Three new polynuclear clusters with the formulae [Mn10O4(OH)(OMe){(py)2C(O)2}2{(py)2C(OMe)(O)}4(MeCO2)6](ClO4)2(
- Award ID(s):
- 1361779
- NSF-PAR ID:
- 10061909
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Chemistry - A European Journal
- Volume:
- 24
- Issue:
- 42
- ISSN:
- 0947-6539
- Page Range / eLocation ID:
- p. 10773-10783
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
Abstract 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 of1 –3 . The crystal structures of1 –3 are 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 within1 –3 . Alternating current (ac ) magnetic susceptibility studies revealed the presence of out‐of‐phase signals below 3.0 K for2 and3 indicating the slow relaxation of the magnetization vector, characteristic of single‐molecule magnets; theUeff value of2 was found to be 23 K and the preexponential factorτ0 ~7.6×10−9 s. -
Abstract Three binuclear species [LCoIII2(μ‐Pz)2](ClO4)3(
1 ), [LNiII2(CH3OH)2Cl2]ClO4(2 ), and [LZnII2Cl2]PF6(3 ) supported by the deprotonated form of the ligand 2,6‐bis[bis(2‐pyridylmethyl) amino‐methyl]‐4‐methylphenol were synthesized, structurally characterized as solids and in solution, and had their electrochemical and spectroscopic behavior established. Species1 –3 had their water reduction ability studied aiming to interrogate the possible cooperative catalytic activity between two neighboring metal centers. Species1 and2 reduced H2O to H2effectively at an applied potential of −1.6 VAg/AgCl, yielding turnover numbers of 2,820 and 2,290, respectively, after 30 minutes. Species3 lacked activity and was used as a negative control to eliminate the possibility of ligand‐based catalysis. Pre‐ and post‐catalytic data gave evidence of the molecular nature of the process within the timeframe of the experiments. Species1 showed structural, rather than electronic cooperativity, while species2 displayed no obvious cooperativity. DFT methods complemented the experimental results determining plausible mechanisms.