A new G-(H₂L)-Pd heterogeneous catalyst has been prepared via a self-assembly process consisting in the spontaneous adsorption, in water at room temperature, of a macrocyclic H₂L ligand on graphene (G) (G + H₂L = G-(H₂L)), followed by decoration of the macrocycle with Pd²⁺ ions (G-(H₂L) + Pd²⁺ = G-(H₂L)-Pd) under the same mild conditions. This supramolecular approach is a sustainable (green) procedure that preserves the special characteristics of graphene and furnishes an efficient catalyst for the Cu-free Sonogashira cross coupling reaction between iodobenzene and phenylacetylene. Indeed, G-(H₂L)-Pd shows an excellent conversion (90%) of reactants into diphenylacetylene under mild conditions (50 °C, water, aerobic atmosphere, 14 h). The catalyst proved to be reusable for at least four cycles, although decreasing yields down to 50% were observed.

Polyamine ligands are water-soluble receptors that are able to coordinate, depending on their protonation degree, either metal ions, anionic, or neutral species. Furthermore, the presence of fluorescent signaling units allows an immediate visual response/signal. For these reasons, they can find applications in a wide variety of fields, mainly those where aqueous media is necessary, such as biological studies, wastewater analysis, soil contamination, etc. This review provides an overview of the recent developments in the research of chemosensors based on polyamine ligands functionalized with fluorescent signaling units. The discussion focuses on the design, synthesis, and physicochemical properties of this type of fluorescent chemosensors in order to analyze the applications associated to the sensing of metal ions, anions, and neutral molecules of environmental and/or biological interest. To facilitate a quick access and overview of all the chemosensors covered in this review, a summary table of the chemosensor structures and analytes, with all the corresponding references, is also presented.

Three new [1 + 1] macrocycles formed by the reaction of 1H-3,5-bis(chloromethyl)pyrazole with the tosylated amines 1,4,7,10-tetraazadecane (L1), 1,4,8,11-tetraazaundecane (L2) and 1,5,10,14-tetraazatetradecane (L3) are described. Potentiometric studies and HR-ESI-Mass spectrometry show the formation of dimeric binuclear Cu²⁺ complexes whose organization depends on the type of hydrocarbon chains connecting the amine groups. Furthermore, trinuclear or/and tetranuclear complexes are formed depending also on the length of the polyaminic bridge and on the sequence of the hydrocarbon chains. The crystal structures of the [2 + 2] [Cu₂(H(H₋₁L2))₂](ClO₄)₄·4H₂O (1) and [Cu₂(H₋₁L2)₂](ClO₄)₂ (2) complexes show in both of them two macrocycles self-assembled by the metal ions which interconnect their pyrazolate fragments that behave as bis(monodentate) ligands. While in 1 one central amine of each macrocycle binds to the axial position of a distorted square-pyramid and the other ones remain protonated, in 2 all the amine groups are involved in the coordination giving rise to a strongly distorted octahedral geometry. Paramagnetic ¹H NMR measurements support that these structures also form in solution. Interestingly, tetranuclear complexes [Cu₄(H₋₁L4)₂(OH)_2.08](ClO₄)_2.92Br_0.54Cl_0.46 (3) and [Pd_2.39Cu_1.61(H₋₁L4)₂(OH)₂](ClO₄)₂Cl_1.33Br_0.67·2.87H₂O (4) have been isolated for the macrocycle containing the 1,5,9,13-tetraamine chain (L4). 3 has two binucleating units, one of them formed by the pyrazolate moieties and their neighbouring secondary amines and the other by the two central amines of both macrocycles. This latter Cu²⁺ coordination site is completed by two hydroxide anions as bridging ligands. 4 was obtained from a solution prepared to achieve full formation of the dimeric cage [Cu₂(H₋₁(HL4))₂]⁴⁺ by addition of K₂PdCl₄. The Pd²⁺ ion due to its softer acidic characteristics displaces the Cu²⁺ ions from the pyrazolate site. UV-vis spectroscopy suggests that the exchange is completed at room temperature after one hour.

The synthesis and Pb ²⁺ coordination of azamacrocyclic ligands have been described. This paper includes one of the few kinetic studies so far reported on the acid-promoted dissociation of Pb ²⁺ macrocyclic complexes.

A ligand comprised of a macrocyclic pyridinophane core having a pendant arm containing a secondary amine group linked through a methylene spacer to a pyridyl–oxadiazole–phenyl (PyPD) fluorescent system has been prepared (L). The crystal structures of [ZnL](ClO₄)₂ and [CuL](ClO₄)₂ show that M²⁺ is coordinated to all the nitrogen atoms of the macrocyclic core, the secondary amine of the pendant arm and the nitrogen atom of the pyridine group of the fluorescent moiety, the latter bond being clearly weaker than the one with the pyridine of the macrocycle. Solution studies showed the formation of a highly stable Cu²⁺ complex with 1 : 1 stoichiometry, whereas with Zn²⁺ least stable complexes were formed and, given the right conditions, a [Zn₃L₂]⁶⁺ species was also detected, but it was not possible to isolate this species in the solid state. Following Zn²⁺ coordination, a strong chelation-induced enhancement of fluorescence was observed, a behaviour that was not observed with any of the other metal cations tested.