NDLI: Benzoquinolateplatinum(II) complexes as building blocks in the synthesis of Pt

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Martín, Antonio Lalinde, Elena Ibáñez, Susana Moreno, M. Teresa Forniés, Juan Tsipis, Athanassios C.
Description	Author Affiliation: Forniés J ( Departamento de Química Inorgánica-Instituto de Síntesis Química y Catálisis Homógenea, Universidad de Zaragoza-C.S.I.C, 50009 Zaragoza, Spain.)
Abstract	The reaction between $(NBu_{4})[Pt(bzq)(C_{6}F_{5})_{2}]$ (1, bzq = 7,8-benzoquinolate) and $AgClO_{4}$ in a 1:1 molar ratio, in acetone , gives the polymer $[\{Pt(bzq)(C_{6}F_{5})_{2}\}Ag]_{n}$ (2). The reaction of 2 with equimolecular amounts of $PPh_{3}$ and $SC_{4}H_{8}$ (tht) produces the bimetallic complexes $[\{Pt(bzq)(C_{6}F_{5})_{2}\}AgL]$ (L = $PPh_{3}$ (3), tht (4)). For L = py, decomposition takes place and $[Pt(bzq)(C_{6}F_{5})py]$ (5) is obtained. All these complexes have been characterized by X-ray diffraction . The most interesting features of complexes 2–4 is the presence of Pt–Ag bonds, with Pt–Ag distances of ca. 2.75 Å. Besides, the silver centres establish short $η^{1}$ bonding interactions with the $C_{ipso}$ of the bzq ligands , with distances Ag–C of ca. 2.45 Å. Complex 2 is a one-dimensional infinite chain in which the fragments $“Pt(bzq)(C_{6}F_{5})_{2}^{−}”$ and $Ag^{+}$ alternate. On the other hand, complexes 1 and 3–5 show intermolecular pairing through π⋯π interactions between the aromatic rings of the bzq ligand , having interplanar separations of ca. 3.5 Å. Complex 2 dissolves in donor solvents ( acetone , THF) as discrete bimetallic solvated fragments $[\{Pt(bzq)(C_{6}F_{5})_{2}\}AgS_{n}]$ (S = solvent ), similar to complexes 3 and 4. The persistence of the Pt–Ag bond in 2–4, supported by multinuclear NMR spectroscopy , causes a significant blue-shift in the lowest-lying absorption in relation to 1. This fact is attributed (TD-DFT) to a remarkable modification of the orbitals contributing to the HOMO, which changes the character of the transition from $^{1}LC/^{1}MLCT$ in 1 to admixture $^{1}L′LCT/^{1}MLCT$ in the bimetallic complexes. The low energy feature (490–530 nm) of 2 in solid state is attributed to CT from the Pt fragments to the Ag centers. Complexes 2–4 are only emissive in rigid media (solid and glasses). In the solid state, the metallic chain 2 exhibits a bright orange emission (560 nm, 298 K; 590 nm, 77 K), assigned to an excited state involving charge transfer from the platinum fragment with a remarkable contribution of $C_{6}F_{5}$ $(Ar_{f})$ rings to the Pt–Ag bond $(^{3}LMM′CT/^{3}L′M′CT).$ However, 3 and 4 exhibit in solid state at 298 K a vibronic band, which is clearly resolved in two close non-equilibrated bands at 77 K in 3, tentatively ascribed to a mixture of $^{3}MLCT/^{3}L′LCT$ transitions modified by the formation of the Pt–Ag bond. In glassy solution (77 K) 2–4 display a vibronic emission ascribed primarily to $^{3}LC$ character.
ISSN	14779226
Issue Number	12
Journal	Dalton Trans.
Volume Number	41
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2012-03-28
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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