Inside Cover: Anion‐Guided Stepwise Assembly of High‐Nuclearity Lanthanide Hydroxide Clusters (Angew. Chem. Int. Ed. 33/2022)

Abstract

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.

Platonic and Archimedean solids in discrete metal-containing clusters

“…391,392 In addition, two different research groups revealed two different ways to generate similar Ln 60 clusters. 393,394 By controlling the hydrolysis of Ln(ClO 55 These clusters represent the second largest lanthanide-exclusive cluster to date, while the largest is the {Gd 140 } wheel. 52 These huge Ln oxyhydroxide clusters (Fig.…”

“…[654][655][656] In recent years, with some exploration on the role of various anion templates in directing the multi-step assembly process of high-nuclearity metal clusters, the guiding role of the homo-/hetero-anions in the ''dynamic'' process becomes clearer, which is not limited to the somewhat ''static'' role for directing structure or supporting construction. 387,393,394,501,516,657 Recently, the study by Zheng and Feng provided a rare groundbreaking example, i.e., how to generate a large target-lanthanide hydroxide cluster (Ln 60 cluster with an individual sodalite cage structure, Fig. 42d) through hetero-anion-guided rational stepwise assembly (Fig.…”

“…74). 393 A reasonable ''dynamic'' route starting from the Er(ClO In addition to the structural template effect, the strategy of intercalating a large number of anions has shown increasing ; O@V 6 , V 6 Rh 4 ; Cl@V 4 , Cl 6 @V 24 As 8 ; Cl@Gd 5 , Gd 50 ; S@Ag 6 , Ag 192 ; S@Ag 8 , Ag 90 ; Si@Al 8 , Al 14 ; CO 3 @Gd 5 , Gd 20 ; CO 3 @Gd 6 , Gd 60 ; SO 4 @Ce 3 , Ce 12 V 6 ; MoO 4 @Co 6 , Co 24 ; SO 4 @Ag 9 , Ag 192 ; SO 4 @Ag 12 , Ag 192 ; and SO 4 @Ag 12 , Ag 90 .…”

“…391,392 In addition, two different research groups revealed two different ways to generate similar Ln 60 clusters. 393,394…”

“…74). 393 A reasonable “dynamic” route starting from the Er(ClO 4 ) 3 metal salt to Er 60 ([Er 60 (μ 6 -CO 3 ) 8 (μ 4 -I) 7 (μ 2 -NO 3 ) 12 (μ 3 -OH) 96 (His) 24 (H 2 O) 36 ](ClO 4 ) 5 I 4 -(NO 3 ) 16 , H-His = l -histidine) was outlined (Fig. 74a) by capturing three key intermediates ( Er 12 ([Er 12 (μ 4 -I) 2 (μ 3 -OH) 16 (His) 8 (H 2 O) 20 ](ClO 4 ) 10 ), Er 34 ([Er 34 (μ 6 -CO 3 ) 2 (μ 5 -CO 3 ) 2 (μ 4 -I) 2 (μ 3 -OH) 48 (His) 20 (H-His) 8 (H 2 O) 24 ](ClO 4 ) 15 I 9 ), and Er 48 ([Er 48 (μ 6 -CO 3 ) 4 (μ 5 -CO 3 ) 3 (μ 4 -I) 4 (μ 2 -NO 3 ) 3 (μ 3 -OH) 72 (His) 24 (H-His) 6 (H 2 O) 24 ](ClO 4 ) 11 I 6 (NO 3 ) 10 ) with the guidance of I − , I − /CO 3 2− , I − /CO 3 2− /NO 3 − , respectively, Fig.…”