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Title: Electronic influences of bridging and chelating diimine ligand coordination in formamidinate-bridged Rh2 (II,II) dimers

Journal Article · · Polyhedron
 [1]; ORCiD logo [2];  [3]; ORCiD logo [1]
  1. The Ohio State Univ., Columbus, OH (United States). Department of Chemistry and Biochemistry
  2. Texas A & M Univ., College Station, TX (United States). Department of Chemistry
  3. University of Houston, TX (United States). Department of Chemistry
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We report two new formamidinate-bridged Rh2II,II complexes, cis-[Rh2II,II(μ-DTolF)2(μ-np)2]2+ (3; DTolF = N,N'-di-p-tolylformamidinate; np = 1,8-naphthyridine) and cis-[Rh2II,II(μ-DTolF)2(κ2-dap)2]2+ (4; dap = 1,12-diazaperylene), were synthesized from cis-[Rh2II,II(μ-DTolF)2(CH3CN)6](BF4)2 (1), and their properties were compared to those of cis-[Rh2II,II(μ-DTolF)2(phen)2](BF4)2 (2). Density functional theory (DFT) and electrochemical analyses support the description of the highest occupied molecular orbitals (HOMOs) of 3 and 4 as possessing contributions from the metals and formamidinate bridging ligands, with Rh2/form character, and lowest unoccupied molecular orbitals (LUMOs) localized on the respective diimine ligand np and dap π* orbitals. Both 3 and 4 display strong, low energy Rh2/form → diimine(π*) metal/ligand-to-ligand charger transfer (1ML–LCT) transitions with maxima at 566 nm (ε = 3600 M-1 cm-1) for 3 and at 630 nm (ε = 2900 M-1 cm-1) for 4 in CH3CN. Time dependent-DFT (TD-DFT) calculations support these assignments. Finally, the ability of both the bridging np and chelating dap diimine ligands to produce strong absorption of these Rh2II,II complexes throughout the visible region is potentially useful for the development of new photocatalysts for H2 production and photochemotherapeutics.

Research Organization:
The Ohio State Univ., Columbus, OH (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0010542; SC0010721
OSTI ID:
1430205
Alternate ID(s):
OSTI ID: 1359777
Journal Information:
Polyhedron, Vol. 103, Issue PA; ISSN 0277-5387
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 9 works
Citation information provided by
Web of Science

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Cited By (3)

The crystal structure of 1,12-diazaperylene, C18H10N2 journal November 2019
Electrospray mass spectrometry and molecular modeling study of formation and stability of silver complexes with diazaperylene and bisisoquinoline journal March 2018
The crystal structure of 1,12-diazaperylene, C₁₈H₁₀N₂ text January 2019

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Related Subjects

14 SOLAR ENERGY
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Dirhodium
Naphthyridine
Diazaperylene
Light absorption
Electrochemistry