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Updated: Jan 30, 2026
Synthesis and Characterization of Fe-doped Aluminosilicate Nanotubes with Enhanced Electron Conductive Properties
Published on: November 15, 2016
Synthesis, Characterization, Absorption Properties, and Electronic Structures of Paddlewheel-Type Dirhodium(II)
Yusuke Kataoka1, Raiki Fukumoto2, Natsumi Yano3
1Department of Chemistry, Interdisciplinary Graduate School of Science and Engineering, Shimane University, 1060 Nishikawatsu, Matsue, Shimane 690-8504, Japan. kataoka@riko.shimane-u.ac.jp.
Abstract:
The reactions of [Rh₂(O₂CCH₃)₄(OH₂)₂] with n-naphthalenecarboxylic acids (n = 1: 1-HNC, n = 2: 2-HNC) afford the dirhodium tetra-μ-(n-naphthoate) complexes [Rh₂(1-NC)₄] (1) and [Rh₂(2-NC)₄] (2), respectively. Single crystal X-ray diffraction analyses of [1(OCMe₂)₂] and [2(OCMe₂)₂], which were obtained by recrystallization from acetone (OCMe₂) solutions of 1 and 2, reveal that the dirhodium cores are coordinated by four equatorially bridging naphthoate ligands and two axial OCMe₂ ligands. Density functional theory (DFT) calculation confirmed that (i) the single Rh⁻Rh bond is formed between the two Rh ions and (ii) the electronic structures between two Rh ions in [1(OCMe₂)₂] and [2(OCMe₂)₂] are best described as π⁴δ²σ²δ*²π*⁴ and δ²π⁴σ²δ*²π*⁴, respectively. Time-dependent DFT (TDDFT) calculations clarify the absorption band characters of [1(OCMe₂)₂] and [2(OCMe₂)₂]; the former shows the bands due to d⁻d and metal⁻to⁻metal-ligand charge transfer (MMLCT) excitations in the visible light region, whereas the latter shows the bands due to only d⁻d excitations in the same region. The electrochemical properties and thermal stabilities of [1(OCMe₂)₂] and [2(OCMe₂)₂] were also investigated in this study.
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