Three new polynuclear clusters with the formulae [Mn10O4(OH)(OMe){(py)2C(O)2}2{(py)2C(OMe)(O)}4(MeCO2)6](ClO4)2(
Structural Control of 1 A 2u -to- 3 A 2u Intersystem Crossing in Diplatinum(II,II) Complexes
- Award ID(s):
- 0802907
- NSF-PAR ID:
- 10041089
- Date Published:
- Journal Name:
- Journal of the American Chemical Society
- Volume:
- 134
- Issue:
- 34
- ISSN:
- 0002-7863
- Page Range / eLocation ID:
- 14201 to 14207
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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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.