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Title: Hydroxo-Bridged Dicopper(II,III) and -(III,III) Complexes: Models for Putative Intermediates in Oxidation Catalysis
NSF-PAR ID:
10000296
Author(s) / Creator(s):
; ; ; ; ; ; ;
Publisher / Repository:
American Chemical Society
Date Published:
Journal Name:
Journal of the American Chemical Society
Volume:
136
Issue:
20
ISSN:
0002-7863
Page Range / eLocation ID:
7269 to 7272
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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  1. Abstract

    Three new polynuclear clusters with the formulae [Mn10O4(OH)(OMe){(py)2C(O)2}2{(py)2C(OMe)(O)}4(MeCO2)6](ClO4)2(1), Na[Mn12O2(OH)3(OMe){(py)2C(O)2}6{(py)2C(OH)(O)}2(MeCO2)2(H2O)10](ClO4)8(2) and [Mn12O4(OH)2{(py)2C(O)2}6{(py)2C(OMe)(O)}(MeCO2)3(NO3)3(H2O)(DMF)2](NO3)2(3) were prepared from the combination of di‐2‐pyridyl ketone, (py)2CO, with the aliphatic diols (1,3‐propanediol (pdH2) or 1,4‐butanediol (1,4‐bdH2)) in Mn carboxylate chemistry. The reported compounds do not include the aliphatic diols employed in this reaction scheme; however, their use is essential for the formation of13. The crystal structures of13are based on multilayer cores which, to our knowledge, are reported for the first time in Mn cluster chemistry. Direct current (dc) magnetic susceptibility studies showed the presence of dominant antiferromagnetic exchange interactions within13. Alternating current (ac) magnetic susceptibility studies revealed the presence of out‐of‐phase signals below 3.0 K for2and3indicating the slow relaxation of the magnetization vector, characteristic of single‐molecule magnets; theUeffvalue of2was found to be 23 K and the preexponential factorτ0~7.6×10−9 s.

     
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