Experimental and theoretical study of <i>dimer-of-dimers</i>-type tetrarhodium(<scp>ii</scp>) complexes bridged by 1,4-benzenedicarboxylate linkers

Kataoka, Yosuke; Arakawa, Kazuki; Ueda, Hikaru; Yano, Natsumi; Kawamoto, Tatsuya; Handa, Makoto

doi:10.1039/c8dt03293a

Cited by 6 publications

(3 citation statements)

References 51 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Crystals 2019, 9, x FOR PEER REVIEW 6 of 11 PABC ligand in 1P are almost coplanar (2.87˚) relative to the Rh2-carboxylate(PABC) plane. This result suggests the formation of the transition dipole moment between the PABC ligand and the Rh2 moiety [25]. As shown in Figure S5, the one-dimensional chains of 1P were closely assembled in the crystal without non-coordinated DMF molecules.…”

Section: Self-assembly and Disassembly Phenomenamentioning

confidence: 76%

“…Recently, paddlewheel-type Rh 2 complexes have been utilized as secondary building units (SBUs) for supra-molecular complexes [24,25], such as coordination polymers (CPs) [26][27][28][29][30] and two conventional synthetic strategies for the production of Rh2-SBU-based CPs and MOFs. The first strategy is the ligand-exchange reaction between the equatorial carboxylate ligands of the Rh2 complex precursor and organic poly-carboxylic acids at high temperature [14,[31][32][33][34].…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Coordination-Induced Self-Assembly of a Heteroleptic Paddlewheel-Type Dirhodium Complex

et al. 2020

Self Cite

View full text Add to dashboard Cite

A novel heteroleptic paddlewheel-type dirhodium (Rh2) complex [Rh2(O2CCH3)3(PABC)] (1; PABC = para-aminobenzenecarboxylate), which has an amino group as a potential donor site for coordination with the metal ion, was synthesized and characterized by 1H NMR, ESI-TOF-MS, infrared spectra, and elemental analysis. The slow evaporation of N,N-dimethylformamide (DMF)-dissolved 1 produces the purple-colored crystalline polymeric species [Rh2(O2CCH3)3 (PABC)(DMF)]n (1P). Single-crystal and powder X-ray diffraction analyses, as well as thermo-gravimetric analysis, clarified that 1P formed a one-dimensional polymeric structure, in which the two axial sites of the Rh2 ion in 1P are coordinated by a DMF molecule and an amino group of the PABC ligand of the neighboring molecule 1, by coordination-induced self-assembly (polymerization) with an Rh-amino bond. The reversible structural change (self-assembly and disassembly transformations) between the discrete species [Rh2(O2CCH3)3(PABC)(DMF)2] (1D; green solution) and the polymeric species 1P (purple solid) was accompanied by a color change, which easily occurred by the dissolution and evaporation procedures with DMF.

show abstract

Section: Self-assembly and Disassembly Phenomenamentioning

confidence: 76%

Section: Introductionmentioning

confidence: 99%

Coordination-Induced Self-Assembly of a Heteroleptic Paddlewheel-Type Dirhodium Complex

et al. 2020

Self Cite

View full text Add to dashboard Cite

show abstract

“…The intriguing properties of dirhodium complexes are derived from specific molecular orbital (MO) interactions (e.g., σ 2 π 4 δ 2 π* 4 δ* 2 ) between the two rhodium ions [8,9]. Further, on account of their chemical and water stabilities, these types of complexes have been recently utilized as robust building blocks for supramolecular complexes [10,11,12], coordination cages [13,14], coordination polymers [15,16,17,18], and porous metal organic frameworks (MOFs) [19,20,21,22]. The conventional synthetic strategy for paddlewheel-type dirhodium complexes involves a ligand-exchange reaction between dirhodium tetraacetate and organic carboxylic acids, at high temperature under inert gas.…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2019

Self Cite

View full text Add to dashboard Cite

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.

show abstract

Metal–Metal Bonded Compounds of the Group IX Elements

Berry

2021

Comprehensive Coordination Chemistry III

View full text Add to dashboard Cite

Experimental and theoretical study of dimer-of-dimers-type tetrarhodium(ii) complexes bridged by 1,4-benzenedicarboxylate linkers

Abstract: Two dimer-of-dimers-type tetrarhodium complexes, [Rh4(piv)6(BDC)] and [Rh4(piv)6(F4BDC)], in which two paddlewheel-type dirhodium units are linked by dicarboxylate ligands, have been synthesized and characterized.

Cited by 6 publications

References 51 publications

Coordination-Induced Self-Assembly of a Heteroleptic Paddlewheel-Type Dirhodium Complex

Coordination-Induced Self-Assembly of a Heteroleptic Paddlewheel-Type Dirhodium Complex

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

Metal–Metal Bonded Compounds of the Group IX Elements

Contact Info

Product

Resources

About