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Publicly Available Published by De Gruyter June 21, 2013

Photoinduced charge separation in a PtII acetylide donor–acceptor triad based on 2-(1-pyrazole)-pyridine modified with naphthalene mono-imide electron acceptor

Igor V. Sazanovich , Mohammed A. H. Alamiry , Anthony J. H. M. Meijer , Michael Towrie , E. Stephen Davies , Robert D. Bennett and Julia A. Weinstein

A class of molecular electron transfer cascades—those based on PtII complexes of 2-(1-pyrazole)-pyridine (pzpy) ligands—are reported. The synthesis of a new electron-acceptor imide-modified pzpy ligands is reported, and their application to transition-metal chemistry demonstrated by the synthesis of the PtII chloride and acetylide complexes. These donor–acceptor assemblies are promising models for investigation of photoinduced charge separation. Accordingly, picosecond time-resolved infrared (TRIR) and femtosecond transient absorption (TA) studies have been undertaken to elucidate the nature and dynamics of the lowest excited states in Pt(NAP-pyr-pyrazole)(–CC–Ph–C7H15)2. It has been established that the initial population of an MLL'CT excited state in the chromophoric [Pt(pyridine-pyrazole)(acetylide)] core is followed by an electron transfer to the naphthalimide (NAP) acceptor, forming a charge-separated state. This state is characterized by a large shift in ν(CO) vibrations of the NAP acceptor, as well as by a very intense and broad [×10 times in comparison to ν(CO)] asymmetric acetylide stretch which incorporates –CC–Pt–CC– framework and occurs at approximately 300 cm–1 lower in energy than its ground-state counterpart. In CH2Cl2 at room temperature, the charge-separated state with the lifetime of 150 ps collapses into an almost isoenergetic NAP-localized triplet state; the rate of this transformation changes upon decreasing the temperature to 263 K. This final excited state, 3NAP-(pyr-pyrazole)Pt(–CC–Ph–C7H15)2, has an unusually long, for PtII complexes, excited-state lifetime of tens of microseconds. The work demonstrates the possibility of tuning excited-state properties in this new class of PtII chromophores designed for electron-transfer cascades.


Conference

IUPAC Symposium on Photochemistry, International Symposium on Photochemistry, PHOTO, Photochemistry, XXIVth, Coimbra, Portugal, 2012-07-15–2012-07-20


References

1 10.1126/science.1172247, R. Eisenberg. Science324, 44 (2009).Search in Google Scholar PubMed

2 10.1021/ic050904r, J. H. Alstrum-Acevedo, M. K. Brennaman, T. J. Meyer. Inorg. Chem.44, 6802 (2005).Search in Google Scholar PubMed

3 10.1021/ic0505605, S. Chakraborty, T. J. Wadas, H. Hester, R. Schmehl, R. Eisenberg. Inorg. Chem.44, 6865 (2005).Search in Google Scholar PubMed

4 10.1016/j.ccr.2012.07.010, S. Archer, J. A. Weinstein. Coord. Chem. Rev. 2530 (2012).Search in Google Scholar

5 10.1021/ic034026d, J. E. McGarrah, R. Eisenberg. Inorg. Chem.42, 4355 (2003).Search in Google Scholar PubMed

6 10.1039/b503794h, U. Siemeling, K. Bausch, H. Fink, C. Bruhn, M. Baldus, B. Angerstein, R. Plessow, A. Brockhinke. Dalton Trans. 2365 (2005).Search in Google Scholar PubMed

7 10.1021/ic048886l, T. J. Wadas, S. Chakraborty, R. J. Lachicotte, Q. M. Wang, R. Eisenberg. Inorg. Chem.44, 2628 (2005).Search in Google Scholar PubMed

8 10.1021/ic048573q, C. Monnereau, J. Gomez, E. Blart, F. Odobel, S. Wallin, A. Fallberg, L. Hammarstrom. Inorg. Chem.44, 4806 (2005).Search in Google Scholar PubMed

9 10.1073/pnas.1212254109, J. J. Concepcion, R. L. House, J. M. Papanikolas. Proc. Natl. Acad. Sci. USA109, 15560 (2012).Search in Google Scholar PubMed PubMed Central

