Electronic communication in luminescent dicyanorhenate-bridged homotrinuclear rhenium(I) complexes

Yelan XIAO, Apple Wai-Yi CHEUNG, Sze-Wing LAI, Shun-Cheung CHENG, Shek-Man YIU, Chi Fai LEUNG, Chi-Chiu KO

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Abstract

A series of cyano-bridged homotrinuclear Re(I) complexes with the general formula of {[Re]´[Re][Re]´}+ {[Re]´ = −[ReI(CO)₂(LL)(X)]; [Re] = −[(NC)ReI(CO)₂(phen)(CN)]–; LL = diimine, diphosphine, or two carbonyl ligands; X = triphenylphosphine or carbonyl ligand} and the corresponding mononuclear complex analogues were synthesized. The structures of most of the trinuclear Re(I) complexes have been determined by X-ray crystallography. The relative orientations of peripheral to central Re(I) units in these structures vary considerably. The photophysical properties of these trinuclear Re(I) complexes have been examined. Except for the trinuclear Re(I) complex with Br₂phen ligand, all the other triads display orange to red photoluminescence derived from the ³MLCT [dπ(Re) → π*(phen)] origin of the central Re(I) unit, suggestive of efficient energy transfer between the peripheral chromophores and the central unit. In addition to the efficient energy transfer processes between the Re(I) chromophores in these trinuclear complexes, the ability of the [NC–Re–CN] bridging ligands for electronic coupling between the rhenium metal centers is evidenced by ca. 0.2–0.3 V separation of the two rhenium metal-based oxidation potentials of the chemically equivalent peripheral units. Copyright © 2019 American Chemical Society.
Original languageEnglish
Pages (from-to)6696-6705
JournalInorganic Chemistry
Volume58
Issue number10
DOIs
Publication statusPublished - May 2019

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Rhenium
rhenium
communication
Ligands
ligands
Communication
Carbon Monoxide
Chromophores
electronics
Energy transfer
chromophores
Metals
energy transfer
X ray crystallography
Crystal orientation
metals
crystallography
Photoluminescence
analogs
photoluminescence

Citation

Xiao, Y., Cheung, A. W.-Y., Lai, S.-W., Cheng, S.-C., Yiu, S.-M., Leung, C.-F., & Ko, C.-C. (2019). Electronic communication in luminescent dicyanorhenate-bridged homotrinuclear rhenium(I) complexes. Inorganic Chemistry, 58(10), 6696-6705. doi: 10.1021/acs.inorgchem.9b00072