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New Water‐Soluble Cluster Compound {Zn(en) 3 } 3 [V 15 Sb 6 O 42 (H 2 O)]⋅ (Ethylenediamine) 3 ⋅10 H 2 O as a Synthon for the Generation of Two New Antimonato Polyoxovanadates
Author(s) -
Mahnke Lisa K.,
Warzok Ulrike,
Lin Mengxi,
Näther Christian,
Schalley Christoph A.,
Bensch Wolfgang
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201705732
Subject(s) - chemistry , ethylenediamine , aqueous solution , crystallography , crystallization , electrospray ionization , crystal structure , zinc , isostructural , nuclear chemistry , inorganic chemistry , ion , organic chemistry
A new antimonato polyoxovanadate {Zn(en) 3 } 3 [V 15 Sb 6 O 42 (H 2 O)] ⋅ 3 en ⋅ 10 H 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 72 h. At longer times, slow transformation into a {V 14 Sb 8 O 42 } cluster is observed. The conversion reaches 50 % after 14 days and is complete after approximately 20 days. The rate of this {V 15 Sb 6 }→{V 14 Sb 8 } 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 V 15 Sb 6 O 42 (H 2 O)] ⋅ 23 H 2 O after a short reaction time, whereas addition of Sb 2 O 3 led to fast crystallization of {(Zn(en) 2 (H 2 O) 2 )(Zn(en) 2 )}[Zn(en) 2 V 15 Sb 6 O 42 (H 2 O)] ⋅ 8.5 H 2 O. In the crystal structure of {Zn(en) 3 } 3 [V 15 Sb 6 O 42 (H 2 O)] ⋅ 3 en ⋅ 10 H 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 [V 15 Sb 6 O 42 (H 2 O)] 6− anions are expanded by Zn 2+ ‐centered complexes through Zn−O−V bond formation.