Construction of green nanostructured heterogeneous catalysts via non-covalent surface decoration of multi-walled carbon nanotubes with Pd(II) complexes of azamacrocycles

Savastano, Matteo; Arranz‐Mascarós, Paloma; Bazzicalupi, Carla; Clares, M. Paz; Godino-Salido, M. Luz; Valero, M. Dolores Gutiérrez; Inclán, Mario; Bianchi, Antonio; Garcı́a-España, Enrique; López‐Garzón, Rafael

doi:10.1016/j.jcat.2017.07.023

Cited by 29 publications

(110 citation statements)

References 96 publications

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“…It was later in the spotlight for its ability to form metal complexes [6][7][8], but its wider success was achieved thanks to its utilisation as a scaffold for the preparation of new materials that have proven effective in a variety of applications. Indeed, L derivatives decorated with different hanging functionalities have been studied for several biomedical (MRI contrast agents [9][10][11][12], antiproliferative treatments [13][14][15][16], radiotherapy [17,18], enzyme mimicking [19,20] and antioxidant activity [21][22][23]), chemosensing [24][25][26][27] and catalytic [28][29][30][31][32][33] applications. Very recently, (MRI contrast agents [9][10][11][12], antiproliferative treatments [13][14][15][16], radiotherapy [17,18], enzyme mimicking [19,20] and antioxidant activity [21][22][23]), chemosensing [24][25]…”

Section: Introductionmentioning

confidence: 99%

Stabilisation of Exotic Tribromide (Br3−) Anions via Supramolecular Interaction with a Tosylated Macrocyclic Pyridinophane. A Serendipitous Case

et al. 2020

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Tetraaza-macrocyclic pyridinophane L-Ts, decorated with a p-toluenesulfonyl (tosyl; Ts) group, appear to be a useful tool to provide evidence on how the interplay of various supramolecular forces can help stabilise exotic anionic species such as tribromide (Br3−) anions. Indeed, crystals of (H2L-Ts)(Br3)1.5(NO3)0.5 unexpectedly grew from an acidic (HNO3) aqueous solution of L-Ts in the presence of Br− anions. The crystal structure of this compound was determined by single crystal XRD analysis. Hydrogen bonds, salt-bridges, anion-, - stacking, and van der Waals interactions contribute to stabilising the crystal lattice. The observation of two independent Br3− anions stuck over the π-electron densities of pyridine and tosyl ligand groups, one of them being sandwiched between two pyridine rings, corroborates the significance of anion-π interactions for N-containing heterocycles. We show herein the possibility of detecting anion-π contacts from fingerprint plots generated by Hirshfeld surface analysis, demonstrating the effective usage of this structural investigation technique to further dissect individual contributions of stabilising supramolecular forces.

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Section: Introductionmentioning

confidence: 99%

Stabilisation of Exotic Tribromide (Br3−) Anions via Supramolecular Interaction with a Tosylated Macrocyclic Pyridinophane. A Serendipitous Case

et al. 2020

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“…Scorpiand type aza-macrocyclic ligands, that is aza-macrocyclic ligands with coordinating tails [1], and their metal complexes have attracted considerable interest thanks to the numerous uses they have been tested for, including but not limited to various biomedical applications [2,3] (MRI contrast agents [4,5], radioisotopes complexation and radiolabelling [6][7][8][9], radiotherapy [10][11][12][13][14], chelation therapy [15][16][17], antiproliferative treatments [18][19][20][21], enzyme mimicking [22][23][24][25][26][27][28][29]), catalysis [30][31][32][33][34][35][36] and chemosensing [37][38][39][40][41][42][43].…”

Section: Introductionmentioning

confidence: 99%

Sensing Zn2+ in Aqueous Solution with a Fluorescent Scorpiand Macrocyclic Ligand Decorated with an Anthracene Bearing Tail

et al. 2020

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Synthesis of the new scorpiand ligand L composed of a [9]aneN3 macrocyclic ring bearing a CH2CH2NHCH2-anthracene tail is reported. L forms both cation (Zn2+) and anion (phosphate, benzoate) complexes. In addition, the zinc complexes of L bind these anions. The equilibrium constants for ligand protonation and complex formation were determined in 0.1 M NaCl aqueous solution at 298.1 ± 0.1 K by means of potentiometric (pH-metric) titrations. pH Controlled coordination/detachment of the ligand tail to Zn2+ switch on and off the fluorescence emission from the anthracene fluorophore. Accordingly, L is able to sense Zn2+ in the pH range 6–10 down to nM concentrations of the metal ion. L can efficiently sense Zn2+ even in the presence of large excess of coordinating anions, such as cyanide, sulphide, phosphate and benzoate, despite their ability to bind the metal ion.

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“…− anions, each lying on the crystallographic planes ( Figure 7). The ligand assumes a bent conformation, typical of small macrocycles incorporating rigid aromatic units [22][23][24]26,27], which can be described by the 84 • dihedral angle between the aromatic ring plane and the mean plane defined by the aliphatic nitrogen atoms. The acidic protons are located on the benzylic nitrogen atoms [22][23][24], yet their interaction with the polyiodide anions are very limited, consisting of a sole contact, and moreover quite long to be considered a typical salt bridge (N2(H2A) anions define a slightly distorted void cubic lattice hosting the countercations.…”

Section: Crystal Structure Of [H 2 L2-me 3 (I 7 ) 2 ]mentioning

confidence: 99%

Stabilization of Supramolecular Networks of Polyiodides with Protonated Small Tetra-azacyclophanes

et al. 2019

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Polyiodide chemistry is among the first historically reported examples of supramolecular forces at work. To date, owing to the increasingly recognized role of halogen bonding and the incorporation of iodine-based components in several devices, it remains an active field of theoretical and applied research. Herein we re-examine azacyclophanes as a class of ligands for the stabilization of iodine-dense three-dimensional networks, showing how we devised novel possible strategies starting from literature material. The new set of azacyclophane ligands affords novel crystal structures possessing intriguing properties, which develop on a double layer. At a macroscopic level, the obtained networks possess a very high iodine packing density (less than 2 times more diluted than crystalline I2): a simple parameter, IN, is also introduced to quickly measure and compare iodine packing density in different crystals. On the microscopic level, the present study provides evidence about the ability of one of the ligands to act as a three-dimensional supramolecular mold for the template synthesis of the rarely observed heptaiodide (I7−) anion. Therefore, we believe our approach and strategy might be relevant for crystal engineering purposes.

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Construction of green nanostructured heterogeneous catalysts via non-covalent surface decoration of multi-walled carbon nanotubes with Pd(II) complexes of azamacrocycles

Cited by 29 publications

References 96 publications

Stabilisation of Exotic Tribromide (Br3−) Anions via Supramolecular Interaction with a Tosylated Macrocyclic Pyridinophane. A Serendipitous Case

Stabilisation of Exotic Tribromide (Br3−) Anions via Supramolecular Interaction with a Tosylated Macrocyclic Pyridinophane. A Serendipitous Case

Sensing Zn2+ in Aqueous Solution with a Fluorescent Scorpiand Macrocyclic Ligand Decorated with an Anthracene Bearing Tail

Stabilization of Supramolecular Networks of Polyiodides with Protonated Small Tetra-azacyclophanes

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