Two Vanadogermanates from 1-Dimensional Chain to 2-Dimensional Network Built from Di-Cd-Substituted Ge–V–O Clusters and Transition Metal Complex Bridges

Abstract

Two novel vanadogermanates [Cd(en)(H 2 O) 2 ][Cd-(en) 2 ][Cd(en)]{[Cd(en)] 2 [Ge 8 V 12 O 42.5 (OH) 5 ]}•2H 2 O (1) and [Cd(en) 3 ][Cd(en)] 2 {[Cd(en)] 2 [Ge 8 V 12 O 42 (OH) 6 ]}•10H 2 O (2, en = ethylenediamine) have been hydrothermally synthesized and structurally characterized by elemental analysis, infrared spectroscopy, powder X-ray diffractions, thermogravimetric analysis, UV−vis spectroscopy, and single-crystal X-ray diffractions. Structural analysis reveals that the Ge−V−O cluster anions in the two compounds are derived from the classical saturated {V 18 O 42 } cluster by replacing four VO 5 square pyramids with four Ge 2 O 7 groups. Especially, the Ge−V−O cluster anion in 2 is a new configuration of Ge−V−O clusters with four Ge 2 O 7 groups and first reported in this work. 1 is the first 1-dimensional (1-D) chain based on the linkage of c e n t r o s y m m e t r i c d i m e r i c c l u s t e r s { [ C d -(en)] 2 [Ge 8 V 12 O 42.5 (OH) 5 ]} 2 12− and trinuclearity [Cd 3 O 4 (en) 4 (H 2 O) 2 ] 2− complexes. 2 is an unprecedented 2-D network built from unique {[Cd(en)] 2 [Ge 8 V 12 O 42 (OH) 6 ]} 8− clusters and 1-D coordination chains {Cd 3 O 2 (en) 5 } 2+ . Magnetic measurements illustrate that these compounds have overall antiferromagnetic exchange interactions between metal ions.

A Bicadmium-Substituted Polyoxometalate Network Based on a Vanadosilicate Cluster for the Selective Oxidation of Styrene to Benzaldehyde

“…The bond-valence-sum calculations show that the valence states of V atoms are from 4.086 to 4.158 (Table S4). Moreover, the {(en) 2 Cd 2 Si 8 V 12 O 40 (OH) 8 } cluster also displays a structural feature similar to those of the reported {(en) 2 Cd 2 Ge 8 V 12 O 48 } clusters − and {(en) 2 M x As 8 V 13/12 O 40 } (M = Zn/Cd/Ni, x = 1 or 2). − Nevertheless, to the best of our knowledge, compound 1 is the first observation of TM-substituted vanadosilicate cages.…”

Exploring the Magnetic Interaction of Asymmetric Structures Based on Chiral VIII8 Clusters

“…Thus, far, it has been demonstrated that a majority of reported POVs presented antiferromagnetic coupling interactions, − while it is rarely known about the ferromagnetic exchange interactions based on POVs. ,− What’s more, the ferromagnetic exchange interactions of reported POVs are usually existed in the high value vanadium ions and to the best of our knowledge, only two cases of highly reduced POVs with ferromagnetism reported before. , Besides, most of the heteropolyvanadates like phosphovanadate, polyoxovanadogermanates, polyoxovanadatoarsenates, polyoxovanadatoantimonates, etc. also have magnetic properties, which are almost presented as antiferromagnetic coupling interactions. − Therefore, it is very meaningful to explore the potential of novel highly reduced POVs with ferromagnetic interactions, providing magnetic model systems.…”

In‐situ Complex and Sb–N Bond Formation in an Antimonato Polyoxovanadate Reaction System

“…Selected examples are [Mn 4 V 4 O 17 (OAc) 3 ] 3– or ( n Bu 4 N) 3 [Co(AcO)V 4 O 12 ] . The polyoxovanadate cluster can also be modified by integration of main group semi‐metals leading to compounds like [Cd(en) 3 ][Cd(en)] 2 {[Cd(en)] 2 [V 12 Ge 8 VO 42 (OH) 6 ]} · 10H 2 O, [V 14 Ge 8 O 42 S 8 ] 12– , (V 15 (H 2 pdn) 3 (Hpdn)[V 15 Si 6 O 42 (OH) 6 (Cl)] · n H 2 O ( n = 7–10) (pdn = 1,3‐propanediamine), (H 1.5 pdn) 6 [{H 2 V 15 Si 6 O 48 (Cl)}(VO 2 ) 2 ] · 4H 2 O, K 6 [V 15 As 6 O 42 (H 2 O)] · 8H 2 O, or [Co(en) 3 ][{Co(en) 2 } 2 V 15 As 6 O 42 ] · 4H 2 O (en = ethylenediamine) …”