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The alteration of intra-ligand donor-acceptor interactions through torsional connectivity in substituted Re-dppz complexes

Adams, Bethany; Shillito, Georgina E.; Salm, Holly van der; Horvath, Raphael; Larsen, Christopher B.; Sun, Xue-Zhong; Lucas, Nigel T.; George, Michael W.; Gordon, Keith C.

Authors

Bethany Adams

Georgina E. Shillito

Holly van der Salm

Raphael Horvath

Christopher B. Larsen

Xue-Zhong Sun

Nigel T. Lucas

Michael W. George

Keith C. Gordon



Abstract

The ground and excited properties of a series of [ReCl(CO)3(dppz)] complexes with substituted donor groups have been investigated. Alteration of donor-acceptor communication through modulation of torsional angle and the number and nature of the donor substituent allowed the effects on the photophysical properties to be characterized though both computational and spectroscopic techniques, including TD-DFT, resonance Raman and time resolved infrared. The ground state optical properties show significant variation as a result of donor group modulation, with increased angle between the donor and acceptor blue-shifting and depleting the intensity of the lowest energy transition, which was consistently ILCT in nature. However, across all complexes studied there was minimal perturbation to the excited state properties and dynamics. Three excited states on the picosecond, nanosecond and microsecond time scales were observed in all cases, corresponding to 1ILCT, ππ* and 3ILCT respectively.

Journal Article Type Article
Publication Date Oct 6, 2017
Journal Inorganic Chemistry
Print ISSN 0020-1669
Electronic ISSN 1520-510X
Publisher American Chemical Society
Peer Reviewed Peer Reviewed
Volume 56
Issue 21
APA6 Citation Adams, B., Shillito, G. E., Salm, H. V. D., Horvath, R., Larsen, C. B., Sun, . X., …Gordon, K. C. (2017). The alteration of intra-ligand donor-acceptor interactions through torsional connectivity in substituted Re-dppz complexes. Inorganic Chemistry, 56(21), doi:10.1021/acs.inorgchem.7b01710
DOI https://doi.org/10.1021/acs.inorgchem.7b01710
Publisher URL http://pubs.acs.org/doi/abs/10.1021/acs.inorgchem.7b01710
Copyright Statement Copyright information regarding this work can be found at the following address: http://eprints.nottingh.../end_user_agreement.pdf
Additional Information This material is excerpted from a work that was published in Inorganic Chemistry, copyright American Chemical Society after peer review. To access the final edited and published work see see http://pubs.acs.org/doi...sonrequest/index.html].

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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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