10 10.1021/ja711090w, P. Du, J. Schneider, F. Li, W. Zhao, U. Patel, F. N. Castellano, R. Eisenberg. J. Am. Chem. Soc.130, 5056 (2008).Search in Google Scholar PubMed

11 10.1021/ic060102b, F. Hua, S. Kinayyigit, J. R. Cable, F. N. Castellano. Inorg. Chem.45, 4304 (2006).Search in Google Scholar

12 10.1016/S0022-328X(98)01106-1, V. W.-W. Yam, K. Kam-Wing Lo, K. Man-Chung Wong. J. Organomet. Chem.578, 3 (1999).Search in Google Scholar

13 10.1007/s11164-012-0642-6, R. Sugimura, S. Suzuki, M. Kozaki, K. Keyaki, K. Nozaki, H. Matsushita, N. Ikeda, K. Okada. Res. Chem. Intermed.39, 185 (2013).Search in Google Scholar

14 M. L. Muro, A. A. Rachford, X. H. Wang, F. N. Castellano. In Photophysics of Organometallics, A. J. Lees (Ed.), Topics in Organometallic Chemistry29, 159 (2010).Search in Google Scholar

15 10.1246/bcsj.54.1191, Y. Nagao, T. Misono. Bull. Chem. Soc. Japan54, 1191 (1981).Search in Google Scholar

16 10.1016/S0040-4039(99)01468-9, Y. Zhao, M. R. Wasielewski. Tetrahedron Lett.40, 7047 (1999).Search in Google Scholar

17 10.1016/S0040-4020(00)00452-X, H. Langhals, R. Ismael, O. Yuruk. Tetrahedron56, 5435 (2000).Search in Google Scholar

18 10.1016/S0040-4020(03)00020-6, K.-Y. Tomizaki, P. Thamyongkit, R. S. Loewe, J. S. Lindsey. Tetrahedron59, 1191 (2003).Search in Google Scholar

19 10.1039/b401630k, F. Würthner. Chem. Commun. 1564 (2004).Search in Google Scholar PubMed

20 10.1016/j.tetlet.2004.12.094, J. Wu, J. Qu, N. Tchebotareva, K. Müllen. Tetrahedron Lett.46, 1565 (2006).Search in Google Scholar

21 10.1021/jp000706f, D. Gosztola, M. P. Niemczyk, W. Svec, A. S. Lukas, M. R. Wasielewski. J. Phys. Chem. A104, 6545 (2000).Search in Google Scholar

22 10.1071/CH04130, G. Andric, J. F. Boas, A. M. Bond, G. D. Fallon, K. P. Ghiggino, C. F. Hogan, J. A. Hutchison, M. A.-P. Lee, S. J. Langford, J. R. Pilbrow, G. J. Troup, C. P. Woodward. Aust. J. Chem.57, 1011 (2004).Search in Google Scholar

23 10.1021/ic971446s, D. W. Dixon, N. B. Thornton, V. Steullet, T. Netzel. Inorg. Chem.38, 5526 (1999).Search in Google Scholar PubMed

24 10.1135/cccc20010307, M. D. Hossain, M.-A. Haga, B. Gholamkhass, K. Nozaki, M. Tsushima, N. Ikeda, T. Ohno. Collect. Czech. Chem. Commun.66, 307 (2001).Search in Google Scholar

25 10.1039/c2dt30765k, F. N. Castellano. Dalton Trans.41, 8493 (2012).Search in Google Scholar PubMed

26 10.1039/b308101j, O. Johansson, H. Wolpher, M. Borgström, L. Hammarström, J. Bergquist, L. Sun, B. Akermark. Chem. Commun. 194 (2004).Search in Google Scholar PubMed

27 10.1021/ja045379u, A. Prodi, C. Chiorboli, F. Scandola, E. Iengo, E. Alessio, R. Dobrawa, F. Würthner. J. Am. Chem. Soc.127, 1454 (2005).Search in Google Scholar PubMed

28 10.1002/chem.200600002, L. Flamigni, E. Baranoff, J.-P. Collin, J.-P. Sauvage. Chem.—Eur. J.12, 6592 (2006).Search in Google Scholar PubMed

29 10.1039/b208582h, F. Würthner, A. Sautter. Org. Biomol. Chem.1, 240 (2003).Search in Google Scholar PubMed

