Thiacalixarene assembled heterotrinuclear lanthanide clusters comprising Tb^III and Yb^III enable f–f communication to enhance Yb^III-centred luminescence

Abstract

A mixture of heterotrinuclear lanthanide cluster complexes, Tb3-xYbxTCAS2 (x = 1, 2), was obtained by mixing thiacalix[4]arene-p-tetrasulfonate (TCAS), Tb(III), and Yb(III), which shows enhanced Yb(III)-centred luminescence and shortened lifetime for Tb(III)-centred luminescence as compared to Yb3TCAS2 and Tb3TCAS2, indicating f-f communication, i.e., energy transfer from Tb(III) to Yb(III).

Sorting Phenomena and Chirality Transfer in Fluoride-Bridged Macrocyclic Rare Earth Complexes

“…Similarly, our attempts to isolate the heterodinuclear complex containing two different macrocyclic units as pure solids were so far unsuccessful, and the crystallization process seems to shift the equilibrium between various dinuclear forms. It should be mentioned that the heteronuclear mixed-lanthanide complexes characterized in solution are rare. − …”

Achieving stable photoluminescence by double thiacalix[4]arene-capping: the lanthanide-oxo cluster core matters

“…[1][2][3][4][5][6][7][8][9][10] Among these different properties, photoluminescence of the lanthanide-oxo clusters is of particular interest and has been widely investigated. [11][12][13][14][15] In homometallic lanthanide clusters, the 4f orbitals of Ln 3+ ions are shielded by the 5s 2 5p 6 subshells and therefore give highly intensive narrow-band emissions, making them attractive for a wide range of applications such as displays, luminescent sensors, and medical-probes for clinical use. 9,10,14 Famous examples include Eu 3+ and Tb 3+ based clusters with red ( 5 D 0 / 7 F n transition) and green ( 5 D 4 / 7 F n transition) luminescence, respectively.…”

Thiacalix[4]arene‐Supported Tetranuclear TbIII and EuIII Compounds: Synthesis, Structure, Luminescence, and Magnetism

“…Compared with calix[4]arene, the introduction of sulfur atoms in thiacalix[4]arene makes more donor atoms both on the lower rim position (four phenol oxygen atoms) and on the cyclic framework itself (four sulfur atoms) . Moreover, the larger π‐conjugate system of thiacalix[4]arene is also beneficial for a superior antenna chromophore . In our previous report, a series of lanthanide pentanuclear compounds were synthesized based on thiacalix[4]arene and its derivatives, in which the dysprosium analogue exhibits obvious SMM behavior .…”