New Water-Soluble Cluster Compound {Zn(en)(3)}(3)[V15Sb6O42(H2O)]center dot(Ethylenediamine)(3)center dot 10H(2)O as a Synthon for the Generation of Two New Antimonato Polyoxovanadates

作者：Mahnke Lisa K; Warzok Ulrike; Lin Mengxi; Naether Christian; Schalley Christoph A; Bensch Wolfgang^*

来源：Chemistry - A European Journal, 2018, 24(21): 5522-5528.

DOI：10.1002/chem.201705732

• cluster compounds
• crystal structure
• ESI-MS
• solvothermal synthesis
• water-soluble precursor

A new antimonato polyoxovanadate {Zn(en)(3)}(3)[V15Sb6O42(H2O)]center dot 3en center dot 10H(2)O (en = ethylenediamine) synthesized under hydrothermal conditions exhibits remarkable solubility in water. Electrospray ionization mass spectrometry (ESI-MS) investigations on an aqueous solution demonstrate that the cluster core remains fully intact for 72h. At longer times, slow transformation into a {V14Sb8O42} cluster is observed. The conversion reaches 50% after 14days and is complete after approximately 20days. The rate of this {V15Sb6}->{V14Sb8} cluster transformation is significantly increased in the presence of ammonium acetate. Applying the new compound as a synthon in the presence of 1,10-phenanthroline (phen) led to crystallization of {Zn(phen)(3)}(2)[Zn(en)(2)V15Sb6O42(H2O)]center dot 23H(2)O after a short reaction time, whereas addition of Sb2O3 led to fast crystallization of {(Zn(en)(2)(H2O)(2))(Zn(en)(2))}[Zn(en)(2)V15Sb6O42(H2O)]center dot 8.5H(2)O. In the crystal structure of {Zn(en)(3)}(3)[V15Sb6O42(H2O)]center dot 3en center dot 10H(2)O, the en molecules are seen to be attached to the cluster anion through Sb-N bonds. In the structures of the two new compounds obtained, the [V15Sb6O42(H2O)](6-) anions are expanded by Zn2+-centered complexes through Zn-O-V bond formation.

• 出版日期2018-4-11