Luminescent platinum(II) complexes. Electronic spectroscopy of platinum(II) complexes of 2,2′:6′,2″-terpyridine (terpy) and p-substituted phenylterpyridines and crystal structure of [Pt(terpy)CI][CF3SO3]
- 1 January 1993
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 19,p. 2933-2938
- https://doi.org/10.1039/dt9930002933
Abstract
The complexes [Pt(terpy)L′]n+(terpy = 2,2′:6′,2″-terpyridine; L′= Cl, Br, I, N3 or SCN–, n= 1; L′= NH3, n= 2) have been prepared and their spectroscopic and emission properties studied. Absorption bands are found at 300–350 and at 370–450 nm, which are assigned to the intraligand and metal-to-ligand change-transfer (m.l.c.t.) transitions, respectively. The complexes [Pt(4′R-terpy)Cl]ClO4(R′= C6H4OMe-p,C6H4Me-p, C6H4Br-p or C6H4CN-p) were prepared by the reaction of K2[PtCl4] with 4′R-terpy in water–MeCN. Unlike [Pt(terpy)L′]n+ which show emission in the solid state only, [Pt(4′R-terpy)Cl]+ display 3m.l.c.t. emission in fluid solution at room temperature. The crystal structure of [Pt(terpy)Cl][CF3SO3] has been determined: monoclinic, space group P21/n, a= 13.808(4), b= 6.873(1), c= 19.477(5)Å, β= 105.54(2)°, and Z= 4. In the unit cell, two [Pt(terpy)Cl]+ cations stack in a head-to-tail fashion with an intermolecular Pt ⋯ Pt distance of 3.329(1)Å. The solid-state emission of [Pt(terpy)Cl][CF3SO3] is similar to that of the 3(dσ*πb) emission of the dinuclear complex [Pt2(terpy)2L][ClO4]3(L = guadinate) having intramolecular Pt ⋯ Pt separations of 3.090(1) and 3.071(1)Å.Keywords
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