Structural and spectroscopic investigation of new luminescent hybrid materials based on calix[4]arene-tetracarboxylate and Ln 3+ ions (Ln = Gd, Tb or Eu)

Metallocalix[n]arenes in catalysis: A 13-year update

“…To the best of our knowledge, this is the sole recent example of rare earth metal-calixarene complexes employed in catalytic reactions. Other recent reports concern the use calix[n]arenes in the selective extraction of rare earth metal ion from a number of different matrixes [136], while well-defined complexes have been mainly investigated in terms of their structural/luminescent features and coordination behavior [137,138].…”

Mixed Tb/Dy coordination ladders based on tetra(carboxymethyl)thiacalix[4]arene: a new avenue towards luminescent molecular nanomagnets

“…77 The capability of calixarene carboxylate derivatives to act as antennae for Tb 3+ complexes has already been documented. 53 The room-temperature emission spectra of the HL3-Tb and HL3-Dy coordination networks, when excited at l ex ¼ 350 nm, are depicted in Fig. 4.…”

“…The s obs values (Tables S2 and S3 in ESI †) were in accordance with those reported for other calixarene-based coordination compounds in the solid-state. 53,78…”

“…Among them, the use of calixarenes bearing carboxylic coordinating sites, for which the lanthanides cations present great affinity, has been reported for the formation of isolated complexes. 52,53 It is important to note that, to date, only a few lanthanidebased coordination networks involving calixarene derivatives, which are mainly formed by the tetrasulfonate derivatives of (thia)calix [4]arenes in cone conformation, [54][55][56][57] have been reported. To the best of our knowledge, no examples involving carboxylate derivatives or (thia)calix [4]arenes in 1,3-alternate conformation have been reported so far.…”

Exploiting complementary ligands for the construction of square antiprismatic monometallic lanthanide SMMs

“…20,[36][37][38] Despite this rational design, there is just one report of a mononuclear lanthanide-based SMM with TBC [4]; a seven-coordinate dysprosium ion encapsulated between a TBC [4] and a Kläui tripodal ligand. This complex displays fieldinduced (dc = 900 Oe) SMM behaviour with Ueff = 73.7 K and τ0 = 9.1 × 10 -9 s. 39 A small number of TBC [4]-based mononuclear lanthanide complexes have also been constructed to investigate luminescence, [40][41][42][43] metal extraction 44,45 and synthetic methodology. [46][47][48][49][50][51] In order to achieve high levels of control over the coordination sphere of a metal ion at the TBC [4] lower-rim, one must first overcome the preference for TBC [4] to bridge to neighbouring metal centres.…”