Construction of supramolecular structures with internal functionalities is a promising approach to build enzyme‐like cavities. The endo‐functionalized [Pd12L24] and [Pd2L4] coordination cages represent the most successful systems in this regard. However, these systems mainly contain one type of endo‐moiety. We herein provide a solution for the controlled endo‐functionalization of [Pd2L4] cages. Site‐selective introduction of the endo‐functional group was achieved through the formation of heteroleptic [Pd2(LA)2(LB)(LC)] cages. Using two orthogonal steric control elements is the key for the selective formation of the hetero‐assemblies. We demonstrated the construction of two hetero‐cages with a single internal functional group as well as a hetero‐cage with two distinct endohedral functionalities. The endo‐functionalized hetero‐cages bound sulfonate guests with fast‐exchange dynamics. This strategy provides a new solution for the controlled endo‐functionalization of supramolecular cavities.
The rational synthesis … …ofhigh-nuclearity lanthanide clusters remains challenging.Intheir Research Article (e202205385), Min Feng, Zhiping Zheng,and co-workers developed astepwise synthesis of ahigh-nuclearity sodalite cage-like cluster Er 60 ,guided by judiciously selected anions. Thesuccessive introduction of I À ,CO 3 2À ,and NO 3 À led to the isolation of three crucial intermediate clusters,n amely the wheel-like Er 12 ,s hip-like Er 34 ,a nd bowl-like Er 48 . These findings opened the "black box" of the elusive self-assembly process and provided mechanistic insights.
Mechanically interlocked molecules (MIMs) and host-guest chemistry have received great attention in the past few decades. However, it remains challenging to design architectures with mechanically interlocked features and construct cavities for guest molecule recognition using similar building blocks. In this study, we designed and constructed a series of novel twisted supramolecular structures by assembling various multitopic terpyridinyl (tpy) ligands with the same diameter and Zn(II) ions. The obtained complexes exhibited evolutional architectures and showed distinctively different space-constraint effects. Specifically, the assembled dimer SA, SB, and SBH displayed mechanically interlocked phenomena with the increase of concentration, including [2]catenane and [3]catenane. However, no interlocked structures were observed in complexes SC and SCH constructed by hexatopic tpy ligands, due to the significant space constraints. The single-crystal data of complex SCH further proved significant space constraints and illustrated the formation
Water-stable anionic Ln2L2-type (Ln = LaIII, EuIII) lanthanide-organic macrocycles have been constructed from deprotonation self-assembly of a bis-tridentate ligand consisting of two 2,6-bis-(1,2,4-triazole)-pyridine chelation arms bridged by a dibenzofuran chromophore,...
Water-soluble metallo-supramolecular cages with well-defined nanosized cavities have a wide range of functions and applications. Herein, we design and synthesize two series of metallo-supramolecular octahedral cages based on the selfassembly of two congeneric truxene-derived tripyridyl ligands modified with two polyethylene glycol (PEG) chains, i.e., monodispersed tetraethylene glycol (TEG) and polydispersed PEG-1000, with four divalent transition metals (i.e., Pd, Cu, Ni, and Zn). The resulting monodispersed cages C1−C4 are fully characterized by electrospray ionization mass spectrometry (ESI-MS), nuclear magnetic resonance (NMR) spectroscopy, and single-crystal X-ray diffraction. The polydispersed cages C5−C8 display good water solubilities and can act as nanoreactors to mediate visible-light-promoted C(sp 3 )−C(sp 2 ) crossdehydrogenative coupling reactions in an aqueous phase. In particular, the most robust Pd(II)-linked water-soluble polydispersed nanoreactor C5 is characterized by ESI-MS and capable of mediating the reactions with the highest efficiencies. Detailed host−guest binding studies in conjunction with control studies suggest that these cages could encapsulate the substrates simultaneously inside its hydrophobic cavity while interacting with the photosensitizer (i.e., eosin Y).
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...
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.
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