Linkage Isomerization as a Mechanism for Photochromic Materials: Cyclopentadienylmanganese Tricarbonyl Derivatives with Chelatable Functional Groups
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- 作者：Tung T. To ; Charles B. Duke III ; Christopher S. Junker ; Casey M. O’ ; Brien ; Charles R. Ross II ; Craig E. Barnes ; Charles Edwin Webster ; Theodore J. Burkey
- 刊名：Organometallics
- 出版年：2008
- 出版时间：January 28, 2008
- 年：2008
- 卷：27
- 期：2
- 页码：289 - 296
- 全文大小：491K
- 年卷期：v.27,no.2(January 28, 2008)
- ISSN：1520-6041
文摘
Two, bifunctional side-chain cyclopentadienylmanganese tricarbonyl complexes, 7 (pyridine and ketone side chain) and 14 (thioamide and pyridine side chain), were prepared and converted to chelates following CO dissociation by UV irradiation. Both pyridine (8) and carbonyl (9) chelates are observed following irradiation of 7. In contrast, only thioamide chelate (16) is observed following irradiation of 14 even though a pyridine group was available. Visible irradiation isomerizes the pyridine chelate 8 to the carbonyl chelate 9, which thermally isomerizes back to 8 at 25 °C in a few minutes, demonstrating a photochromic response from a cyclopentadienyl-manganese complex based on a linkage isomerization of a tethered functional group. DFT calculations predicted that the activation enthalpy of thermal linkage isomerization would be 20.8 kcal/mol and that the mechanism is likely an associative process that does not involve a simple dissociation of the manganese bond to the side-chain ketone. The DFT calculations were supported by subsequent dynamic NMR experiments that yielded an activation enthalpy and entropy of 21.4 ± 0.8 kcal/mol and 3.5 ± 0.1 eu, respectively. The studies indicate that a compound with a tethered, coordinated functional group, which is otherwise not labile, can isomerize by a low-energy pathway if there is an appropriate “conduit” to another functional group with a stronger metal–ligand bond. Thus, the preparation of photochromic organometallic complexes based on linkage isomerization will require a bridge that inhibits an associative walk between functional groups if they are to be bistable.