Navegar

Colección

Datos Estadísticas

Artículo

El editor solo permite decargar el artículo en su versión post-print desde el repositorio. Por favor, si usted posee dicha versión, enviela a
Consulte el artículo en la página del editor
Consulte la política de Acceso Abierto del editor

Abstract:

We report here the spectroscopic properties of four very closely related mixed-valence cyanide-bridged bimetallic complexes, trans-[Ru(T)(bpy)(μ-NC) Ru(L)4(CN)]3+ (T = tris(1-pyrazolyl)methane (tpm, a) or 2,2′;6′,2″-terpyridine, (tpy, b), and L = pyridine (py, 1) or 4-methoxypyridine (MeOpy, 2)). In acetonitrile all the complexes present intervalence charge transfer (IVCT) transitions in the NIR region, but their intensities are widely different, with the intensity of the transition observed for 1a-b3+ around four times larger than that observed for 2a-b 3+. This contrasting behavior can be traced to the different nature of the dπ acceptor orbitals involved in these transitions, as confirmed by (TD)DFT calculations. The spectroscopy of 1a-b3+ provides evidence that the spin density is delocalized over the two ruthenium ions, such as a narrowing of the IVCT bands that results in the resolution of the expected three bands, and a weak solvent dependence of the energy of these transitions. The spectroscopy of 2a-b3+ instead indicates that the spin density is localized on one ruthenium ion. The IVCT in these systems is particularly weak due to the configuration of the Ru(III), where the vacant orbital is perpendicular to the cyanide bridge. © 2014 American Chemical Society.

Registro:

Documento: Artículo
Título:Influence of the electronic configuration in the properties of d 6-d5 mixed-valence complexes
Autor:Pieslinger, G.E.; Aramburu-Trošelj, B.M.; Cadranel, A.; Baraldo, L.M.
Filiación:Departamento de Química Analítica, Inorgánica y Química Física, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Pabellón 2, C1428EHA, Buenos Aires, Argentina
Año:2014
Volumen:53
Número:16
Página de inicio:8221
Página de fin:8229
DOI: http://dx.doi.org/10.1021/ic5002539
Título revista:Inorganic Chemistry
Título revista abreviado:Inorg. Chem.
ISSN:00201669
CODEN:INOCA
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v53_n16_p8221_Pieslinger

Referencias:

