Calixsmaragdyrin

A Versatile Ligand for Coordination Complexes

Tamal Chatterjee, Brian Molnar, G. G. Theophall, Way-Zen Lee, K. V. Lakshmi, Mangalampalli Ravikanth

Research output: Contribution to journalArticle

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Abstract

The Ru(II) and BF2 complexes of calixsmaragdyrin were prepared under simple reaction conditions and characterized by HR-MS, 1D and 2D NMR spectroscopy, optical spectroscopy, and electrochemistry, and the structure of the Ru(II) complex of calixsmaragdyrin was elucidated by X-ray crystallography. The crystal structure of the Ru(II) complex revealed that the Ru(II) ion is hexacoordinate with the three pyrrole nitrogen ligands from the tripyrrin unit of the calixsmaragdyrin macrocycle, and the remaining coordination sites of Ru(II) ion were occupied by two carbonyl groups and one hydroxyl (-OH) group. The calixsmaragdyrin macrocycle in the Ru(II) complex was distorted with a dome-like structure. In the BF2 complex of calixsmaragdyrin, the BF2 unit was bound to two pyrrolic nitrogens of the dipyrrin moiety of calixsmaragdyrin as deduced by detailed 1- and 2-dimensional NMR spectroscopy studies. The Ru(II) complex displayed a strong Soret-like absorption band at 449 nm with the absence of Q-bands, whereas the BF2 complex showed a Soret-like band at 475 nm with two well-defined Q-bands at 787 and 883 nm, respectively. Quantum mechanical DFT calculations yielded relaxed equilibrium structures that were similar to the X-ray crystal structures, and the related charge density distributions indicated that the d orbital of the Ru(II) ion was contributing to the HOMO and LUMO states. In addition, TD-DFT calculations successfully reproduced the large bathochromic shifts, oscillator strengths, and electronic transitions that were observed in the experimental absorption spectra of all three complexes. Both the Ru(II) and the BF2 complexes of calixsmaragdyrin were stable under redox conditions.

Original languageEnglish
Pages (from-to)3763-3772
Number of pages10
JournalInorganic Chemistry
Volume56
Issue number7
DOIs
Publication statusPublished - 2017 Apr 3

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Coordination Complexes
Ions
Ligands
Discrete Fourier transforms
ligands
Nuclear magnetic resonance spectroscopy
Absorption spectra
Magnetic Resonance Spectroscopy
Nitrogen
Crystal structure
spectroscopy
Electrochemistry
absorption spectra
nitrogen
nuclear magnetic resonance
ions
Pyrroles
crystal structure
X ray crystallography
X Ray Crystallography

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Chatterjee, T., Molnar, B., Theophall, G. G., Lee, W-Z., Lakshmi, K. V., & Ravikanth, M. (2017). Calixsmaragdyrin: A Versatile Ligand for Coordination Complexes. Inorganic Chemistry, 56(7), 3763-3772. https://doi.org/10.1021/acs.inorgchem.6b02225

Calixsmaragdyrin : A Versatile Ligand for Coordination Complexes. / Chatterjee, Tamal; Molnar, Brian; Theophall, G. G.; Lee, Way-Zen; Lakshmi, K. V.; Ravikanth, Mangalampalli.

In: Inorganic Chemistry, Vol. 56, No. 7, 03.04.2017, p. 3763-3772.

Research output: Contribution to journalArticle

Chatterjee, T, Molnar, B, Theophall, GG, Lee, W-Z, Lakshmi, KV & Ravikanth, M 2017, 'Calixsmaragdyrin: A Versatile Ligand for Coordination Complexes', Inorganic Chemistry, vol. 56, no. 7, pp. 3763-3772. https://doi.org/10.1021/acs.inorgchem.6b02225
Chatterjee T, Molnar B, Theophall GG, Lee W-Z, Lakshmi KV, Ravikanth M. Calixsmaragdyrin: A Versatile Ligand for Coordination Complexes. Inorganic Chemistry. 2017 Apr 3;56(7):3763-3772. https://doi.org/10.1021/acs.inorgchem.6b02225
Chatterjee, Tamal ; Molnar, Brian ; Theophall, G. G. ; Lee, Way-Zen ; Lakshmi, K. V. ; Ravikanth, Mangalampalli. / Calixsmaragdyrin : A Versatile Ligand for Coordination Complexes. In: Inorganic Chemistry. 2017 ; Vol. 56, No. 7. pp. 3763-3772.
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