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.

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

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.

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,...