  • Creutz, C., Taube, H., (1969) J. Am. Chem. Soc., 91, pp. 3988-3989
  • Endicott, J.F., Chen, Y.-J., (2013) Coord. Chem. Rev., 257, pp. 1676-1698
  • Shatruk, M., Avendaño, C., Dunbar, K.R., (2009) Progress in Inorganic Chemistry, 56, pp. 155-334. , John Wiley & Sons, Inc. Hoboken, NJ
  • Rossi, M.B., Abboud, K.A., Alborés, P., Baraldo, L.M., (2010) Eur. J. Inorg. Chem., pp. 5613-5616
  • Pieslinger, G.E., Alborés, P., Slep, L.D., Baraldo, L.M., (2014) Angew. Chem., Int. Ed., 53, pp. 1293-1296
  • Hush, N.S., (1967) Prog. Inorg. Chem., 8, pp. 391-444
  • Hush, N.S., (1968) Electrochim. Acta, 13, pp. 1005-1023
  • Sutin, N., (1983) Prog. Inorg. Chem., 30, pp. 441-498
  • Marcus, R.A., Sutin, N., (1985) Biochim. Biophys. Acta, 811, pp. 265-322
  • Neyhart, G.A., Timpson, C.J., Bates, W.D., Meyer, T.J., (1996) J. Am. Chem. Soc., 118, pp. 3730-3737
  • Demadis, K.D., Hartshorn, C.M., Meyer, T.J., (2001) Chem. Rev., 101, pp. 2655-2685
  • Concepcion, J.J., Dattelbaum, D.M., Meyer, T.J., Rocha, R.C., (2008) Philos. Trans. Ser. A, 366, pp. 163-175
  • Rocha, R.C., Rein, F.N., Jude, H., Shreve, A.P., Concepcion, J.J., Meyer, T.J., (2008) Angew. Chem., Int. Ed., 47, pp. 503-506
  • Llobet, A., Doppelt, P., Meyer, T.J., (1988) Inorg. Chem., 27, pp. 514-520
  • Takeuchi, K.J., Thompson, M.S., Pipes, D.W., Meyer, T.J., (1984) Inorg. Chem., 23, pp. 1845-1851
  • Coe, B.J., Meyer, T.J., White, P.S., Meyer, J.T.J., (1995) Inorg. Chem., 34, pp. 593-602
  • Pieslinger, G.E., Alborés, P., Slep, L.D., Coe, B.J., Timpson, C.J., Baraldo, L.M., (2013) Inorg. Chem., 52, pp. 2906-2917
  • Cadranel, A., Aramburu Trošelj, B.M., Yamazaki, S., Alborés, P., Kleiman, V.D., Baraldo, L.M., (2013) Dalton Trans., 42, pp. 16723-16732
  • Noviandri, I., Brown, K.N., Fleming, D.S., Gulyas, P.T., Lay, P.A., Masters, A.F., Phillips, L., (1999) J. Phys. Chem. B, 103, pp. 6713-6722
  • Kaim, W., Fiedler, J., (2009) Chem. Soc. Rev., 38, pp. 3373-3382
  • Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Scalmani, G., Fox, D.J., (2009) Gaussian 09 Rev. C.01, , Gaussian, Inc. Wallingford, CT
  • Szabo, A., Ostlund, N.S., (1989) Modern Quantum Chemistry: Introduction to Advanced Electronic Structure Theory, , McGraw-Hill: New York
  • Scalmani, G., Frisch, M.J., (2010) J. Chem. Phys., 132, p. 114110
  • Tomasi, J., Mennucci, B., Cammi, R., (2005) Chem. Rev., 105, pp. 2999-3093
  • Miertuš, S., Scrocco, E., Tomasi, J., (1981) Chem. Phys., 55, pp. 117-129
  • Schlegel, H.B., (1982) J. Comput. Chem., 3, pp. 214-218
  • Petit, L., Maldivi, P., Adamo, C., (2005) J. Chem. Theory Comput., 1, pp. 953-962
  • Stratmann, R., Scuseria, G., Frisch, M.J., (1998) J. Chem. Phys., 109, pp. 8218-8224
  • Flükiger, P., Lüthi, H.P., Portmann, S., Weber, J., MOLEKEL 4.3
  • Portmann, S., Luthi, H., (2000) Chimia, 54, pp. 766-770
  • Oboyle, N.M., Tenderholt, A.L., Langner, K.M., (2008) J. Comput. Chem., 29, pp. 839-845
  • Crosby, G.A., (1975) Acc. Chem. Res., 8, p. 231
  • Macatangay, A.V., Endicott, J.F., (2000) Inorg. Chem., 39, pp. 437-446
  • Kaemper, S., Paretzki, A., Fiedler, J., Zalis, S., Kaim, W., (2012) Inorg. Chem., 51, pp. 2097-2104
  • Braun-Sand, S.B., Wiest, O., (2003) J. Phys. Chem. A, 107, pp. 285-291
  • Lundberg, M., Siegbahn, P.E.M., (2005) J. Chem. Phys., 122, p. 224103
  • Zhang, Y., Yang, W., (1998) J. Chem. Phys., 109, pp. 2604-2608
  • Perdew, J.P., Levy, M., (1997) Phys. Rev. B, 56, pp. 16021-16028
  • Cohen, A.J., Mori-Sánchez, P., Yang, W., (2008) Science, 321, pp. 792-794
  • Vydrov, O.A., Scuseria, G.E., Perdew, J.P., (2007) J. Chem. Phys., 126, p. 154109
  • Robin, M.B., Day, P., (1968) Adv. Inorg. Chem. Radiochem., 10, p. 247
  • Kaduk, B., Kowalczyk, T., Van Voorhis, T., (2012) Chem. Rev., 112, pp. 321-370
  • Cai, Z.-L., Crossley, M.J., Reimers, J.R., Kobayashi, R., Amos, R.D., (2006) J. Phys. Chem. B, 110, pp. 15624-15632
  • Cohen, A.J., Mori-Sánchez, P., Yang, W., (2012) Chem. Rev., 112, pp. 289-320
  • Ma, X., Hu, S.-M., Tan, C.-H., Wen, Y.-H., Zhu, Q.-L., Shen, C.-J., Sheng, T.-L., Wu, X.-T., (2012) Dalton Trans., 41, pp. 12163-12169
  • Rossi, M.B., Alborés, P., Baraldo, L.M., (2011) Inorg. Chim. Acta, 374, pp. 334-340
  • Watzky, M.A., Macatangay, A.V., Vancamp, R.A., Mazzetto, S.E., Song, X.Q., Endicott, J.F., Buranda, T., (1997) J. Phys. Chem. A, 101, pp. 8441-8459
  • Timpson, C.J., Bignozzi, C.A., Sullivan, B.P., Kober, E.M., Meyer, T.J., (1996) J. Phys. Chem., 100, pp. 2915-2925
  • Dalessandro, D.M., Keene, F.R., (2006) Chem. Soc. Rev., 35, pp. 424-440
  • Watzky, M.A., Endicott, J.F., Song, X., Lei, Y., Macatangay, A.V., (1996) Inorg. Chem., 35, pp. 3463-3473
  • Rocha, R.C., Shreve, A.P., (2006) Chem. Phys., 326, pp. 24-32
  • Roncaroli, F., Baraldo, L.M., Slep, L.D., Olabe, J.A., (2002) Inorg. Chem., 41, pp. 1930-1939
  • Siddiqui, S., Henderson, W.W., Shepherd, R.E., (1987) Inorg. Chem., 26, pp. 3101-3107
  • Cutin, E.H., Katz, N.E., (1993) Polyhedron, 12, pp. 955-960
  • Laidlaw, W.M., Denning, R.G., (1994) J. Chem. Soc., Dalton Trans., pp. 1987-1994
  • Pfennig, B.W., Fritchman, V.A., Hayman, K.A., (2001) Inorg. Chem., 40, pp. 255-263
  • Sheng, T.-L., Vahrenkamp, H., (2004) Eur. J. Inorg. Chem., pp. 1198-1203

