The copper subgroup metal ions in the oxidation state +1 are classical candidates for the aggregation via non-covalent metal–metal interactions, which are supported by a number of the bridging ligands....
The fully oxidized Lindqvist-type hexavanadate compounds decorated by phosphine-derivatized Au(I) moieties oriented in a transoid fashion (n-BuAu ) have been prepared by azide−alkyne cycloaddition reactions and characterized by various techniques, including NMR, IR, and UV/vis spectroscopy and electrospray ionization mass spectrometry. Electronic structure calculations unveil the potential of these model hybrid junctions for application in controlled charge-transport experiments on substrate surfaces.
A set of alkynyl-tris(2-pyridyl)phosphine Au(I) complexes was synthesized and characterized. Free coordination functions on the ligand environment periphery, namely ‘scorpionate’ PPy3 and C≡C bond, allowed these ditopic metalloligands to be...
The
manipulation of the photophysical properties of molecular emitters
can be realized by composing the close environment of the metal center
with the “heavier pnictogen atom” effect. Replacing
a nitrogen atom with a heavier phosphorus atom in otherwise isostructural
molecular systems results in a significant change of the photophysical
parameters. Herein, we report on the synthesis of four pairs of novel
phosphinine-based and isostructural diimine-based Cu(I) complexes,
which feature peculiar photophysical properties, and show how these
parameters depend on the “heavier pnictogen atom” effect.
The obtained Cu(I) complexes show triplet luminescence with MLCT character,
which was investigated by means of spectroscopic and computational
methods. It has been found that the photophysical properties of the
coordination compounds show a dependency on the rigidity of the ancillary
phosphine ligand in an unexpected manner. Replacing the nitrogen atom
with a heavier phosphorus atom in otherwise isostructural molecular
systems results in a significant change in emission energy and especially
in the lifetime of the excited state. The results obtained demonstrate
an efficient approach to the design of emissive molecular materials,
which allows the construction of luminescent complexes with controlled
photophysical properties.
A series of compounds P1–P4 bearing
terminal alkynyl sites connected with a phosphonium group via different
π-conjugated linkers have been synthesized. The compounds themselves
are efficient push–pull emitters and exhibit bright fluorescence
in blue and near-UV regions. P1–P4 were used as alkynyl ligands to obtain a series of homoleptic bis-alkynyl
Au(I) complexes 1–4. The complexes
demonstrate bright phosphorescence and dual emission with dominating
phosphorescence (2–4). Terphenyl derivative complex 3 exhibits warm white emission in DMSO solution and pure white
emission in PMMA films. Time-dependent density functional theory calculations
have shown that the T1 excited state has a hybrid MLCT/ILCT
nature with a dominant contribution of charge transfer across a ligand-centered
“D-π-A” system. The variation of linker allows
tuning the effect of intermolecular charge transfer and thus changing
the electronic and photophysical properties of the organogold “D-π-A”
system. The results presented unambiguously display the advances of
the conception of organometallic “D-π-A” construction.
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