Controlled Orthogonal Self‐Assembly of Heterometal‐Decorated Coordination Cages

Abstract

Multiple orthogonal coordinative interactions were utilized to construct heterometal-decorated tetrahedral cages from in situ formed trinuclear Zr clusters through the combination with other metal ions such as Cu or Pd . Through effective use of the hard/soft acid/base principle, the orthogonal self-assembly process of Zr-bpydc-CuCl (H bpydc=2,2-bipyridine-5,5-dicarboxylic acid) can be finely controlled using three strategies: post-synthetic metallization, a stepwise metalloligand approach, or a one-pot reaction.

Stabilizing Metal–Organic Polyhedra (MOP): Issues and Strategies

“…All these cationic cages are isostructural in nature. In another report, the same group developed a pair of heterometal (Pd II or Cu II )‐decorated Zr IV carboxylate based cationic tetrahedral cages: Zr‐bpydc‐MCl 2 (H 2 bpydc=2,2‐bipyridine‐5,5‐dicarboxylic acid; M=Cu 2+ or Pd 2+ ) . These cages were prepared by three synthetic strategies: post‐synthetic metallization, a stepwise metalloligand approach, and a one‐pot synthesis.…”

“…74 [68] All these cationic cages are isostructural in nature.I na nother report, the same group developed a pair of heterometal (Pd II or Cu II )-decorated Zr IV carboxylate based cationic tetrahedral cages:Z r-bpydc-MCl 2 (H 2 bpydc = 2,2-bipyridine-5,5-dicarboxylic acid;M= Cu 2 + or Pd 2 + ). [69] These cages were prepared by three synthetic strategies:p ost-synthetic metallization, as tepwise metalloligand approach, and a one-pot synthesis. Chen and co-workers demonstrated porous coordination cages that featured both intrinsic and extrinsic porosities, formulated as [Cp 3 Zr 3 (m 3 12 ·Cl 8 ·n S (d-cam = d-camphoric acid, S = free solventm olecule; Figure 1).…”

Breathing 3D Frameworks with T-Shaped Connecting Ligand Exhibiting Solvent Induction, Metal Ions Effect and Luminescent Properties

“…The multidentate ligand 2,2 -bipyridine-5,5 -dicarboxylic acid (H 2 bpdc) is a good candidate because it contains two types of coordination groups-carboxylate groups and chelating position N-donors-which can act in linear bridging mode and/or T-shaped connecting mode [20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37]. To date, there are 20 different coordination modes for H 2 bpdc ligand observed in the structures retrieved from the Cambridge Structural Database (CSD version 5.38, February 2017) [38] (Figure 1, Scheme S1).…”

“…Among those, type b usually results in zero dimensional molecular complexes, as it only acts as a chelating ligand via N-donors from the bipyridine [28]. To construct 3D flexible PCPs, although type a (T-shaped connecting mode) is reported more frequently, type c (linear bridging mode) is the most favorable option because the bpdc 2− ligands in the former type often act essentially as rigid spacers [20][21][22][23]. Besides that, auxiliary ligands were also introduced to tune the flexibility of the frameworks [24].…”

“…Crystals 2017, 7, 311 2 of 12 favorable option because the bpdc 2− ligands in the former type often act essentially as rigid spacers [20][21][22][23]. Besides that, auxiliary ligands were also introduced to tune the flexibility of the frameworks [24].…”