cis-Conformation of indigo in the coordination complex (indigo-O,O)(Cp*CrIICl)

Dmitri V Konarev; Salavat S Khasanov; Aleksey V Kuzmin; Alexander F Shestakov; Akihiro Otsuka; Hideki Yamochi; Gunzi Saito; Rimma N Lyubovskaya

doi:10.1039/c6dt03545k

cis-Conformation of indigo in the coordination complex (indigo-O,O)(Cp*Cr^IICl)

Dalton Trans. 2016 Nov 1;45(43):17095-17099. doi: 10.1039/c6dt03545k.

Authors

Dmitri V Konarev¹, Salavat S Khasanov², Aleksey V Kuzmin², Alexander F Shestakov¹, Akihiro Otsuka³, Hideki Yamochi³, Gunzi Saito⁴, Rimma N Lyubovskaya¹

Affiliations

¹ Institute of Problems of Chemical Physics RAS, Chernogolovka, Moscow Region, 142432, Russia. konarev3@yandex.ru.
² Institute of Solid State Physics RAS, Chernogolovka, Moscow Region, 142432, Russia.
³ Division of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502, Japan and Research Center for Low Temperature and Materials Sciences, Kyoto University, Sakyo-ku, Kyoto 606-8501, Japan.
⁴ Faculty of Agriculture, Meijo University, 1-501 Shiogamaguchi, Tempaku-ku, Nagoya 468-8502, Japan. gsaito@meijo-u.ac.jp and Toyota Physical and Chemical Research Institute, 41-1, Yokomichi, Nagakute, Aichi 480-1192, Japan.

PMID: 27747350
DOI: 10.1039/c6dt03545k

Abstract

The interaction of decamethylchromocene (Cp*₂Cr) with indigo in the presence of a Cl^- source yields the coordination complex (indigo-O,O)(Cp*Cr^IICl) (1) in which one Cp* ligand at chromium is substituted by indigo. Indigo adopts an unusual cis-conformation in 1, allowing the coordination of both indigo carbonyl groups to one Cr^II center. Complex 1 contains Cr^II with an S = 1 spin state and indigo⁰. At the same time, calculations show that an excited ionic state is positioned close to the neutral ground state, providing the appearance of intense low-energy NIR bands in the spectrum of 1 at 820 and 1002 nm attributed to metal-to-ligand charge transfer.