trans‐Dinitrosyl‐Substituted Hexamolybdate and Study of Its Controllable NO Release

Abstract

On the basis of the well-developed N,NЈ-dicyclohexylcarbodiimide (DCC) imidoylization strategy, the novel trans-dinitrosyl-substituted polyoxometalate (POM) (NBu 4 ) 4 -[Mo 6 O 17 (ϵNO) 2 ] was synthesized in moderate yield with high purity through a highly selective reaction route under mild reaction conditions. Its structure was elucidated by IR and UV/Vis spectroscopy, ESI-MS, and single-crystal X-ray diffraction studies. Furthermore, its ability to undergo con-

Aliphatic Organoimido Derivatives of Polyoxometalates Containing a Bioactive Ligand

“…This peak indeed exists for compound 2 , but for compound 3 ( trans configuration), the peak at 960 cm −1 is hard to distinguish. Compound 3 shows a new band at 910 cm −1 compared with compounds 1 and 2 , which was also observed for ( n Bu 4 N) 4 { trans‐ [Mo 6 O 17 (NO) 2 ]} (Supporting Information, Figure S8) 39. Without considering the effect of the imido ligand, we deduced that the peak at 910 cm −1 may be characteristic of trans ‐disubstituted organoimido hexamolybdates, and this assumption is supported by our previous calculations 40.…”

“…The IR spectra of compounds 1-4 are in good accordance with those of reported organoimido hexamolybdates and similar to each other. [39] Without considering the effect of the imido ligand, we deduced that the peak at 910 cm À1 may be characteristic of trans-disubstituted organoimido hexamolybdates, and this assumption is supported by our previous calculations. In compound 1, the band at 973 cm À1 is a diagnostic of the MoN stretching vibration.…”

“…However, the crystal of 2 contains one ethyl acetate molecule and one diethyl ether molecule, since ethyl acetate was used in workup, and diethyl ether in the process of single‐crystal growth by diffusion. Similar to trans ‐dinitrosyl‐substituted hexamolybdate ( n Bu 4 N) 4 { trans‐ [Mo 6 O 17 (NO) 2 ]},39 compound 3 is also constructed from two crystallographically different but chemically equivalent half‐cluster anions of types A and B, each of which belongs to a crystallographic symmetry center (Figure 1 c, d). Moreover, the cluster anions of 3 show an interesting packing mode.…”

“…Thus, the question arises whether its reaction with O h -symmetric [Mo 6 O 18 ] 2À to form an organic-inorganic cage can also produce an extra chiral rotation axis. Similar to trans-dinitrosyl-substituted hexamolybdate (nBu 4 N) 4 {trans-[Mo 6 O 17 (NO) 2 ]}, [39] compound 3 is also constructed from two crystallographically different but chemically equivalent half-cluster anions of types A and B, each of which belongs to a crystallographic symmetry center (Figure 1 c, d). First, we performed a systematic structural study on the amantadine-substituted substituted hexamolybdates and thoroughly compared their differences.…”

Insights into organic–inorganic hybrid molecular materials: organoimido functionalized polyoxomolybdates

“…Scheme 20 Synthesis of trans-dinitrosyl-substituted polyoxometalate (NBu 4 ) 4 [Mo 6 O 17 (NO) 2 ] (29) 213. …”