NDLI: Shedding light on the bonding, photophysical and magnetotropic properties of triangular $Pt_{3}$ complexes and their “open-face” $TlPt

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Tsipis, Athanassios C. Gkekas, George N.
Description	Author Affiliation: Tsipis AC ( Laboratory of Inorganic and General Chemistry, Department of Chemistry, University of Ioannina, 451 10 Ioannina, Greece. attsipis@uoi.gr)
Abstract	The molecular and electronic structures, stabilities, bonding features, magnetotropic and spectroscopic properties of the triangular $Pt_{3}(μ_{2}-L)_{3}(L′)_{3}$ clusters and their $[(μ_{3}-Tl)Pt_{3}(μ_{2}-L)_{3}(L′)_{3}]^{+}$ (L = CO, $SnR_{2},$ $SnH_{2},$ $SiR_{2},$ $SiH_{2},$ $CH_{3}CN,$ $PH_{2},$ $C_{6}F_{5},$ $SO_{2}$ or HCN and L′ = CO, $PH_{3},$ $CH_{3}CN,$ $C_{6}F_{5},$ HCN) half-sandwiches have been studied by means of density functional theory (DFT) calculations. It is found that the optimized Pt–Pt intermetallic distances in the clusters are well below the sum of the van der Waals radii of the two Pt metal atoms (3.44 Å). The triangular $Pt_{3}(μ_{2}-L)_{3}(L′)_{3}$ clusters trap a thallium(I) cation forming stable “open face” half-sandwiches. The distance between Tl(I) and the centroids of the $Pt_{3}$ rings in the half-sandwiches is calculated to be within the range 2.52–2.86 Å. Energy decomposition analysis (EDA) calculations using a dispersion corrected B3LYP-D functional reveal that the interaction of Tl(I) with the $Pt_{3}$ ring in the half-sandwiches is dominated by the interplay of electrostatic and orbital interactions with a small contribution from dispersion forces as well. In addition, charge decomposition analysis (CDA) calculations indicate strong donor–acceptor interactions between Tl(I) and the rings. The estimated proton affinities (PAs) of the triangular $Pt_{3}(μ_{2}-L)_{3}(L′)_{3}$ clusters illustrate their relatively strong π-basic character. Furthermore, an excellent linear relationship between the PAs of the $Pt_{3}(μ_{2}-L)_{3}(L′)_{3}$ clusters and the bond dissociation energies $(D_{0})$ of the $[(μ_{3}-Tl)Pt_{3}(μ_{2}-L)_{3}(L′)_{3}]^{+}$ half-sandwiches was established. The magnetotropicity of these systems was studied by calculating the $NICS_{zz}-scan$ profiles. The spectroscopic properties of the triangular $Pt_{3}$ clusters and their $TlPt_{3}$ half-sandwiches were studied by means of TDDFT calculations. The simulated absorption spectra are dominated by strong absorption bands in the UV region. The emission band maxima of the triangular $Pt_{3}$ clusters are predicted to lie within the IR region. In order to gain insight into the phosphorescence process of these systems, we have optimized their first triplet excited state, $T_{1}.$ The estimated deep HOMO energy for these compounds makes them promising candidates for use as “hole” blocking materials in LED devices. Also, it is expected to exhibit small non-radiative decay rate constants due to their relatively large $S_{0}–T_{1}$ energy difference making them suitable PHOLED emitters or dopants in organic polymer matrices constituting the recombination layer of an OLED device.
ISSN	14779226
Issue Number	6
Journal	Dalton Trans.
Volume Number	42
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2013-02-14
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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