Unusual luminescent octanuclear stellate platinacycle self-assembled by Pt-Ag bonds.
An unprecedented macrocyclic luminescent octanuclear cluster cyclo-[{Pt(C6Cl5)2(mu-OH)(mu-Ag)}4] (Pt-Ag) 2 was self-assembled by the formation of Pt(II)-Ag(I) bonds; the optical properties of this complex were also investigated.
New dicyano cyclometalated compounds containing Pd(II)-Tl(I) bonds as building blocks in 2D extended structures: synthesis, structure, and luminescence studies.
New mixed metal complexes [PdTl(C^N)(CN)(2)] [C^N = 7,8-benzoquinolinate (bzq, 3); 2-phenylpyridinate (ppy, 4)] have been synthesized by reaction of their corresponding precursors (NBu(4))[Pd(C^N)(CN)(2)] [C^N = bzq (1), ppy (2)] with TlPF(6). Compounds 3 and 4 were studied by X-ray diffraction, showing the not-so-common Pd(II)-Tl(I) bonds. Both crystal structures exhibit 2-D extended networks fashioned by organometallic "PdTl(C^N)(CN)(2)" units, each one containing a donor-acceptor Pd(II)-Tl(I) bond, which are connected through additional Tl···N≡C contacts and weak Tl···π (bzq) contacts in the case of 3. Solid state emissions are red-shifted compared with those of the precursors and have been assigned to metal-metal'-to-ligand charge transfer (MM'LCT [d/s σ*(Pd,Tl) → π*(C^N)]) mixed with some intraligand ((3)IL[π(C^N) → π*(C^N)]) character. In diluted solution either at room temperature or 77 K, the Pd-Tl bond is no longer retained as confirmed by mass spectrometry, NMR, and UV-vis spectroscopic techniques.
Theoretical study of the d10–d8 interaction between Au(I) and Au(III) on the cis/trans-[PH3Au(I)C(L)C(L)Au(III)(R)2PH3] (R=–H, –CH3; L=–H, –CH3) systems
Abstract We have carried out an ab initio study designed to shed some light on the aurophilic attractions between Au(I) and Au(III) in the [PH 3 Au(I)C(L)C(L)Au(III)(R) 2 PH 3 ] (where R=–H, –CH 3 ; L=–H, –CH 3 ) model. Calculations carried out at the MP2 level revealed important facts such as the presence of an intramolecular aurophilic interaction in the cis -complexes that stabilizes them with respect to the trans -isomers. Using two additional models to study the intermolecular interaction between Au(I) and Au(III) we were able to estimate an interaction energy between 21 and 25 kJ mol −1 at the MP2 level of calculation.