Akasaka, W. Ando, K. Kobayashi, S. Nagase, J. Am. Chem. Soc., 1993, 115, 1605.  Received 12 March, 2002 

New ruthenium complexes of fullerene C-60&C-70

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New ruthenium complexes of fullerene C-60&C-70

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