Chromium(III) Bis-alkynyl complexes supported by C-substituted cyclam MPC

•New Cr(III) bisalkynyl complexes supported by MPC•Preferential formation of trans isomers•Long lived phosphorescent 2T /2E states Macrocyclic CrIII bis-alkynyl complexes have recently been used as a precursor in the synthesis of mono-alkynyl complexes, which can serve as synthetic intermediates tow...

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Bibliographic Details
Published in:Journal of organometallic chemistry 2021-12, Vol.954-955, p.122110, Article 122110
Main Authors: Schuman, Ashley J., Mills, Madeline M., Segura, Leobardo Rodriguez, Miller-Clark, Lyndsy A., Ren, Tong
Format: Article
Language:English
Subjects:
Alkynyl
Chromium
Macrocycle
Phosphorescence
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Summary:•New Cr(III) bisalkynyl complexes supported by MPC•Preferential formation of trans isomers•Long lived phosphorescent 2T /2E states Macrocyclic CrIII bis-alkynyl complexes have recently been used as a precursor in the synthesis of mono-alkynyl complexes, which can serve as synthetic intermediates towards the formation of dissymmetric bis-alkynyl complexes. The trans stereochemistry is essential to generate stable macrocyclic CrIII mono-alkynyl complexes, however, previously explored cyclam (1,4,8,11-tetraazacyclotetradecane) and its derivatives heavily favor the cis isomer after Cr insertion. The C-substituted cyclam MPC (5,12-dimethyl-7,14-diphenyl-1,4,8,11-tetraazacyclotetradecane) has shown a noteworthy preference towards the trans isomer upon insertion of Cr, making it desirable for the pursuit of dissymmetric bis-alkynyl complexes in significant quantity. Reported herein are the synthesis and characterization of trans-[Cr(MPC)(C2Ar)2]+ complexes, where Ar is Ph (1), Np (2), or C6H4tBu (3). Complexes 1 – 3 have structural and optical properties similar to previous CrIII bis-alkynyl complexes based on single-crystal X-ray diffraction, UV-vis and phosphorescence spectroscopical characterizations. [Display omitted]
ISSN:0022-328X
1872-8561
DOI:10.1016/j.jorganchem.2021.122110