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Hierarchical Self-Assembly and Chiroptical Studies of Luminescent 4d–4f Cages
journal contribution
posted on 2018-06-13, 14:24 authored by Zhuo Wang, Li-Peng Zhou, Tong-Han Zhao, Li-Xuan Cai, Xiao-Qing Guo, Peng-Fei Duan, Qing-Fu SunMultinuclear
lanthanide-containing supramolecular cages have received increasing
attention recently because of their unique electroptical and magnetic
properties. Here we report the hierarchical self-assembly and chiroptical
studies of a group of 4d–4f heterometallic cages synthesized
from a preformed dimetalloligand [(bpy)2Pd212]2+ (2) (bpy = 2,2-bipyridine)
and a variety of trivalent lanthanide ions (Ln = NdIII,
EuIII, YbIII). The programmable self-assembly
process leading to the trigonal bipyramidal cages formulated as {Ln2[(bpy)2Pd212]3}12+ (3) has been confirmed
by one- and two-dimensional NMR, electro-spray-ionization time-of-flight
mass-spectroscopy, and in one typical case by single-crystal X-ray
diffraction studies. Circular dichroism and circular polarized luminescence
spectra confirmed the strict control of stereoselectivity on the heterometallic
cages, dictated by the chiral amide groups on the ligands. Excitation
(up to 420 nm) on the dipalladium chromophores on these cages leads
to the characteristic lanthanide luminescence at both the visible
and the near-infrared regions, depending on the lanthanide ions used.
Through the assembly–disassembly process, luminescent turn-off
sensing toward penicillin among several widely used antibiotics has
also been demonstrated with the Europium cage, featuring a limit of
detection as low as 0.88 ppb (S/N = 3). Our results pave the way for
the construction of chiral 4d–4f supramolecular cages which
may find potential applications in luminescent sensing and/or labeling
reagents.
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Keywords
Chiroptical Studiesself-assembly processchiral 4Yb III2 Pd 2 1 2lanthanide luminescencebpyheterometallic cageslanthanide ions420 nm0.88 ppbchiral amide groupstrivalent lanthanide ionsNd IIIelectro-spray-ionization time-of-flight mass-spectroscopysingle-crystal X-ray diffraction studiesdipalladium chromophoresEuropium cagechiroptical studiesNMREu IIILuminescent 4luminescence spectraCircular dichroismnear-infrared regionsHierarchical Self-Assemblybipyramidal cages
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