The development and integration of
Single-Molecule Magnets (SMMs)
into molecular electronic devices continue to be an exciting challenge.
In such potential devices, heat generation due to the electric current
is a critical issue that has to be considered upon device fabrication.
To read out accurately the temperature at the submicrometer spatial
range, new multifunctional SMMs need to be developed. Herein, we present
the first self-calibrated molecular thermometer with SMM properties,
which provides an elegant avenue to address these issues. The employment
of 2,2′-bipyrimidine and 1,1,1-trifluoroacetylacetonate ligands
results in a dinuclear compound, [Dy
2
(bpm)(tfaa)
6
], which exhibits slow relaxation of the magnetization along with
remarkable photoluminescent properties. This combination allows the
gaining of fundamental insight in the electronic properties of the
compound and investigation of optomagnetic cross-effects (Zeeman effect).
Importantly, spectral variations stemming from two distinct thermal-dependent
mechanisms taking place at the molecular level are used to perform
luminescence thermometry over the 5–398 K temperature range.
Overall, these properties make the proposed system a unique molecular
luminescent thermometer bearing SMM properties, which preserves its
temperature self-monitoring capability even under applied magnetic
fields.
Three novel 1D, 2D and 3D coordination polymers were successfully isolated using nitrogen based 3,6-bis(2'-pyrimidyl)-1,2,4,5-tetrazine (BPymTz) and 2,4,6-tris(2-pyrimidyl)-1,3,5-triazine (TPymT) ligands with Ag(I) ions. The formation of these supramolecular assemblies was templated through anion-π-system interactions.
An unprecedented trinuclear heteroleptic Ag(I) complex was isolated using a stable multidentate 2,4,6-tris(2-pyrimidyl)-1,3,5-triazine (TPymT) ligand. The obtained compound is an efficient catalyst for the direct aziridination of terminal olefins.
A planar tetradentate 3,6-bis(2-pyrimidyl)-1,2,4,5-tetrazine (BpymTz) templating chelate affords the formation of an unprecedented BpymTz˙ radical anion bridged {Ni} complex. Detailed magnetic measurements performed on the isolated air stable [Ni(BpymTz˙)Cl(DMF)]Cl·0.5(HO) compound reveal strong ferromagnetic Ni-BpymTz˙ interactions with a coupling constant of J = 98.84 cm.
Studies of three related Cd(II) systems (a discrete [Cd(II)2] unit, a one-dimensional [Cd(II)2]n coordination polymer and a Cd(II)-based MOF) all derived from the ligand 2,4,6-tris(2-pyrimidyl)-1,3,5-triazine, reveal an exceptionally rare example of (113)Cd-(113)Cd J coupling in the polymer that is detectable by solid-state NMR ((2)JCd-Cd = ∼65 Hz).
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