ABSTRACT
We report the syntheses of two new organotin sulfide clusters with heteroaromatic substituents. A phenanthroline-functionalized tin sulfide cluster [(RPhenSn)4S6] (1; RPhen = CMe2CH2C(Me)N-NC(H)C12H7N2) and a bipyridyl-terminated cluster [(R4-bipySn)4S6] (2; R4-bipy = CMe2CH2C(Me)N-NC(H)-4-C10H7N2) were obtained from reactions of the hydrazone-functionalized organotin sulfide cluster [(RNSn)4S6] (RN = CMe2CH2C(Me)N-NH2) with 1,10-phenanthroline-5-carboxaldehyde or 2,2'-bipyridine-4-carbaldehyde. 1 and 2 were tested towards their capability of trapping metal ions by means of the terminal chelating ligands. The reaction of 2 with ZnCl2 afforded the cluster compound [(R4-bipyZnCl2Sn)4S6] (5), in which four ZnCl2 units are coordinated by the heteroaromatic organic groups. We discuss the structures and demonstrate the effect of ZnCl2 trapping on optical absorption and luminescence properties.
ABSTRACT
Reactions of Sn-S clusters with [IrCl(cod)]2 afforded an Ir-Sn-S cluster with unprecedented topology, {[Ir3(cod)3(µ3-S)2](µ3-S)SnCl}2, in which two [Ir3S2] units and a central [Sn2S2] unit are connected via Ir-S and Ir-Sn bonds. Each of the crystallographically independent Ir atoms exhibits a specific chemical environment. Quantum chemical studies shed light on the electronic structure of the multinary cluster and the Ir-Sn bonds.
ABSTRACT
Recently, we reported on ferrocenyl-decorated Sn/S clusters; herein, we present the extension of our investigations by attachment of ruthenocenyl units to an according cluster skeleton. The latter was realized upon improvement of the synthesis of acetylruthenocene, its conversion to a hydrazone derivative, and the subsequent reaction with a keto-functionalized Sn/S precursor complex. The report comprises the crystal structures of acetylruthenocene and the ruthenocenyl-terminated Sn/S cluster [(R(Rc)Sn)4Sn2S10] (R(Rc) = CMe2CH2C(Me)âN-NâC(Me)Rc), as well as the discussion of the electrochemical properties of the latter and its behavior during time-resolved photoluminescence investigations.
ABSTRACT
The synthesis of new functionalized organotin-chalcogenide complexes was achieved by systematic optimization of the reaction conditions. The structures of compounds [(R(1, 2) Sn)3 S4 Cl] (1, 2), [((R(2) Sn)2 SnS4 )2 (µ-S)2 ] (3), [(R(1, 2) Sn)3 Se4 ][SnCl3 ] (4, 5), and [Li(thf)n ][(R(3) Sn)(HR(3) Sn)2 Se4 Cl] (6), in which R(1) =CMe2 CH2 C(O)Me, R(2) =CMe2 CH2 C(NNH2 )Me, and R(3) =CH2 CH2 COO, are based on defect heterocubane scaffolds, as shown by X-ray diffraction, (119) Snâ NMR spectroscopy, and ESI mass spectrometry analyses. Compounds 4, 5, and 6 constitute the first examples of defect heterocubane-type metal-chalcogenide complexes that are comprised of selenide ligands. Comprehensive DFT calculations prompted us to search for the formal intermediates [(R(1) SnCl2 )2 (µ-S)] (7) and [(R(1) SnCl)2 (µ-S)2 ] (8), which were isolated and helped to understand the stepwise formation of compounds 1-6.
ABSTRACT
Decoration of tetrelchalcogenide T-E clusters with chelating donor ligands was achieved to capture transition metal ions on their surfaces. We demonstrate that by covalent linking of bispyridyl ligands to an Sn-S complex, [ZnX](+) units can be trapped and incorporated into the cluster framework. Intermediates that were identified using spectroscopy and/or X-ray diffraction gave insight into the formation processes.
