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.

Abstract

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.

Citation

Reade, T. J., Murphy, T. S., Calladine, J. A., Horvath, R., Clark, I. P., Greetham, G. M., …Champness, N. 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), https://doi.org/10.1098/rsta.2016.0033

• Journal Article Type: Article
• Acceptance Date: Sep 5, 2016
• Online Publication Date: Nov 28, 2016
• Publication Date: Jan 13, 2017
• Deposit Date: Dec 12, 2016
• Publicly Available Date: Dec 12, 2016
• Journal: Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences
• Print ISSN: 1364-503X
• Electronic ISSN: 1471-2962
• Publisher: The Royal Society
• Peer Reviewed: Peer Reviewed
• Volume: 375
• Issue: 2084
• DOI: https://doi.org/10.1098/rsta.2016.0033
• Keywords: Metal–organic frameworks, Photochemistry, Supramolecular chemistry
• Public URL: https://nottingham-repository.worktribe.com/output/840561
• Publisher URL: http://rsta.royalsocietypublishing.org/content/375/2084/20160033
• Additional Information: This is the author's accepted manuscript version of the following article: Reade TJ, Murphy TS, Calladine JA, Horvath R, Clark IP, Greetham GM, Towrie M, Lewis W, George MW, Champness NR. 2017 Photochemistry of framework-supported M(diimine)(CO)3X complexes in three-dimensional lithium carboxylate metal–organic frameworks: monitoring the effect of framework cations. Phil.Trans.R.Soc.A 375 : 20160033 http://dx.doi.org/10.1098/rsta.2016.0033