Structural influences of arsenic–vanadium clusters and transition metal complexes on final structures of arsenic–vanadium-based hybrids

An Exotic Layered Compound Consisting of Interconnected Arsenato‐Polyoxovanadate Clusters: Thermal and Magnetic Properties and Liquid Phase Exfoliation

“…A CSD survey shows that only three Mn 2+ containing compounds are known with the meridional conformation ( trans position of the O atoms) but in all these compounds the teta ligand was chemically expanded by further organic groups. For Mn 2+ coordinated by not modified teta only the cis configuration of the O atoms was reported (Supporting Information Table S7) [3,9–17,22–35,38–44,46–53] …”

“…The most common clusters of As‐POVs are {V 12 As 8 O 40 }, [28,31,38–43] {V 14 As 8 O 42 }, [10,12,13,22–35] {V 15 As 6 O 42 } [9–17,44] and {V 16 As 4 O 42 } [3] . We note that the structure of {V 12 As 8 O 40 } is not related to that of {V 18 O 42 } [2] .…”

“…The crystal structures of such hetero‐POVs are often related to the {V 18 O 42 } cluster [2] by formal replacement of two, three or four {VO 5 } pyramids by two, three or four {E 2 O 5 } or {E′ 2 O 7 } units (E=Sb, As, E′=Si, Ge). Focusing on As and Sb, the general formulas are {V 16 E 4 O 42 }, [3–6,7,8] {V 15 E 6 O 42 } [4,5,9–18,19,20,21] and {V 14 E 8 O 42 } [6,8,10,12,13,18,20,22–35,36] . The first high‐nuclearity As‐POV was [V 15 As 6 O 42 ] 6− published in 1988, [11] and due to its unusual magnetic and electronic properties this cluster was investigated intensively [37]…”

Mn2+ substitution within the {V14As8} polyoxovanadate archetype results in {Mn2V12As8} shells with trans‐positioned heterometal positions

“…[13] In the crystal structures of these compounds the cluster anions and cations are either isolated, or cluster shells are joined (or expanded) by transition metal cation-centered complexes. [14][15][16][17][18][19][20][21][22] Additional structural mod-ification is achieved by integration of transition metal cations like Zn 2+ or Cd 2 + into the As-POV cluster shell. [23][24][25][26][27] In the structure of these compounds one or two V centers of the {V 14 As 8 O 42 } moiety are substituted by either Zn 2 + or Cd 2+ .…”

“…In the following years the chemistry of high‐nuclearity As‐POVs was systematically developed by isolation and characterization of cluster anions with different compositions like [V 14 AsO 40 ] 7− , [2] [V 10 AsO 26 (H 2 O)] ⋅ 8H 2 O, [3] [V 5 As 2 O 19 ] 4− , [4] [V 12 As 3 O 42 ] 15− , [5] [V 16 As 4 O 42 (H 2 O)] 8− , [6] [H 3 V 12 As 4 O 43 ] 8− , [7] [V 15 As 6 O 51 ] ∞ 9− , [8] [V 12 As 8 O 40 (HCO 2 )] 3− , [9] [V 12 As 8 O 40 (H 2 O)] 4− , [10] [V 14 As 8 O 42 (H 2 O) 0.5 ] 4− , [11,12] [V 6 As 8 O 26 ] 4− [13] . In the crystal structures of these compounds the cluster anions and cations are either isolated, or cluster shells are joined (or expanded) by transition metal cation‐centered complexes [14–22] . Additional structural modification is achieved by integration of transition metal cations like Zn 2+ or Cd 2+ into the As‐POV cluster shell [23–27] .…”