Solid-state functional luminescent materials arouse an enormous scientific interest due to their diverse applications in lighting, display devices, photonics, optical communication, low energy scintillation, optical storage, light conversion, or photovoltaics. Among all types of solid luminophors, the emissive coordination polymers, especially those based on luminescent trivalent lanthanide ions, exhibit a particularly large scope of light-emitting functionalities, fruitfully investigated in the aspects of chemical sensing, display devices, and bioimaging. Here, we present the complete overview of one of the promising families of photoluminescent coordination compounds, that are heterometallic d–f cyanido-bridged networks composed of lanthanide(3+) ions connected through cyanide bridges with polycyanidometallates of d-block metal ions. We are showing that the combination of cationic lanthanide complexes of selected inorganic and organic ligands with anionic homoligand [M(CN)x]n− (x = 2, 4, 6 and 8) or heteroligand [M(L)(CN)4]2− (L = bidentate organic ligand, M = transition metal ions) anions is the efficient route towards the emissive coordination networks revealing important optical properties, including 4f-metal-centred visible and near-infrared emission sensitized through metal-to-metal and/or ligand-to-metal energy transfer processes, and multi-coloured photoluminescence switchable by external stimuli such as excitation wavelength, temperature, or pressure.
The
ab initio
calculations were correlated with
magnetic and emission characteristics to understand the modulation
of properties of NIR-emissive [Yb
III
(2,2′-bipyridine-1,1′-dioxide)
4
]
3+
single-molecule magnets by cyanido/thiocyanidometallate
counterions, [Ag
I
(CN)
2
]
−
(
1
), [Au
I
(SCN)
2
]
−
(
2
), [Cd
II
(CN)
4
]
2–
/[Cd
II
2
(CN)
7
]
3–
(
3
), and [M
III
(CN)
6
]
3–
[M
III
= Co (
4
), Ir (
5
), Fe
(
6
), Cr (
7
)]. Theoretical studies indicate
easy-axis-type ground doublets for all Yb
III
centers. They
differ in the magnetic axiality; however, transversal
g
-tensor components are always large enough to explain the lack of
zero-dc-field relaxation. The excited doublets lie more than 120 cm
–1
above the ground one for all Yb
III
centers.
It was confirmed by high-resolution emission spectra reproduced from
the
ab initio
calculations that give reliable insight
into energies and oscillator strengths of optical transitions. These
findings indicate the dominance of Raman relaxation with the power
n
varying from 2.93(4) to 6.9(2) in the
4
–
3
–
5
–
1
–
2
series. This trend partially follows the magnetic axiality,
being deeper correlated with the phonon modes schemes of (thio)cyanido
matrices.
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