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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.

Authors

Thomas J. Reade

James A. Calladine

Raphael Horvath

Ian P. Clark

Gregory M. Greetham

Michael Towrie

William Lewis william.lewis@nottingham.ac.uk

Michael W. George

Neil R. Champness



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.

Journal Article Type Article
Publication Date Jan 13, 2017
Journal Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences
Print ISSN 1364-503X
Electronic ISSN 1471-2962
Publisher Royal Society, The
Peer Reviewed Peer Reviewed
Volume 375
Issue 2084
APA6 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
DOI https://doi.org/10.1098/rsta.2016.0033
Keywords Metal–organic frameworks, Photochemistry, Supramolecular chemistry
Publisher URL http://rsta.royalsocietypublishing.org/content/375/2084/20160033
Copyright Statement Copyright information regarding this work can be found at the following address: http://eprints.nottingh.../end_user_agreement.pdf
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

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Copyright Statement
Copyright information regarding this work can be found at the following address: http://eprints.nottingham.ac.uk/end_user_agreement.pdf





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