A mixed-valence polyoxovanadate(III,IV) cluster with a calixarene cap exhibiting ferromagnetic V(III)-V(IV) interactions

Journal of the American Chemical Society
Christophe AronicaDominique Luneau

Abstract

A series of compounds (cat)[V6O6(OCH3)8(calix)(CH3OH)] was obtained under anaerobic conditions and solvothermal reaction of VOSO4 with p-tert-butylcalix[4]arene (calix) in methanol using different types of bases (Et4NOH, NH4OH, pyridine, Et3N). All compounds contain the same polyoxo(alkoxo)hexavanadate anion [V6O6(OCH3)8(calix)(CH3OH)]- (1) exhibiting a mixed valence {VIIIVIV5O19} core with the so-called Lindqvist structure coordinated to a calix[4]arene macrocycle and cocrystallizing with the conjugated acid of the base (cat = Et4N+, NH4(+), pyridinium, Et3NH+) involved in the synthesis process. The structures have been fully established from X-ray diffraction on single crystals and the mixed valence state has been confirmed by bond valence sum calculations. The magnetic behavior of all compounds are the same because of the polyalkoxohexavanadate anion [V6O6(OCH3)8(calix)(CH3OH)]- (1) and have been interpreted by DFT calculations. Thus the V(III)...V(IV) interactions are found to be weakly ferromagnetic (<5.5 cm(-1)) while the V(IV)...V(IV) are antiferromagnetic (-17.6; -67.6 cm(-1)). The set of the coupling exchange parameters allows a good agreement with the magnetic experimental data.

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Citations

Oct 15, 2011·Inorganic Chemistry·Ekaterina M ZuevaSerguei A Borshch
Mar 1, 2012·Inorganic Chemistry·Kecai XiongMaochun Hong
Dec 5, 2013·Inorganic Chemistry·Donghui YangJingyang Niu
Dec 20, 2013·Inorganic Chemistry·Kongzhao SuMaochun Hong
Apr 2, 2010·Chemical Communications : Chem Comm·Jerry L AtwoodSimon J Teat
May 8, 2010·Chemical Communications : Chem Comm·Georgios KarotsisEuan K Brechin
Jul 19, 2011·Chemical Communications : Chem Comm·Sergio SanzEuan K Brechin
May 27, 2017·Inorganic Chemistry·Feng LiEllen M Matson
May 12, 2016·Chemistry : a European Journal·Marco ColettaScott J Dalgarno
Dec 18, 2013·Dalton Transactions : an International Journal of Inorganic Chemistry·Robyn E FairbairnScott J Dalgarno
Sep 8, 2015·Chemical Society Reviews·Kirill Yu MonakhovPaul Kögerler
Mar 5, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Mei-Jie WeiZhong-Min Su
Jun 21, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Xunliang HuYongge Wei
Jul 20, 2017·Chemistry : a European Journal·Takuo MinatoNoritaka Mizuno
Nov 23, 2016·Chemical Communications : Chem Comm·Marco ColettaScott J Dalgarno
Nov 25, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Marco ColettaScott J Dalgarno
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Aug 10, 2017·Chemistry : a European Journal·Marco ColettaScott J Dalgarno
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Nov 8, 2012·Chemistry : a European Journal·Stephanie M TaylorScott J Dalgarno
Apr 4, 2013·Dalton Transactions : an International Journal of Inorganic Chemistry·Ross McLellanScott J Dalgarno
Jan 18, 2014·Chemical Communications : Chem Comm·Ross McLellanScott J Dalgarno
Sep 10, 2011·Chemical Communications : Chem Comm·Sergio SanzScott J Dalgarno
Sep 12, 2013·Chemical Communications : Chem Comm·Ross McLellanScott J Dalgarno
Feb 3, 2015·Chemistry : a European Journal·Ross McLellanScott J Dalgarno
Aug 16, 2017·Chemical Communications : Chem Comm·Kongzhao SuMaochun Hong
Nov 24, 2018·Nature Communications·Kongzhao SuMaochun Hong
Jul 18, 2012·Chemical Communications : Chem Comm·Robyn E FairbairnScott J Dalgarno

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