2011
DOI: 10.1039/c0dt01547d
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Abstract: The reversible thermochromic behaviour of homoleptic [{V(OR)(4)}(n)] complexes in solution [R = Pr(i) (product I), Bu(s) (B(s)), Nep (N) and Cy (C)] is accounted for the existence of an aggregation equilibrium involving dimeric and monomeric species in which vanadium(iv) is respectively five- and four-coordinate. Bulky R groups such as Bu(t) and Pe(t) (tert-pentoxide) prevent aggregation and therefore give rise to exclusively mononuclear compounds (B(t) and P(t), respectively) that are not thermochromic. The c… Show more

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Cited by 19 publications
(34 citation statements)
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References 84 publications
(22 reference statements)
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“…[43] These observations suggest the presence of dimeric or/and trimeric species in the solution ( Figure 2 and Scheme 2). and 600 °C could be assigned to different VO2 phases and include some minor peaks which could not be assigned to any vanadium oxide phase.…”
Section: Space Group P1 P1mentioning
confidence: 99%
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“…[43] These observations suggest the presence of dimeric or/and trimeric species in the solution ( Figure 2 and Scheme 2). and 600 °C could be assigned to different VO2 phases and include some minor peaks which could not be assigned to any vanadium oxide phase.…”
Section: Space Group P1 P1mentioning
confidence: 99%
“…The lower steric demand and higher pKa value of the primary alcohols compared to those of tert-butanol allowed a complete ligand exchange reaction (Scheme 1). [43] Scheme 1: Synthetic protocol of homoleptic vanadium (IV) alkoxides.…”
Section: Precursor Synthesismentioning
confidence: 99%
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“…The nonbonding VÁ Á ÁV distances are nearly identical, with an average value of 3.1126 (6) Å . These distances are slightly shorter than that reported for the structurally related vanadium(IV) cyclohexanolate (OCy) dimer, [{V(OCy) 3 } 2 (-OCy) 2 ] [3.186 (2) Å ; Westrup et al, 2011].…”
Section: Commentmentioning
confidence: 60%
“…Our current interest lies in furthering our understanding of the aggregation equilibria of vanadium alkoxides in solution, with an emphasis on the effects of these equilibria on the thermochromic and magnetic properties of the products (Reis et al, 2009;de Freitas et al, 2010;Westrup et al, 2011). We are now focusing on complexes prepared from relatively bulky alkoxide ligands, which could help in controlling aggregation and reactivity, together with tuning the extent and nature of magnetic exchange interactions between the metal centres.…”
Section: Commentmentioning
confidence: 99%