BEGIN:VCALENDAR VERSION:2.0 PRODID:-//ZContent.net//ZapCalLib 1.0//EN CALSCALE:GREGORIAN METHOD:PUBLISH BEGIN:VEVENT SUMMARY:Organic Chemistry in a Porous Metal-Oxide Capsule LOCATION:Chemistry A101 TZID:America/Denver DTSTART:20198201T000000 UID:2026-03-15-23-52-45@natsci.colostate.edu DTSTAMP:20260315T235245 Description:About the Seminar:\n\nIn recent years\, we have used porous ico sahedral-symmetry metal-oxide capsules\, of the type\,[{MoVI6O21(H2O)6}12{ MoV2O4(L)}30]42– {Mo132} (L = an endohedrally-coordinated carboxylate an ion)\, to investigate organic reactions within nano-confined domains in wa ter. Using the capsule as a soluble analogue of porous solid-state (rigid) oxides\, we initially showed that branched-alkane carboxylate “guests could enter the capsule’s interior by negotiating passage through flex ible subnanometer Mo9O9 apertures whose geometrical dimensions were smalle r than the entering species themselves [1]. Nano-containers in which struc turally integral metal centers serve as catalytic sites for encapsulated s ubstrates are relatively rare\, and the {Mo132} capsules provide a unique opportunity for exploring this class of reactions. These include the cleav age of methyl tert-butyl ether under mild conditions in water\, and for th e Michaelis-Menten compliant hydrolysis of epoxides\, with an enzyme-like rate acceleration (kcat / kuncat) of 182\,800\, the largest yet reported f or a cage or container at room temperature in water [2-3]. Regarding self- assembly a {Mo132} capsule was used to reveal the energetics of individual steps in the formation of a “micelle”-like organic aggregate of n-but yrate ions [4] (see also ref. [5])\, and in related work\, two distinct ho st domains within the capsule were found to be preferentially populated as a function of alkane-guest size [6]. Most recently[7]\, we demonstrated t hat confined conditions can release a latent potential for entropically dr iven (i.e.\, \\'hydrophobic\\') uptake and assembly of alcohol guests. Nam ely\, the spontaneous uptake of L-glycerate ligands by a {Mo132} capsule w as shown to be entropically driven\, revealing the inherently “hydrophob ic” nature of poly-alcohols\, whose sequestration from water bears an en ergetic signature closely analogous to that of “classical” hydrophobes .\n\n[1] Ziv\, A.\; Grego\, A.\; Kopilevich\, S.\; Zeiri\, L.\; Miro\, P.\ ; Bo\, C.\; Müller\, A.\; Weinstock\, I. A. “Flexible Pores of a Metal- Oxide-Based Capsule Permit Entry of Comparatively Larger Organic Guests” J. Am. Chem. Soc. 2009\, 131\, 6380-6382.\n\n[2] Kopilevich\, S.\; Gil\, A.\; Garcia-Ratés\, M.\; Avalos\, J. B.\; Bo\, C.\; Müller\, A.\; Weinst ock\, I. A. “Catalysis in a Porous Molecular Capsule: Activation by Regu lated Access to Sixty Metal Centers Spanning a Truncated Icosahedron” J. Am. Chem. Soc. 2012\, 134\, 13082-13088.\n\n[3] Kopilevich\, S\; Müller\ , A.\; Weinstock\, I. A. “Amplified Rate Acceleration by Simultaneous Up -Regulation of Multiple Active Sites in an Endo-Functionalized Porous Caps ule” J. Am. Chem. Soc. 2015\, 137\, 12740–12743.\n\n[4] Grego\, A.\; M üller\, A.\; Weinstock\, I. A. “Stepwise-Resolved Thermodynamics of Hyd rophobic Self-Assembly” Angew. Chem. Int. Ed. 2013\, 52\, 8358 –8362.\ n\n[5] Garai\, S.\; Bögge\, H.\; Merca\, A.\; Petina\, O.P.\; Grego\, A.\ ; Gouzerh\, P.\; Haupt\, E.T.K.\; Weinstock\, I.A.\; Müller\, A. “Dense ly packed hydrophobic clustering: Encapsulated valerates form a high-tempe rature-stable {Mo132} capsule system” Ang. Chem. Int. Ed. 2016\, 55\, 66 34 –6637.\n\n[6] Kopilevich\, S.\; Gottlieb\, H.\; Keinan-Adamsky\, K.\; Müller\, A.\; Weinstock\, I.A. “The uptake and assembly of alkanes wit hin a porous nanocapsule in water: New information about hydrophobic confi nement” Ang. Chem. Int. Ed.\, 2016\, 55\, 4476 –4481.\n\n[7] Chakrabor ty\, S.\; Shnaiderman-Grego\, A.\; Garai\, S.\; Baranov\, M.\; Müller\, A .\; Weinstock\, I. A. Alcohols as Latent Hydrophobes: Entropically Driven Uptake of 1\,2-Diol Functionalized Ligands by a Porous Capsule in Water. J . Am. Chem. Soc. 2019\, 141\, 9170−9174.\n\n \; 4:00 pm END:VEVENT END:VCALENDAR