Pyrene-Functionalized Fluorescent Nanojars: Synthesis, Mass Spectrometric, and Photophysical Studies

Abstract

Nanojars are a class of supramolecular coordination complexes based on pyrazolate, Cu2+, and OH– ions that self-assemble around highly hydrophilic anions and serve as efficient anion binding and extraction agents. In this work, the synthesis, characterization, and photophysical properties of pyrene-functionalized fluorescent nanojars are presented. Three pyrene derivatives, 4-(pyren-1-yl)­pyrazole (HL1), 4-(5-(pyren-1-yl)­pent-4-yn-1-yl)­pyrazole (HL2), and 4-(3-(pyrazol-4-yl)­propyl)-1-(pyren-1-yl)-1,2,3-triazole (HL3), and the corresponding nanojars were synthesized and characterized using nuclear magnetic resonance spectroscopy and mass spectrometry. Electronic absorption, steady-state, and time-resolved fluorescence measurements were carried out to understand the interaction between the pyrene fluorophore and copper nanojars. Optical absorption measurements have shown minor ground state interaction between the fluorophore and nanojars. The fluorescence of pyrene is significantly quenched when attached to nanojars, suggesting strong contribution from the paramagnetic Cu2+ ions. Significant static quenching is observed in the case of L1, when pyrene is directly bound to the nanojar, whereas in the case of L2 and L3, when pyrene is attached to the nanojars using flexible tethers, both static and dynamic quenching are observed.

Triplet–triplet annihilation-based photon upconversion using nanoparticles and nanoclusters

“…116 Consequently, it is anticipated that metal nanoclusters can be complexed with dye ligands. [117][118][119][120][121][122][123][124][125][126][127][128] Moreover, recent separation techniques enable the isolation of metal nanoclusters based on the number of introduced ligands or isomers. [129][130][131][132][133] Therefore, quantitative insights into how TET and UC properties change depending on the number and position of introduced ligands may be elucidated.…”