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

White, Travis A.; Dunbar, Kim R.; Thummel, Randolph P.; Turro, Claudia

doi:10.1016/j.poly.2015.10.015

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

Journal Article · Thu Oct 22 00:00:00 EDT 2015 · Polyhedron

DOI:https://doi.org/10.1016/j.poly.2015.10.015· OSTI ID:1430205

White, Travis A. ^[1]; ^[2]; Thummel, Randolph P. ^[3]; ^[4]

The Ohio State Univ., Columbus, OH (United States). Department of Chemistry and Biochemistry; The Ohio State University
Texas A & M Univ., College Station, TX (United States). Department of Chemistry
University of Houston, TX (United States). Department of Chemistry
The Ohio State Univ., Columbus, OH (United States). Department of Chemistry and Biochemistry

We report two new formamidinate-bridged Rh₂^II,II complexes, cis-[Rh₂^II,II(μ-DTolF)₂(μ-np)₂]²⁺ (3; DTolF = N,N'-di-p-tolylformamidinate; np = 1,8-naphthyridine) and cis-[Rh₂^II,II(μ-DTolF)₂(κ²-dap)₂]²⁺ (4; dap = 1,12-diazaperylene), were synthesized from cis-[Rh₂^II,II(μ-DTolF)₂(CH₃CN)₆](BF₄)₂ (1), and their properties were compared to those of cis-[Rh₂^II,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 Rh₂^II,II complexes throughout the visible region is potentially useful for the development of new photocatalysts for H₂ production and photochemotherapeutics.

View Accepted Manuscript (DOE)

Research Organization:: The Ohio State Univ., Columbus, OH (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0010542; SC0010721

OSTI ID:: 1430205

Alternate ID(s):: OSTI ID: 1359777

Journal Information:: Polyhedron, Journal Name: Polyhedron Journal Issue: PA Vol. 103; ISSN 0277-5387

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Related Subjects

14 SOLAR ENERGY
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Diazaperylene
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Naphthyridine