Photochemistry of framework-supported M(diimine)(CO)₃X complexes in 3D Lithium-Carboxylate metal−organic frameworks: monitoring the effect of framework cations
The structures and photochemical behaviour of two new metal-organic frameworks are reported. Reaction of Re(2,2ʹ-bipyʹ-5,5ʹ-dicarboxylic acid)(CO)₃Cl or Mn(2,2ʹ-bipyʹ-5,5ʹ- dicarboxylic acid)(CO)₃Br with either LiCl or LiBr, respectively, produces single crystals of {Li₂(DMF)₂[(2,2ʹ-bipyʹ-5,5ʹ-dicar...
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| Format: | Article |
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Royal Society of Chemistry
2017
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| Online Access: | https://eprints.nottingham.ac.uk/39312/ |
| _version_ | 1848795807623413760 |
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| author | Reade, Thomas J. Murphy, Thomas S. Calladine, James A. Horvath, Raphael Clark, Ian P. Greetham, Gregory M. Towrie, Michael Lewis, William George, Michael W. Champness, Neil R. |
| author_facet | Reade, Thomas J. Murphy, Thomas S. Calladine, James A. Horvath, Raphael Clark, Ian P. Greetham, Gregory M. Towrie, Michael Lewis, William George, Michael W. Champness, Neil R. |
| author_sort | Reade, Thomas J. |
| building | Nottingham Research Data Repository |
| collection | Online Access |
| description | The structures and photochemical behaviour of two new metal-organic frameworks are reported. Reaction of Re(2,2ʹ-bipyʹ-5,5ʹ-dicarboxylic acid)(CO)₃Cl or Mn(2,2ʹ-bipyʹ-5,5ʹ- dicarboxylic acid)(CO)₃Br with either LiCl or LiBr, respectively, produces single crystals of {Li₂(DMF)₂[(2,2ʹ-bipyʹ-5,5ʹ-dicarboxylate)Re(CO)₃Cl]}n (ReLi) or {Li₂(DMF)₂[(2,2ʹ-bipyʹ- 5,5ʹ-dicarboxylate)Mn(CO)₃Br]}n (MnLi). The structures formed by the two MOFs comprise one-dimensional chains of carboxylate-bridged Li(I) cations that are cross-linked by units of Re(2,2ʹ-bipyʹ-5,5ʹ-dicarboxylate)(CO)₃Cl (ReLi) or Mn(2,2ʹ-bipyʹ-5,5ʹ- dicarboxylate)(CO)₃Br (MnLi). The photophysical and photochemical behaviour of both ReLi and MnLi are probed. The rhenium-containing MOF, ReLi, exhibits luminescence and the excited state behaviour, as established by time-resolved infra-red measurements, are closer in behaviour to that of unsubstituted [Re(bipy)(CO)₃Cl] rather than a related MOF where the Li(I) cations are replaced by Mn(II) cations. These observations are further supported by DFT calculations. Upon excitation MnLi forms a dicarbonyl species which rapidly recombines with the dissociated CO, in a fashion consistent with the majority of the photoejected CO not escaping the MOF channels. |
| first_indexed | 2025-11-14T19:37:57Z |
| format | Article |
| id | nottingham-39312 |
| institution | University of Nottingham Malaysia Campus |
| institution_category | Local University |
| last_indexed | 2025-11-14T19:37:57Z |
| publishDate | 2017 |
| publisher | Royal Society of Chemistry |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | nottingham-393122020-05-04T18:30:50Z https://eprints.nottingham.ac.uk/39312/ Photochemistry of framework-supported M(diimine)(CO)₃X complexes in 3D Lithium-Carboxylate metal−organic frameworks: monitoring the effect of framework cations Reade, Thomas J. Murphy, Thomas S. Calladine, James A. Horvath, Raphael Clark, Ian P. Greetham, Gregory M. Towrie, Michael Lewis, William George, Michael W. Champness, Neil R. The structures and photochemical behaviour of two new metal-organic frameworks are reported. Reaction of Re(2,2ʹ-bipyʹ-5,5ʹ-dicarboxylic acid)(CO)₃Cl or