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High Nuclearity Antimonato‐Polyoxovanadate Cluster {V 15 Sb 6 O 42 } as a Synthon for the Solvothermal in situ Generation of α‐ and β‐{V 14 Sb 8 O 42 } Isomers
Author(s) -
Wendt Michael,
Näther Christian,
Bensch Wolfgang
Publication year - 2016
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.201601401
Subject(s) - synthon , chemistry , crystallography , ethylenediamine , crystallization , cluster (spacecraft) , heteroatom , crystal structure , stereochemistry , inorganic chemistry , ring (chemistry) , programming language , organic chemistry , computer science
New heteroatom polyoxovanadates (POVs) were synthesized by applying a water‐soluble high‐nuclearity cluster as new synthon. The [V 15 Sb 6 O 42 ] 6− cluster shell exhibiting D 3 symmetry was in situ transformed into completely different cluster shells, namely, the α‐[V 14 Sb 8 O 42 ] 4− isomer with D 2 d and the β‐[V 14 Sb 8 O 42 ] 4− isomer with D 2 h symmetry. The solvothermal reaction of {Ni(en) 3 } 3 [V 15 Sb 6 O 42 (H 2 O) x ] ⋅ 15 H 2 O ( x =0 or 1; en=ethylenediamine) in water led to the crystallization of [{Ni(en) 2 } 2 V 14 Sb 8 O 42 ] ⋅ 5.5 H 2 O containing the β‐isomer. The addition of [Ni(phen) 3 ](ClO 4 ) 2 ⋅ 0.5 H 2 O (phen=1,10‐phenanthroline) to the reaction slurry gave the new compound {Ni(phen) 3 } 2 [V 14 Sb 8 O 42 ] ⋅ phen ⋅ 12 H 2 O with the α‐isomer. Both transformation reactions are complex due the change of symmetry, the chemical composition, and rearrangement of the VO 5 square pyramids and Sb 2 O 5 handle‐like moieties.