Energy Migration Processes in Re(I) MLCT Complexes Featuring a Chromophoric Ancillary Ligand

Wells, Kaylee A.; Yarnell, James E.; Palmer, Jonathan R.; Lee, Tia S.; Papa, Christopher M.; Castellano, Felix N.

doi:10.1021/acs.inorgchem.0c00644

Energy Migration Processes in Re(I) MLCT Complexes Featuring a Chromophoric Ancillary Ligand

Journal Article · Wed Jun 03 00:00:00 EDT 2020 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.0c00644· OSTI ID:1633645

^[1]; Yarnell, James E. ^[2]; Palmer, Jonathan R. ^[3]; ^[3]; Papa, Christopher M. ^[3]; ^[3]

North Carolina State Univ., Raleigh, NC (United States); NC State University
North Carolina State Univ., Raleigh, NC (United States); United States Air Force Academy, Colorado Springs, CO (United States)
North Carolina State Univ., Raleigh, NC (United States)

We present herein the synthesis, structural characterization, electronic structure calculations, and ultrafast and supra-nanosecond photophysical properties of a series of five Re(I) bichromophores exhibiting metal to ligand charge transfer (MLCT) excited states based on the general formula fac-[Re(N^{^}N)(CO)₃(PNI-py)]PF_6, where PNI-py is 4-piperidinyl-1,8-naphthalimidepyridine and N^{^}N is a diimine ligand (Re1–5), along with their corresponding model chromophores where 4-ethylpyridine was substituted for PNI-py (Mod1–5). The diimine ligands used include 1,10-phenanthroline (phen, 1), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (bcp, 2), 4,4'-di-tert-butyl-2,2'-bipyridine (dtbb, 3), 4,4'-diethyl ester-2,2'-bipyridine (deeb, 4), and 2,2'-biquinoline (biq, 5). In these metal–organic bichromophores, structural modification of the diimine ligand resulted in substantial changes to the observed energy transfer efficiencies between the two chromophores as a result of the variation in ³MLCT excited-state energies. The photophysical properties and energetic pathways of the model chromophores were explored in parallel to accurately track the changes that arose from introduction of the organic chromophore pendant on the ancillary ligand. All relevant photophysical and energy transfer processes were probed and characterized using time-resolved photoluminescence spectroscopy, ultrafast and nanosecond transient absorption spectroscopy, and time-dependent density functional theory calculations. Of the five bichromophores in this study, four (Re1–4) exhibited a thermal equilibrium between the ³PNI-py and the ³MLCT excited state, drastically extending the lifetimes of the parent model chromophores.

View Accepted Manuscript (DOE)

Research Organization:: North Carolina State Univ., Raleigh, NC (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF); Air Force Office of Scientific Research (AFOSR)

Contributing Organization:: Air Force Institute of Technology (AFIT)

Grant/Contract Number:: SC0011979

OSTI ID:: 1633645

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 12 Vol. 59; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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