30 10.1021/jo048239b, C. Addicott, I. Oesterling, T. Yamamoto, K. Müllen, P. J. Stang. J. Org. Chem.70, 797 (2005).Search in Google Scholar PubMed

31 10.1021/ja0448216, A. Sautter, B. K. Kaletas, D. G. Schmid, R. Dobrawa, M. Zimine, G. Jung, I. H. M. van Stokkum, L. De Cola, R. M. Williams, F. Würthner. J. Am. Chem. Soc.127, 6719 (2005).Search in Google Scholar PubMed

32 10.1016/S0020-1693(03)00152-X, E. M. McGale, R. E. Murray, C. J. McAdam, J. L. Morgan, B. H. Robinson, J. Simpson. Inorg. Chim. Acta352, 129 (2003).Search in Google Scholar

33 10.1016/j.ica.2004.12.013, C. J. McAdam, A. R. Manning, B. H. Robinson, J. Simpson. Inorg. Chim. Acta358, 1673 (2005).Search in Google Scholar

34 10.1021/ic801022h, I. V. Sazanovich, M. A. H. Alamiry, J. Best, R. D. Bennett, O. V. Bouganov, E. S. Davies, V. P. Grivin, A. J. H. M. Meijer, V. F. Plyusnin, K. L. Ronayne, S. A. Tikhomirov, M. Towrie, J. A. Weinstein. Inorg. Chem.47, 10432 (2008).Search in Google Scholar

35 10.1021/ic3011184, S. F. Parker, K. Refson, R. D. Bennett, J. Best, M. Ya. Mel’nikov, J. A. Weinstein. Inorg. Chem.51, 9748 (2012).Search in Google Scholar

36 10.1016/S0020-1693(00)85025-2, N. Saha, D. Bhattacharyya, S. K. Kar. Inorg. Chim. Acta67, L37 (1982).Search in Google Scholar

37 10.1039/dt9960004055, R. J. Less, J. L. M. Wicks, N. P. Chatterton, M. J. Dewey, N. L. Cromhout, M. A. Halcrow, J. E. Davies. J. Chem. Soc., Dalton Trans. 4055 (1996).Search in Google Scholar

38 10.1016/0277-5387(96)00063-0, A. Gelling, K. G. Orrell, A. G. Osborne, V. Sik, M. B. Hursthouse, S. J. Coles. Polyhedron15, 3203 (1996).Search in Google Scholar

39 10.1021/ic035066k, S. A. Willison, H. Jude, R. M. Antonelli, J. M. Rennekamp, N. A. Eckert, J. A. K. Bauer, W. B. Connick. Inorg. Chem.43, 2548 (2004).Search in Google Scholar PubMed

40 N. Adhikari, N. Saha. Asian J. Chem.20, 521 (2008).Search in Google Scholar

41 10.1016/j.poly.2008.12.013, E. Budzisz, M. Miernicka, I.-P. Lorenz, P. Mayer, U. Krajewska, M. Rozalski. Polyhedron28, 637 (2009).Search in Google Scholar

42 10.1007/BF00899253, M. A. Khan, A. A. A. Pinto. Monatsh. Chem.111, 883 (1980).Search in Google Scholar

43 10.1016/S0040-4039(00)00849-2, X.-J. Wang, J. Tan, K. Grozinger, R. Betageri, T. Kirrane, J. R. Proudfoot. Tetrahedron Lett.41, 5321 (2000).Search in Google Scholar

44 10.1021/ic50112a025, J. H. Price, A. N. Williamson, R. F. Schramm, B. B. Wayland. Inorg. Chem.11, 1280 (1972).Search in Google Scholar

45 10.1016/S0022-328X(00)84078-4, K. Sonogashira, Y. Fujikura, T. Yatake, N. Toyoshima, S. Takahashi, N. Hagihara. J. Organomet. Chem.145, 101 (1978).Search in Google Scholar

46 10.1039/a907028a, C. J. Adams, S. L. James, X. Liu, P. R. Raithby, L. J. Yellowlees. J. Chem. Soc., Dalton Trans. 63 (2000).Search in Google Scholar

47 10.1002/1521-3765(20011001)7:19<4180::AID-CHEM4180>3.0.CO;2-9, S. C. Chan, M. C. W. Chan, Y. Wang, C. M. Che, K. K. Cheung, N. Zhu. Chem.—Eur. J.7, 4180 (2001).Search in Google Scholar

