In this work, a series of novel multistimulus-responsive
lanthanide coordination polymers {[LnL(H2O)4]Cl3·3H2O}
n
(Ln = Dy, Tb, Eu) constructed using a dicarboxylic acid viologen
derivative L (L = N,N′-4,4′-bipyridiniodipropionate)
and LnCl3·6H2O were prepared. All materials
showed positive responses to UV light, and the photochromic phenomena
accompanied by significant photoquenching of photoluminescence could
be observed through a photoelectron transfer mechanism. Strikingly,
the Dy analogue displayed photomagnetic behavior, as well as responded
positively to small molecules of inorganic ammonia/organic amines.
Furthermore, the good photoresponsive and ammonia/amine vapor-responsive
properties of the Dy-based material were further fulfilled in dual-function
papers involving erasable inkless printing and visual amine detection
applications. This work aims to advance the development of multistimulus-responsive
multifunctional materials incorporating viologen derivates and versatile
lanthanide ions and further enriches the research in this field.
A series of di-and tetranuclear lanthanide complexes with the formulas [Dy 2 bmzch(tmhd) 5 (CH 3 OH)]•CH 3 OH (1), [Dy 2 bmzch(dbm) 4 (CH 3 O)(CH 3 OH)]•0.5CH 3 OH•0.5H 2 O (2), and Dy 4 bmzch(btfa) 10 ( 3), where tmhd = 2,2,6,6-tetramethyl-3,5-heptanedionate, dbm = dibenzoylmethane, btfa = benzoyltrifluoroacetone, and bmzch = (Z)-N-[(E)-pyrimidin-2-ylmethylene]pyrimidine-2-carbohydrazonate, were structurally and magnetically characterized. More strikingly, although the nitrogen-enriched bridged ligand 3,6-di-(pyrimidin-2-yl)-1,2,4,5-tetrazine (bmtz) was initially adopted, the structures of the complexes obtained indicated that bmtz underwent unprecedented asymmetric ring opening and generated a new ligand bmzch. Combined with different β-diketonates, di-and tetranuclear dysprosium complexes were constructed in which the structural patterns are very sensitive to the selected β-diketonates. In view of this, the bilateral and unilateral dinuclear Dy2 complexes 1 and 2 and tetranuclear Dy4 complex 3 were obtained by choosing different β-diketonates. Magnetic test results reveal that both complexes 1 and 3 showcase typical slow magnetic relaxation behavior without an external direct-current field and the effective energy barrier of the latter is almost twice that of the former, while complex 2 only displays in-field single-molecule-magnetic behavior. Also of note is that these are the first tetrazine-type dysprosium-based single-molecule-magnets undergoing in situ asymmetric ring-opening reaction of this ligand that are formed.
Two tetranuclear lanthanide complexes with the formula [Dy4(HL)4(OAc)2(H2O)2]•(Et3NH)2 (1) and [Gd4(HL)4(OAc)2(H2O)2]•(Et3NH)2•(CH3OH)2 (2) (H4L = N, N'-bis(3-hydroxylsalicylidene)benzene-1,2-diamine) were structurally and magnetically characterized. Dynamic magnetic studies shown that complex 1 exhibits two...
The studies of lanthanide-based single-molecule magnets (SMMs) have captivated the attention of researchers due to their great potential application in quantum information processing, storage and spintronics etc. Recent years have...
Two novel wheel-like lanthanide nanoclusters with 42 nuclearity [Ln42L14(OH)28(OAc)84] (abbreviated as Ln42, 1-Gd; 2-Dy, HL=3-methoxysalicylaldehyde O-vanillin) were structurally and magnetically characterized. The Ln42 species were constructed by O-vanillin and lanthanide...
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