Lanthanide‐Based Molecular Cluster‐Aggregates: Optical Barcoding and White‐Light Emission with Nanosized {Ln₂₀} Compounds

Abstract

Counterfeit goods represent a major problem to companies, governments, and customers, affecting the global economy. In order to protect the authenticity of products and documents, optical anti‐counterfeit technologies have widely been employed via the use of discrete molecular species, extended metal–organic frameworks (MOFs), and nanoparticles. Herein, for the first time we demonstrate the potential use of molecular cluster‐aggregates (MCA) as optical barcodes via composition and energy transfer control. The tuneable optical properties for the [Ln20(chp)30(CO3)12(NO3)6(H2O)6], where chp−=deprotonated 6‐chloro‐2‐pyridinol, allow the fine control of the emission colour output, resulting in high‐security level optical labelling with a precise read‐out. Moreover, a unique tri‐doped composition of GdIII, TbIII, and EuIII led to MCAs with white‐light emission. The presented methodology is a unique approach to probe the effect of composition control on the luminescent properties of nanosized molecular material.

Fluorescence detection of malachite green and cations (Cr3+, Fe3+ and Cu2+) by a europium-based coordination polymer

“…Due to multiple coordination modes and remarkable uorescence characteristics, [44][45][46][47][48][49][50][51][52][53] lanthanide CP (such as Tb-CP, Eu-CP) have been widely employed in uorescent detection, [54][55][56][57][58][59][60][61][62][63][64][65] such as detecting metal cations, 66-75 inorganic anions, [69][70][71][72][73][74][75] small organic molecules [76][77][78][79][80] and explosives. [81][82][83] However, it is rarely recorded that lanthanide CP as multifunctional luminescent probe dedicated to detecting MG and various metal ions.…”

Icosahedron [Cl12]12- Templated Gigantic Gd158Co38 Nanocluster with the Largest Ln158 Core for Magnetic Cooling

“…Synthesis and structural characterization of giant molecules have long been one of the most attractive elds, owing to their fascinating topological structures, complex intramolecular assembly behavior, and numerous physical-chemical properties different from small molecules [1][2][3][4][5][6][7][8][9][10] . High-nuclearity lanthanide(Ln)-containing clusters are one of the new members of the giant molecular family and has received extensive attention in the past decade associated with charming structures and excellent properties in magnetism, catalysis, and luminescence [11][12][13][14][15][16][17][18][19][20] .…”

Half‐Sandwich Complexes [Cp′4Ln4I8]4 (Ln=Ce, Pr):Emergence of Donor‐Free Organolanthanide Nanowheels

“…The main driving force behind rare-earth-metal (Ln) cluster research is marked by a wide range of potential applications. [1][2][3][4][5][6][7][8][9][10][11][12][13] While organolanthanide clusters assist in unravelling the active species of industrial 1,3-diene polymerization catalysis, [14] luminescent coordination clusters do impress with intriguing structural motifs and bright colors. [8,10,13,[15][16][17][18][19][20] As for cerium(III) (4 f 1 ), the photoluminescent properties are determined by dipole-allowed 5 d!4 f transitions, which enables efficient tuning of the emission wavelength of complexes.…”

“…[1][2][3][4][5][6][7][8][9][10][11][12][13] While organolanthanide clusters assist in unravelling the active species of industrial 1,3-diene polymerization catalysis, [14] luminescent coordination clusters do impress with intriguing structural motifs and bright colors. [8,10,13,[15][16][17][18][19][20] As for cerium(III) (4 f 1 ), the photoluminescent properties are determined by dipole-allowed 5 d!4 f transitions, which enables efficient tuning of the emission wavelength of complexes. [21][22][23] This effect can be further enhanced in terms of the luminescence intensity in combination with a variety of ligand systems, including cyclopentadienyl derivatives [24] or hydridotris(pyrazolyl)borato ligands, [25] given their stabilizing properties.…”