48 10.1016/j.ccr.2006.03.007, F. N. Castellano, I. E. Pomestchenko, E. Shikhova, F. Hua, M. L. Muro, N. Rajapakse. Coord. Chem. Rev.250, 1819 (2006).Search in Google Scholar

49 10.1021/ic991250n, M. Hissler, W. B. Connick, D. K. Geiger, J. E. McGarrah, D. Lipa, R. J. Lachicotte, R. Eisenberg. Inorg. Chem.39, 447 (2000).Search in Google Scholar

50 10.1039/b411341a, N. M. Shavaleev, Z. R. Bell, T. L. Easun, R. Rutkaite, L. Swanson, M. D. Ward. Dalton Trans. 3678 (2004).Search in Google Scholar

51 10.1021/ic00082a017, T. K. Aldridge, E. M. Stacy, D. R. McMillin. Inorg. Chem.33, 722 (1994).Search in Google Scholar

52 10.1021/ic0102182, C. E. Whittle, J. A. Weinstein, M. W. George, K. S. Schanze. Inorg. Chem.40, 4053 (2001).Search in Google Scholar

53 10.1021/ic800850h, C. J. Adams, N. Fey, Z. A. Harrison, I. V. Sazanovich, M. Towrie, J. A. Weinstein. Inorg. Chem.47, 8242 (2008).Search in Google Scholar PubMed

54 10.1021/ic800578h, E. A. Glik, S. Kinayyigit, K. L. Ronayne, M. Towrie, I. V. Sazanovich, J. A. Weinstein, F. N. Castellano. Inorg. Chem.47, 6974 (2008).Search in Google Scholar PubMed

55 10.1016/j.ccr.2006.12.002, J. M. Butler, M. W. George, J. R. Schoonover, D. M. Dattelbaum, T. J. Meyer. Coord. Chem. Rev.251, 492 (2007).Search in Google Scholar

56 10.1039/b109919a, J. A. Weinstein, D. C. Grills, M. Towrie, P. Matousek, A. W. Parker, M. W. George. Chem. Comm. 382 (2002).Search in Google Scholar PubMed

57 10.1146/annurev.pc.42.100191.000503, T. Elsaesser, W. Kaiser. Annu. Rev. Phys. Chem.42, 83 (1991).Search in Google Scholar

58 10.1126/science.289.5481.935, A. T. Yeh, C. V. Shank, J. K. McCusker. Science289, 935 (2000).Search in Google Scholar PubMed

59 10.1002/anie.200600125, A. Cannizzo, F. van Mourik, W. Gawelda, G. Zgrablic, C. Bressler, M. Chergui. Angew. Chem., Int. Ed.45, 3174 (2006).Search in Google Scholar PubMed

60 10.1021/jp045269+, E. O. Danilov, I. E. Pomestchenko, S. Kinayyigit, P. L. Gentili, M. Hissler, R. Ziessel, F. N. Castellano. J. Phys. Chem. A109, 2465 (2005).Search in Google Scholar PubMed

61 10.1021/jp807176y, G. Ramakrishna, T. Goodson III, J. E. Rogers-Haley, T. M. Cooper, D. G. McLean, A. Urbas. J. Phys. Chem. C113, 1060 (2009).Search in Google Scholar

62 10.1021/ic702454k, A. A. Rachford, S. Goeb, R. Ziessel, F. N. Castellano. Inorg. Chem.47, 4348 (2008).Search in Google Scholar PubMed

63 10.1039/ft9949000411, V. Wintgens, P. Valat, J. Kossanyi, L. Biczok, A. Demeter, T. Bérces. J. Chem. Soc., Faraday Trans.90, 411 (1994).Search in Google Scholar

64 10.1021/ja971993c, B. M. Aveline, S. Matsugo, R. W. Redmond. J. Am. Chem. Soc.119, 11785 (1997).Search in Google Scholar

65 10.1021/ja9841299, J. E. Rogers, L. A. Kelly. J. Am. Chem. Soc.121, 3854 (1999).Search in Google Scholar

66 10.1366/00037020360625899, M. Towrie, D. C. Grills, J. Dyer, J. A. Weinstein, P. Matousek, R. Barton, P. D. Bailey, N. Subramaniam, W. M. Kwok, C. S. Ma, D. Phillips, A. W. Parker, M. W. George. Appl. Spectrosc.57, 367 (2003).Search in Google Scholar

