Due to the dynamic reversibility of coordination-driven force, the structures of metallo-cages are sensitive to many stimulus, including ligand geometry, temperature, concentration, anions, pH, light, and so on. Among them,...
Materials for organic
light-emitting devices which exhibit superior
emission properties in both the solution and solid states with a high
fluorescence quantum yield have been extensively sought after. Herein,
two metallocages, S1 and S2, were constructed,
and both showed typical aggregation-induced emission (AIE) features
with intense yellow fluorescence. By adding blue-emissive 9,10-dimethylanthracene,
pure white light emission can be produced in the solution of S1 and S2. Furthermore, due to the remarkable
AIE feature and good fluorescence quantum yield in the solid state,
metallocages are highly emissive in the solid state and can be utilized
to coat blue LED bulbs or integrate with blue-emitting chips to obtain
white light. This study advances the usage of metallocages as practical
solid-state fluorescent materials and provides a fresh perspective
on highly emissive AIE materials.
Two metallo-triangles SA and SB with cis-TPE motifs were constructed and their fluorescence properties were explored. Compared with dilute solution, both triangles SA and SB exhibited significant AIE behavior in...
Three‐dimensional (3D) structures constructed via coordination‐driven self‐assemblies have recently garnered increasing attention due to the challenges in structural design and potential applications. In particular, developing new strategy for the convenient and precise self‐assemblies of 3D supramolecular structures is of utmost interest. Introducing the concept of self‐coordination ligands, herein the design and synthesis of two meta‐modified terpyridyl ligands with selective self‐complementary coordination moiety are reported and their capability to assemble into two hourglass‐shaped nanocages SA and SB is demonstrated. Within these 3D structures, the meta‐modified terpyridyl unit preferably coordinates with itself to serve as concave part. By changing the arm length of the ligands, hexamer (SA) and tetramer (SB) are obtained respectively. In‐depth studies on the assembly mechanism of SA and SB indicate that the dimers could be formed first via self‐complementary coordination and play crucial roles in controlling the final structures. Moreover, both SA and SB can go through hierarchical self‐assemblies in solution as well as on solid–liquid interface, which are characterized by transmission electron microscope (TEM) and scanning tunneling microscopy (STM). It is further demonstrated that various higher‐order assembly structures can be achieved by tuning the environmental conditions.
In
this study, two trigonal prisms based on the 1,3,5-triazine
motif (SA and SB), distinguished by hydrophobic
groups, were prepared by the self-assembly of tritopic terpyridine
ligands and Zn(II) ions. SA and SB exhibited
high luminescence efficiencies in the solid state, overcoming the
fluorescence quenching of the 1,3,5-triazine group caused by π–π
interactions. Notably, SA and SB exhibited
different luminescence behaviors in the solution state and aggregation
state. SB with 12 alkyl chains exhibited extremely weak
fluorescence in a dilute solution, but its fluorescence intensity
and photoluminescence quantum yield (PLQY) were significantly enhanced
in the aggregated state (with the increase in the water fraction),
especially in the solid state. Different from the gradually enhanced
efficiency of SB, the PLQY of SA gradually
decreased with the increase in aggregation but still maintained a
high luminescence efficiency. These two complexes exhibited different
modes to solve the fluorescence quenching of 1,3,5-triazine in the
solid state. The hierarchical self-assembly of SB exhibited
nanorods owing to the hydrophobic interactions of alky chains, while SA aggregated into spheres under the influence of π–π
interactions.
Terpyridine‐based discrete supramolecular architectures with metal ions at the corners have rarely been reported. Herein, we report two dissymmetric terpyridyl ligands LA and LB decorated at the 5‐position and 4‐position of terpyridine respectively. The complexes constructed by the self‐assembly of LA and LB with Zn(II) exhibit hand‐circle‐like structures. Moreover, all Zn(II) are successfully fixed in the corners. A series of dimeric to hexameric macrocycles is obtained by head‐to‐tail connections with changing concentration. This work will pave the way for preparation of more elaborate self‐assembled structures based on dissymetric ligands.
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