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How fast do metal organic polyhedra form in solution? Kinetics of [Cu2(5-OH-bdc)2L2]12 formation in methanol
1Department of Chemistry, University of South Florida, 4202 East Fowler Avenue, Tampa, Florida 33620, USA. rlarsen@cas.usf.edu
Abstract:
The present study utilizes rapid mixing techniques together with fast optical spectroscopy to probe the assembly of [Cu2(5-OH-bdc)2L2]12 formation in methanol. The data reveal five distinct kinetic steps involved in the formation of the Cu-nanoball in methanol with lifetimes of <15 ms, 26 ms, 310 ms, 4 s, and 45 s. From these results two possible mechanistic pathways are proposed based upon fragment isomerization followed by condensation. Both mechanisms involve fast building unit assembly (<15 ms) followed by either concerted or sequential fragment isomerization (activation controlled) coupled with condensation.
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