Luminescence properties of salts of the [Pt(4 ' Ph-terpy)Cl](+) chromophore: crystal structure of the red form of [Pt(4 '-Ph-terpy)Cl]BF4 (4 ' Ph-terpy=4 '-phenyl-2,2 ': 6 ',2 ''-terpyridine)

The complexes [Pt(4'Ph-terpy)Cl]A (4'Ph-terpy = 4'-phenyl-2,2':6',2 "-terpy ridine; A = SbF6, CF3SO3, or BF4) have been prepared by reaction of [Pt(PhC N)(2)Cl-2] with the appropriate silver salt followed by addition of the 4'- phenyl-2,2':6',2"-terpyridyl ligand, The hexafluoroantimonate salt is yello w but, depending on the method of crystallisation, the triflate and tetrafl uoroborate salts can be isolated in two forms, one yellow and the other red , the red forms only being stable at low temperatures. The crystal structur e of red [Pt(4'Ph-terpy)Cl]BF4. CH3CN has been determined at 153 K by X-ray diffraction methods. The [Pt(4'Ph-terpy)Cl](+) cations are stacked face-to -face in an extended chain of stepped tetramers, with essentially equal Pt ... Pt distances of ca. 3.3 Angstrom within a tetramer and a Pt ... Pt dist ance of 4.680 Angstrom between successive tetramers. The spectroscopic and solid state emission properties of the salts have been recorded. The yellow salts are characterised by emission from an isolated chromophore in an exc ited state that reflects the admixture of (MLCT)-M-3 (MLCT = metal-to-ligan d charge-transfer) and (IL)-I-3 (IL = intraligand) character. This assignme nt is supported by the presence of vibrational structure in the emission ba nd as well as by a lifetime of ca. 1 mu s for the emission. The red [Pt(4'P h-terpy)Cl]BF4. CH3CN salt, in contrast, exhibits emission from a (MMLCT)-M -3 (MMLCT = metal-metal-ligand charge-transfer) state as a consequence of t he strong platinum d(z2)-d(z2) orbital interactions This assignment is cons istent with the observation of a narrow structureless and asymmetric band a s well as an emission lifetime of cn. 0.1 mu s. There is a systematic and s ubstantial red-shift of 75 nm in the emission maximum on cooling the red sa lt from 280 to 80 K, an unexpected result since bathochromic shifts of this kind are normally associated with stacked structures with a uniform Pr ... Pt separation. The above assignments are further supported by measurements of the emission spectra of solutions of varying concentrations of the tetr afluoroborate salt in a dimethylformamide-methanol-ethanol glass at 77 K an d by lifetime measurements. Interestingly, pressure in the form of grinding the salts modifies their luminescent properties. Thus crushed samples of t he yellow hexafluoroantimonate salt exhibit multiple emission at 80 K from both the (MMLC)-M-3-T and the mixed parentage (MLCT)-M-3/(IL)-I-3 excited s tates, whereas at room temperature the emission spectrum is dominated by a broad band centred at 644 nm associated entirely with the (MMLCT)-M-3 emiss ion.