Supramolecular Construction of Cyanide-Bridged Re I Diimine Multichromophores

Kristina S. Kisel, Alexei S. Melnikov, Elena V. Grachova, Antti J. Karttunen, Antonio Doménech-Carbó, Kirill Yu Monakhov, Valentin G. Semenov, Sergey P. Tunik, Igor O. Koshevoy*

*Corresponding author for this work

Research output: Contribution to journalArticleScientificpeer-review

1 Citation (Scopus)

Abstract

The reactions of labile [Re(diimine)(CO) 3 (H 2 O)] + precursors (diimine = 2,2′-bipyridine, bpy; 1,10-phenanthroline, phen) with dicyanoargentate anion produce the dirhenium cyanide-bridged compounds [{Re(diimine)(CO) 3 } 2 CN)] + (1 and 2). Substitution of the axial carbonyl ligands in 2 for triphenylphosphine gives the derivative [{Re(phen)(CO) 2 (PPh 3 )} 2 CN] + (3), while the employment of a neutral metalloligand [Au(PPh 3 )(CN)] affords heterobimetallic complex [{Re(phen)(CO) 3 }NCAu(PPh 3 )] + (4). Furthermore, the utilization of [Au(CN) 2 ] - , [Pt(CN) 4 ] 2- , and [Fe(CN) 6 ] 4-/3- cyanometallates leads to the higher nuclearity aggregates [{Re(diimine)(CO) 3 NC} x M] m+ (M = Au, x = 2, 5 and 6; Pt, x = 4, 7 and 8; Fe, x = 6, 9 and 10). All novel compounds were characterized crystallographically. Assemblies 1-8 are phosphorescent both in solution and in the solid state; according to the DFT analysis, the optical properties are mainly associated with charge transfer from Re tricarbonyl motif to the diimine fragment. The energy of this process can be substantially modified by the properties of the ancillary ligands that allows to attain near-IR emission for 3 (λ em = 737 nm in CH 2 Cl 2 ). The Re-Fe II/III complexes 9 and 10 are not luminescent but exhibit low energy absorptions, reaching 846 nm (10) due to Re I → Fe III transition.

Original languageEnglish
Pages (from-to)1988-2000
Number of pages13
JournalInorganic Chemistry
Volume58
Issue number3
DOIs
Publication statusPublished - 4 Feb 2019
MoE publication typeA1 Journal article-refereed

Keywords

  • RHENIUM(I) TRICARBONYL COMPLEXES
  • DENSITY-FUNCTIONAL METHODS
  • EXCITED-STATE
  • COORDINATION POLYMERS
  • SPECTROSCOPIC PROPERTIES
  • PHOTOPHYSICAL PROPERTIES
  • CARBONYL-COMPLEXES
  • MULTIPLE EMISSIONS
  • LUMINESCENT RE(I)
  • CRYSTAL-STRUCTURE

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    Kisel, K. S., Melnikov, A. S., Grachova, E. V., Karttunen, A. J., Doménech-Carbó, A., Monakhov, K. Y., Semenov, V. G., Tunik, S. P., & Koshevoy, I. O. (2019). Supramolecular Construction of Cyanide-Bridged Re I Diimine Multichromophores. Inorganic Chemistry, 58(3), 1988-2000. https://doi.org/10.1021/acs.inorgchem.8b02974