ABSTRACT
We report the synthesis, characterization, and optoelectronic properties of a series of four new luminescent iridium(III) complexes, 1-4, of the form [Ir(Câ§N)2(Nâ§N)]PF6 (where Câ§N is the nonconjugated benzylpyridinato (bnpy) and Nâ§N is a neutral diimine ancillary ligand) with the goal of investigating the effect of the methylene spacer between the coordination moieties of the Câ§N ligand on the optoelectronic properties of the complexes. The crystal structures of 1-3 illustrate two possible orientations of the methylene unit of the bnpy ligand. The formation of these two separate conformers is a result of the conformational flexibility of the bnpy ligand. In complexes 3 and 4, mixtures of the two conformers were observed by 1H NMR spectroscopy in CDCl3 at room temperature, whereas only a single conformer is detected for 1 and 2. Detailed DFT calculations corroborate NMR experiments, accounting for the presence and relative populations of the two conformers. The optoelectronic properties of all four complexes, rationalized by the theoretical study, demonstrate that the interruption of conjugation in the Câ§N ligands results in a reduced electrochemical gap but similar triplet state energies and lower photoluminescence quantum yields in comparison to the reference complexes R1-R4. Depending on the nature of the Nâ§N ligand, we observe (1) marked variations of the ratio of the conformers at ambient temperature and (2) phosphorescence ranging from yellow to red.
ABSTRACT
Molecules containing catenated heavy group 14 atoms are known to exhibit the interesting property of σ-bond electron delocalization. While this is well studied for oligo- and polysilanes the current paper addresses the UV-absorption properties of small tin containing oligosilanes in order to evaluate the effects of Sn-Si and Sn-Sn bonds as well as the results of substituent exchange from methyl to phenyl groups. The new stannasilanes were compared to previously investigated oligosilanes of equal chain lengths and substituent pattern. Replacing the central SiMe2 group in a pentasilane by a SnMe2 unit caused a bathochromic shift of the low-energy band (λmax = 260 nm) of 14 nm in the UV spectrum. If, instead of a SnMe2, a SnPh2 unit is incorporated, the bathochromic shift of 33 nm is substantially larger. Keeping the SnMe2 unit and replacing the two central silicon with tin atoms causes shift of the respective band (λ = 286 nm) some 26 nm to the red. A similar approach for hexasilanes where the model oligosilane [(Me3Si)3Si]2(SiMe2)2 (λmax = 253 nm) was modified in a way that the central tetramethyldisilanylene unit was exchanged for a tetraphenyldistannanylene caused a 50 nm bathochromic shift to a low-energy band with λmax = 303 nm.
Subject(s)
Organotin Compounds/chemistry , Polymers/chemistry , Silanes/chemistry , Spectrophotometry, Ultraviolet/methods , Light , Magnetic Resonance Spectroscopy/methods , Mass Spectrometry/methods , Models, Molecular , Molecular Structure , Organotin Compounds/chemical synthesis , Polymers/chemical synthesis , Silanes/chemical synthesis , Structure-Activity Relationship , Tin/chemistryABSTRACT
Polysilanes are known to exhibit the interesting property of σ-bond electron delocalization. By employing optical spectroscopy (UV-vis), it is possible to judge the degree of delocalization and also differentiate parts of the molecules which are conjugated or not. The current study compares oligosilanes of similar chain length but different substitution pattern. The size of the substituents determines the spatial orientation of the main chain and also controls the conformational flexibility. The chemical nature of the substituents affects the orbital energies of the molecules and thus the positions of the absorption bands.
Subject(s)
Silanes/chemistry , Electrons , Models, Molecular , Molecular Conformation , Orientation, Spatial , Quantum TheoryABSTRACT
In order to evaluate the influence of germanium atoms in oligo- and polysilanes, a number of oligosilane compounds were prepared where two or more silicon atoms were replaced by germanium. While it can be expected that the structural features of thus altered molecules do not change much, the more interesting question is, whether this modification would have a profound influence on the electronic structure, in particular on the property of σ-bond electron delocalization. The UV-spectroscopic comparison of the oligosilanes with germanium enriched oligosilanes and also with oligogermanes showed a remarkable uniform picture. The expected bathochromic shift for oligogermanes and Ge-enriched oligosilanes was observed but its extent was very small. For the low energy absorption band the bathochromic shift from a hexasilane chain (256 nm) to a hexagermane chain with identical substituent patterns (259 nm) amounts to a mere 3 nm.