Mn(2,2ʹ-bipyʹ-5,5ʹ- dicarboxylic acid)(CO)₃Br with either LiCl or LiBr, respectively, produces single crystals of {Li₂(DMF)₂[(2,2ʹ-bipyʹ-5,5ʹ-dicarboxylate)Re(CO)₃Cl]}n (ReLi) or {Li₂(DMF)₂[(2,2ʹ-bipyʹ- 5,5ʹ-dicarboxylate)Mn(CO)₃Br]}n (MnLi). The structures formed by the two MOFs comprise one-dimensional chains of carboxylate-bridged Li(I) cations that are cross-linked by units of Re(2,2ʹ-bipyʹ-5,5ʹ-dicarboxylate)(CO)₃Cl (ReLi) or Mn(2,2ʹ-bipyʹ-5,5ʹ- dicarboxylate)(CO)₃Br (MnLi). The photophysical and photochemical behaviour of both ReLi and MnLi are probed. The rhenium-containing MOF, ReLi, exhibits luminescence and the excited state behaviour, as established by time-resolved infra-red measurements, are closer in behaviour to that of unsubstituted [Re(bipy)(CO)₃Cl] rather than a related MOF where the Li(I) cations are replaced by Mn(II) cations. These observations are further supported by DFT calculations. Upon excitation MnLi forms a dicarbonyl species which rapidly recombines with the dissociated CO, in a fashion consistent with the majority of the photoejected CO not escaping the MOF channels. Royal Society of Chemistry 2017-01-13 Article PeerReviewed Reade, Thomas J., Murphy, Thomas S., Calladine, James A., Horvath, Raphael, Clark, Ian P., Greetham, Gregory M., Towrie, Michael, Lewis, William, George, Michael W. and Champness, Neil R. (2017) Photochemistry of framework-supported M(diimine)(CO)₃X complexes in 3D Lithium-Carboxylate metal−organic frameworks: monitoring the effect of framework cations. Philosophical Transactions A: Mathematical, Physical and Engineering Sciences, 375 (2084). pp. 1-17. ISSN 1471-2962 Metal–organic frameworks Photochemistry Supramolecular chemistry http://rsta.royalsocietypublishing.org/content/375/2084/20160033 doi:10.1098/rsta.2016.0033 doi:10.1098/rsta.2016.0033 |
| spellingShingle | Metal–organic frameworks Photochemistry Supramolecular chemistry Reade, Thomas J. Murphy, Thomas S. Calladine, James A. Horvath, Raphael Clark, Ian P. Greetham, Gregory M. Towrie, Michael Lewis, William George, Michael W. Champness, Neil R. Photochemistry of framework-supported M(diimine)(CO)₃X complexes in 3D Lithium-Carboxylate metal−organic frameworks: monitoring the effect of framework cations |
| title | Photochemistry of framework-supported M(diimine)(CO)₃X complexes in 3D Lithium-Carboxylate metal−organic frameworks: monitoring the effect of framework cations |
| title_full | Photochemistry of framework-supported M(diimine)(CO)₃X complexes in 3D Lithium-Carboxylate metal−organic frameworks: monitoring the effect of framework cations |
| title_fullStr | Photochemistry of framework-supported M(diimine)(CO)₃X complexes in 3D Lithium-Carboxylate metal−organic frameworks: monitoring the effect of framework cations |
| title_full_unstemmed | Photochemistry of framework-supported M(diimine)(CO)₃X complexes in 3D Lithium-Carboxylate metal−organic frameworks: monitoring the effect of framework cations |
| title_short | Photochemistry of framework-supported M(diimine)(CO)₃X complexes in 3D Lithium-Carboxylate metal−organic frameworks: monitoring the effect of framework cations |
| title_sort | photochemistry of framework-supported m(diimine)(co)₃x complexes in 3d lithium-carboxylate metal−organic frameworks: monitoring the effect of framework cations |
| topic | Metal–organic frameworks Photochemistry Supramolecular chemistry |
| url | https://eprints.nottingham.ac.uk/39312/ https://eprints.nottingham.ac.uk/39312/ https://eprints.nottingham.ac.uk/39312/ |