In Situ Construction of a Coordination Zirconocene Tetrahedron

Abstract

The current study describes the first in situ synthesis and characterization of a new family of cationic coordination tetrahedra of both the V4F4 and V4E6 type, which are constructed by a new building block based on a trinuclear zirconocene moiety and the dicarboxylate or tricarboxylate anions.

An Amine‐Functionalized Zirconium Metal–Organic Polyhedron Photocatalyst with High Visible‐Light Activity for Hydrogen Production

“…Zr‐MOPs are constructed through the slow hydrolysis of Cp 2 ZrCl 2 , which results in a trinuclear ligand‐bridged Zr‐cation polyhedron (Figure a) . Single‐crystal X‐ray crystallography results indicate that an isolated cationic zirconocene coordination tetrahedron with V 4 E 6 topology (V=vertex, E=edge), {[Cp 3 Zr 3 O−(OH) 3 ] 4 (BDC) 6 } 4+ (ZrT‐1), is formed, and Cl − acts as a counterion to balance charges.…”

“…[13] Expanding upon research into Zr-MOFs, some researchers have reported the synthesis of zirconium-basedMOPs, which are composed of trinuclearz irconium clusters and different carboxylate ligands. [14] Yuan and co-workers synthesized as eries of tetrahedral Zr-MOPs, the stabilities of which were systematicallys tudied at differentp Hv alues. All of these polyhedra exhibited excellent stabilityi na cidic, neutral, and even alkaline aqueous solution environments.…”

Controlled Orthogonal Self‐Assembly of Heterometal‐Decorated Coordination Cages

“…The different binding characteristics meet the essential requirement for fabrication of HDCCs through multiple orthogonal coordinative interactions. Our previous works showed that the “hard” trinuclear Zr IV cluster can selectively coordinate to carboxylic acids to construct a coordination tetrahedron . When H 2 bpydc is combined with zirconocene dichloride to form a coordination tetrahedron cage, the bipyridyl groups can at the same time orthogonally coordinate with other “soft” metal ions such as Cu II or Pd II , thus inducing the formation of a HDCC.…”

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

“…In 2013, Liu et al. synthesized four Zr IV ‐based tetrahedral carboxylate cages with the molecular formula {[Cp 3 Zr 3 μ 3 ‐O(μ 2 ‐OH) 3 ] 4 (bdc) 6 } ⋅ Cl 4 ⋅ n S; {[Cp 3 Zr 3 μ 3 ‐O(μ 2 ‐OH) 3 ] 4 (btc) 4 } ⋅ Cl 4 ⋅ 4 DMF ⋅ n S; {[Cp 3 Zr 3 μ 3 ‐O(μ 2 ‐OH) 3 ] 4 (bpdc) 6 } ⋅ Cl 4 ⋅ n S; and {[Cp 3 Zr 3 μ 3 ‐O(μ 2 ‐OH) 3 ] 4 (btb) 4 } ⋅ Cl 4 ⋅ n S, in which Cp=cyclopentadienyl, bdc=benzene‐1,4‐dicarboxylate, btc=benzene‐1,3,5‐tricarboxylate, bpdc=4,4′‐biphenyldicarboxylate, H 3 btb=4,4′,4′′‐benzene‐1,3,5‐triyltris (benzoic acid), and S represents free solvent molecules . All these cationic cages are isostructural in nature.…”

“…[67] The NBO charge on Oa toms in OH À is higher than that of Oa toms in COOH groups (À1.403 vs. À0. 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.…”