Solvothermal synthesis and crystal structure of a heterometal-bridged {V 15 Sb 6 } dimer: [Ni 2 (tren) 3 (V 15 Sb 6 O 42 (H 2 O) 0.5 )] 2 [Ni(trenH) 2 ]·H 2 O

Covalent Co–O–V and Sb–N Bonds Enable Polyoxovanadate Charge Control

“…Dimeric {[Ni 2 (tren) 3 (V 15 Sb 6 O 42 (H 2 O) 0.5 )] 2 } 4– fragments were found in [Ni(trenH) 2 ][Ni 2 (tren) 3 (V 15 Sb 6 O 42 (H 2 O) 0.5 )] 2 ·H 2 O containing in situ produced [Ni 2 (tren) 3 ] 4+ complexes. 14 Adjusting the reaction temperature afforded the crystallization of two pseudopolymorphic compounds with compositions [Ni(dien) 2 ] 3 [V 15 Sb 6 O 42 (H 2 O)]· n H 2 O ( n = 12 and 8). 15 The two pseudopolymorphs differ in the occurrence of {Ni(dien) 2 } 2+ complexes adopting the s-fac , mer , and u-fac configurations in one compound and only a mer -{Ni(dien) 2 } 2+ complex in the other compound.…”

Unprecedented Connection Mode of [V16Sb4O42(H2O)]8– Cluster Anions by Mn2+ Centered Complexes: Solvothermal Synthesis and Properties of {[Mn(teta)]4V16Sb4O42(H2O}n·[(H2O)12]n

“…All geometric parameters are in the range reported for POVs. [4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][25][26][27][28][29][30][31][32][33][34][35] (Tables S2 and S3). There are only two structures reported in the CCDC, in which a Mn 2+ cation is coordinated by one teta ligand and two O atoms.…”

“…[1] Since the discovery of the first hetero-POV [V 15 As 6 O 42 (H 2 O)] 6-, [2,3] which is structurally related to the V 18 O 42 cluster by replacing three VO 5 square pyramids by three handle-like As 2 O 5 moieties, many efforts were undertaken preparing new hetero-POVs displaying different chemical compositions and physical properties. Antimony-POVs (Sb-POVs) are a sub-class of the hetero-POVs, of which three cluster types are known: [V 14 16 }.…”

“…[5] A V-richer Sb-POV was discovered by our group in the compound (C 6 H 17 N 3 ) 4 [V 16 Sb 4 O 42 ]·2H 2 O (C 6 H 17 N 3 = doubly protonated 2-piperazine-N-ethylamine). [6] By systematically varying the solvothermal reaction conditions we were able to synthesize the antimony analogue of the spin-frustrated [V 15 As 6 O 42 (H 2 O)] 6-molecular magnet. [7] A charge tion mode between cluster anions and complex cations generates two individual layers stacked onto each other.…”

“…[8] While in this compound the {V 16 Sb 4 } core is expanded by a central V IV atom, the application of other transition metal cations in the reaction slurries generated a variety of Sb-POVs with variable dimensionalities. [9][10][11][12][13][14][15][16][17] The chemistry and structural diversity could be expanded by formation of inorganic-organic hybrid structures like observed in [V 14 [18] or in [{Co II (teta) 2 [19] While all these compounds were synthesized under solvothermal conditions applying Sb and V compounds as starting materials, further Sb-POVs could be prepared recently applying a water soluble Sb-POV. [20][21][22] In literature 34 Sb-POVs have been reported, of which 11 belong to the {V 14 16 } cluster is interconnected by a transition metal complex to form a chain, [9] while in all other {V 16 } anion based compounds cations and anions are isolated.…”