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Synthesis, Characterization, Absorption Properties, and Electronic Structures of Paddlewheel-Type Dirhodium(II) Tetra-?-(n-naphthoate) Complexes: An Experimental and Theoretical Study.

ABSTRACT: The reactions of [Rh?(O?CCH?)?(OH?)?] with n-naphthalenecarboxylic acids (n = 1: 1-HNC, n = 2: 2-HNC) afford the dirhodium tetra-?-(n-naphthoate) complexes [Rh?(1-NC)?] (1) and [Rh?(2-NC)?] (2), respectively. Single crystal X-ray diffraction analyses of [1(OCMe?)?] and [2(OCMe?)?], which were obtained by recrystallization from acetone (OCMe?) solutions of 1 and 2, reveal that the dirhodium cores are coordinated by four equatorially bridging naphthoate ligands and two axial OCMe? 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(OCMe?)?] and [2(OCMe?)?] are best described as ???²?²?*²?*? and ?²???²?*²?*?, respectively. Time-dependent DFT (TDDFT) calculations clarify the absorption band characters of [1(OCMe?)?] and [2(OCMe?)?]; 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(OCMe?)?] and [2(OCMe?)?] were also investigated in this study.

SUBMITTER: Kataoka Y

PROVIDER: S-EPMC6384905 | biostudies-literature | 2019 Jan

REPOSITORIES: biostudies-literature

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Synthesis, Characterization, Absorption Properties, and Electronic Structures of Paddlewheel-Type Dirhodium(II) Tetra-μ-(n-naphthoate) Complexes: An Experimental and Theoretical Study.

Kataoka Yusuke Y Fukumoto Raiki R Yano Natsumi N Atarashi Daiki D Tanaka Hidekazu H Kawamoto Tatsuya T Handa Makoto M

Molecules (Basel, Switzerland) 20190127 3

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 ...[more]

PMID: 30691216

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Project description:The electronic structure relevant to low spin (LS)?high spin (HS) transitions in Fe(II) coordination compounds with a FeN6 core are studied. The selected [Fe(tz)6]2+ (1) (tz = 1H-tetrazole), [Fe(bipy)3]2+ (2) (bipy = 2,2'-bipyridine), and [Fe(terpy)2]2+ (3) (terpy = 2,2':6',2?-terpyridine) complexes have been actively studied experimentally, and with their respective mono-, bi-, and tridentate ligands, they constitute a comprehensive set for theoretical case studies. The methods in this work include density functional theory (DFT), time-dependent DFT (TD-DFT), and multiconfigurational second order perturbation theory (CASPT2). We determine the structural parameters as well as the energy splitting of the LS-HS states (?EHL) applying the above methods and comparing their performance. We also determine the potential energy curves representing the ground and low-energy excited singlet, triplet, and quintet d6 states along the mode(s) that connect the LS and HS states. The results indicate that while DFT is well suited for the prediction of structural parameters, an accurate multiconfigurational approach is essential for the quantitative determination of ?EHL. In addition, a good qualitative agreement is found between the TD-DFT and CASPT2 potential energy curves. Although the TD-DFT results might differ in some respect (in our case, we found a discrepancy at the triplet states), our results suggest that this approach, with due care, is very promising as an alternative for the very expensive CASPT2 method. Finally, the two-dimensional (2D) potential energy surfaces above the plane spanned by the two relevant configuration coordinates in [Fe(terpy)2]2+ were computed at both the DFT and CASPT2 levels. These 2D surfaces indicate that the singlet-triplet and triplet-quintet states are separated along different coordinates, i.e., different vibration modes. Our results confirm that in contrast to the case of complexes with mono- and bidentate ligands, the singlet-quintet transitions in [Fe(terpy)2]2+ cannot be described using a single configuration coordinate.

Dataset Information

Synthesis, Characterization, Absorption Properties, and Electronic Structures of Paddlewheel-Type Dirhodium(II) Tetra-?-(n-naphthoate) Complexes: An Experimental and Theoretical Study.

Publications

Synthesis, Characterization, Absorption Properties, and Electronic Structures of Paddlewheel-Type Dirhodium(II) Tetra-μ-(<i>n</i>-naphthoate) Complexes: An Experimental and Theoretical Study.

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