Citas:

---------- APA ----------
Pieslinger, G.E., Aramburu-Trošelj, B.M., Cadranel, A. & Baraldo, L.M. (2014) . Influence of the electronic configuration in the properties of d 6-d5 mixed-valence complexes. Inorganic Chemistry, 53(16), 8221-8229.
http://dx.doi.org/10.1021/ic5002539
---------- CHICAGO ----------
Pieslinger, G.E., Aramburu-Trošelj, B.M., Cadranel, A., Baraldo, L.M. "Influence of the electronic configuration in the properties of d 6-d5 mixed-valence complexes" . Inorganic Chemistry 53, no. 16 (2014) : 8221-8229.
http://dx.doi.org/10.1021/ic5002539
---------- MLA ----------
Pieslinger, G.E., Aramburu-Trošelj, B.M., Cadranel, A., Baraldo, L.M. "Influence of the electronic configuration in the properties of d 6-d5 mixed-valence complexes" . Inorganic Chemistry, vol. 53, no. 16, 2014, pp. 8221-8229.
http://dx.doi.org/10.1021/ic5002539
---------- VANCOUVER ----------
Pieslinger, G.E., Aramburu-Trošelj, B.M., Cadranel, A., Baraldo, L.M. Influence of the electronic configuration in the properties of d 6-d5 mixed-valence complexes. Inorg. Chem. 2014;53(16):8221-8229.
http://dx.doi.org/10.1021/ic5002539