Electronic structure of cobalt valence tautomeric molecules in different environments

Esha Mishra; Thilini K. Ekanayaka; Theodoros Panagiotakopoulos; Duy Le; Talat S. Rahman; Ping Wang; Kayleigh A. McElveen; Jared P. Phillips; M. Zaid Zaz; Saeed Yazdani; Alpha T. N'Diaye; Rebecca Y. Lai; Robert Streubel; Ruihua Cheng; Michael Shatruk; Peter A. Dowben

doi:10.1039/D2NR06834F

Electronic structure of cobalt valence tautomeric molecules in different environments†

Esha Mishra,

^a Thilini K. Ekanayaka,

^a Theodoros Panagiotakopoulos,

^b Duy Le,

^b Talat S. Rahman,

*^b Ping Wang,

^c Kayleigh A. McElveen,^d Jared P. Phillips,

^e M. Zaid Zaz,^a Saeed Yazdani,

^e Alpha T. N'Diaye,

^f Rebecca Y. Lai,

^d Robert Streubel,

*^ag Ruihua Cheng,^e Michael Shatruk

^c and Peter A. Dowben

*^a

Author affiliations

* Corresponding authors

^a Department of Physics and Astronomy, University of Nebraska-Lincoln, Lincoln, NE 68588, USA
E-mail: Streubel@unl.edu, pdowben@unl.edu

^b Department of Physics, University of Central Florida, Orlando, FL 32816, USA
E-mail: talat@ucf.edu

^c Department of Chemistry and Biochemistry, Florida State University, Tallahassee, FL 32306, USA

^d Department of Chemistry, University of Nebraska-Lincoln, Lincoln, NE, USA

^e Department of Physics, Indiana University-Purdue University Indianapolis, Indianapolis, Indiana 46202, USA

^f Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA

^g Nebraska Center for Materials and Nanoscience, University of Nebraska-Lincoln, Lincoln, NE 68588, USA

Abstract

Future molecular microelectronics require the electronic conductivity of the device to be tunable without impairing the voltage control of the molecular electronic properties. This work reports the influence of an interface between a semiconducting polyaniline polymer or a polar poly-D-lysine molecular film and one of two valence tautomeric complexes, i.e., [Co^III(SQ)(Cat)(4-CN-py)₂] ↔ [Co^II(SQ)₂(4-CN-py)₂] and [Co^III(SQ)(Cat)(3-tpp)₂] ↔ [Co^II(SQ)₂(3-tpp)₂]. The electronic transitions and orbitals are identified using X-ray photoemission, X-ray absorption, inverse photoemission, and optical absorption spectroscopy measurements that are guided by density functional theory. Except for slightly modified binding energies and shifted orbital levels, the choice of the underlying substrate layer has little effect on the electronic structure. A prominent unoccupied ligand-to-metal charge transfer state exists in [Co^III(SQ)(Cat)(3-tpp)₂] ↔ [Co^II(SQ)₂(3-tpp)₂] that is virtually insensitive to the interface between the polymer and tautomeric complexes in the Co^II high-spin state.

This article is part of the themed collection: Nanoscale 2023 Emerging Investigators

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Electronic structure of cobalt valence tautomeric molecules in different environments†

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