67 10.1366/000370210793561673, G. M. Greetham, P. Burgos, Q. Cao, I. P. Clark, P. S. Codd, R. C. Farrow, M. W. George, M. Kogimtzis, P. Matousek, A. W. Parker, M. R. Pollard, D. A. Robinson, Z.-J. Xin, M. Towrie. Appl. Spectrosc.64, 1311 (2010).Search in Google Scholar

68 K. L. Ronayne, M. Towrie. In Central Laser Facility Annual Report 2006–2007, B. Wyborn (Ed.), pp. 192–193, Ampersand Design, Ardington, UK (2007).Search in Google Scholar

69 M. Towrie, A. W. Parker, K. L. Ronayne, S. Manolopoulos, S. Martin, P. Seller. In Central Laser Facility Annual Report 2004–2005, B. Wyborn (Ed.), pp. 235–236, RAL Reprographics Section, Didcot, UK (2005).Search in Google Scholar

70 M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. J. A. Montgomery, J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, Ö. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, D. J. Fox. Gaussian 09, Revision A.2, Gaussian, Inc., Wallingford CT (2009).Search in Google Scholar

71 10.1002/spe.626, R. C. Whaley, A. Petitet. Software: Practice Experience35, 10 (2005).Search in Google Scholar

72 10.1016/S0167-8191(00)00087-9, R. C. Whaley, A. Petitet, J. J. Dongarra. Parallel Computing27, 3 (2001).Search in Google Scholar

73 10.1063/1.464913, A. D. Becke. J. Chem. Phys.98, 5648 (1993).Search in Google Scholar

74 10.1063/1.438980, A. D. McLean, G. S. Chandler. J. Chem. Phys.72, 5639 (1980).Search in Google Scholar

75 10.1063/1.438955, R. Krishnan, J. S. Binkley, R. Seeger, J. A. Pople. J. Chem. Phys.72, 650 (1980).Search in Google Scholar

76 10.1063/1.1406535, X. Y. Cao, M. Dolg. J. Chem. Phys.115, 7348 (2001).Search in Google Scholar

77 10.1063/1.468948, A. Nicklass, M. Dolg, H. Stoll, H. Preuss. J. Chem. Phys.102, 8942 (1995).Search in Google Scholar

78 10.1021/ic201914h, S. P. Foxon, C. Green, M. Walker, A. Wragg, H. Adams, J. A. Weinstein, S. C. Parker, A. J. H. M. Meijer, J. A. Thomas. Inorg. Chem.51, 463 (2012).Search in Google Scholar

79 J. A. Thomas, H. Ahmad, A. J. H. M. Meijer. Chem. Asian J.6, 2339 (2011).Search in Google Scholar

80 10.1039/c2dt31001e, A. B. Wragg, S. Derossi, T. L. Easun, M. W. George, X.-Z. Sun, F. Hartl, A. H. Shelton, A. J. H. M. Meijer, M. D. Ward. Dalton Trans.41, 10354 (2012).Search in Google Scholar

81 10.1063/1.473558, B. Mennucci, J. Tomassi. J. Chem. Phys.106, 5151 (1997).Search in Google Scholar

82 10.1016/S0009-2614(98)00106-7, M. Cossi, V. Barone, B. Menucci, J. Tomassi. Chem. Phys. Lett.286, 253 (1998).Search in Google Scholar

83 10.1002/jcc.20823, N. M. O’Boyle, A. L. Tenderholt, K. M. Langner. J. Comput. Chem.29, 839 (2008).Search in Google Scholar PubMed

84 10.1021/jp052793n, K. K. Irikura, R. D. Johnson, R. N. Kacker. J. Phys. Chem. A109, 8430 (2005).Search in Google Scholar PubMed

85 Jmol: an open-source Java viewer for chemical structures in 3D. http://www.jmol.org/ [last accessed: 21 May 2013].Search in Google Scholar

86 Povray: Persistence of Vision Pty. Ltd. (2004). Persistence of Vision Raytracer (Version 3.6) [Computer software]. Retrieved from http://www.povray.org/download/ [last accessed 21 May 2013].Search in Google Scholar

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