Heterometallic one-dimensional chain with tetradeca metal repetition constructed by amidate bridged dirhodium and pivalate bridged diplatinum complexes influenced by hydrogen bonding

Yamada, Tomofumi; Ebihara, Masahiro; Uemura, Kazuhiro

doi:10.1039/c6dt01601d

Cited by 12 publications

(10 citation statements)

References 53 publications

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“…Thus, the reaction of [Rh 2 (μ-O 2 CCF 3 ) 4 OCMe 2 ] 2 with the tetranuclear species [Cu 4 (O 2 CCF 3 ) 4 ] afforded a bidimensional coordination polymer of {[Rh 2 (μ-O 2 CCF 3 ) 4 ]·μ 2 -OCMe 2 ·[Cu 4 (O 2 CCF 3 ) 4 ]} formula. In addition, several heterometallic Rh-Pt one-dimensional complexes have been described [26,27,28,29,30]. For example, {[Rh 2 ]−[Pt 2 ] −[Pt 2 ]} n or [Rh 2 ]−[Pt−Cu−Pt] polymers with dimetallic units joined by unbridged Pt-Rh metal-metal bonds have been obtained [26,27,28,29,30,31].…”

Section: Introductionmentioning

confidence: 99%

“…In addition, several heterometallic Rh-Pt one-dimensional complexes have been described [26,27,28,29,30]. For example, {[Rh 2 ]−[Pt 2 ] −[Pt 2 ]} n or [Rh 2 ]−[Pt−Cu−Pt] polymers with dimetallic units joined by unbridged Pt-Rh metal-metal bonds have been obtained [26,27,28,29,30,31]. Moreover, a strategy to construct one-dimensional compounds from dirhodiumtetracarboxylato units, [Rh 2 (μ-O 2 CR) 4 ] + (R = Me, Et) using dicyanoaurate, [Au(CN) 2 ] − groups as linker has been developed by our research group [32].…”

Section: Introductionmentioning

confidence: 99%

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Synthesis and Structural Characterization of a Series of One-Dimensional Heteronuclear Dirhodium-Silver Coordination Polymers

et al. 2019

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Herein, we describe the preparation of heteronuclear dirhodium-silver complexes by reaction between molecular Rh(II)-Rh(II) compounds [Rh2(μ-O2CR)4L2] (R = Me, Ph (1), CH2OEt (2); L = solvent molecules) with paddlewheel structure and PPh4[Ag(CN)2]. One-dimensional coordination polymers of (PPh4)n[Rh2(μ-O2CR)4Ag(CN)2]n (R = Me (3), Ph (4), CH2OEt (5)) formula have been obtained by replacement of the two labile molecules in the axial positions of the paddlewheel structures by a [Ag(CN)2]− bridging unit. The crystal structures of 3–5 display a similar arrangement, having anionic chains with a wavy structure and bulky (PPh4)+ cations placed between the chains. The presence of the (PPh4)+ cations hinders the existence of intermolecular Ag-Ag interactions although several C-H····π interactions have been observed. A similar reaction between [Rh2(μ-O2CCMe3)4(HO2CCMe3)2] and PPh4[Ag(CN)2] led to the molecular compound (PPh4)2{Rh2(μ-O2CCMe3)4[Ag(CN)2]2} (6) by replacement of the axial HO2CCMe3 ligands by two [Ag(CN)2]− units. The trimethylacetate ligand increases the solubility of the complex during the crystallization favouring the formation of discrete heteronuclear species.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Synthesis and Structural Characterization of a Series of One-Dimensional Heteronuclear Dirhodium-Silver Coordination Polymers

et al. 2019

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“…The use of other metal complexes as connectors between the paddlewheel units can lead to the formation of heterometallic one-dimensional coordination polymers, whose versatile chemical and physical properties, such as temperature dependent luminescence or modulation of their electronic structures, make those polymers promising materials [22][23][24][25]. An interesting approach to obtain this kind of heterometallic one-dimensional polymers is the use of platinum complexes to form {[Rh 2 ]-[Pt 2 ]-[Pt 2 ]} n chains, in which the different dimetallic units show direct Rh-Pt metal-metal bonds [26][27][28][29]. Paramagnetic [Rh 2 ]-[Pt-Cu-Pt] chains can be synthesized, also inserting a copper complex [30,31].…”

Section: Introductionmentioning

confidence: 99%

Linear One-Dimensional Coordination Polymers Constructed by Dirhodium Paddlewheel and Tetracyanido-Metallate Building Blocks

et al. 2019

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In this article, we describe the preparation of anionic heteronuclear one-dimensional coordination polymers made by dirhodium paddlewheels and tetracyanido-metallatate building blocks. A series of complexes of (PPh4)2n[{Rh2(µ-O2CCH3)4}{M(CN)4}]n (M = Ni (1), Pd (2), Pt (3)) formulae were obtained by reaction of [Rh2(μ-O2CCH3)4] with (PPh4)2[M(CN)4] in a 1:1 or 2:1 ratio. Crystals of 1−3 suitable for single crystal X-ray diffraction were grown by slow diffusion of a dichloromethane solution of the dirhodium complex into a chloroform solution of the corresponding tetracyanido–metallatate salt. Compounds 1 and 2 are isostructural and crystallize in the triclinic P-1 space group, while compound 3 crystallizes in the monoclinic P21/n space group. A detailed description of the structures is presented, including the analysis of the packing of anionic chains and PPh4+ cations.

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“…In the crystal, there are two crystallographically independent octanuclear complexes (Fig- Table 1 summarizes the Rh−Pt distance of 5, 6′, and related compounds. [81][82][83][84][85]102,103 In all compounds, unbridged Rh−Pt distances are shorter than the sum of the van der Waals radii (4.1 Å) of the Rh and Pt atoms, 104 − ions, being components of single crystals for octanuclear complex 6′, whose ions obstruct further 1-D extension by hydrogen bonding. As described in the Experimental Section, elemental analyses evidently indicate whether infinite chain or octanuclear compound: the weight ratio of C, H, and N in the octanuclear compound becomes higher than those in the infinite chain because the amount of piam and NH 3 in the octanuclear compound becomes larger.…”

Section: ■ Results and Discussionmentioning

confidence: 98%

Modulation of Band Gaps toward Varying Conductivities in Heterometallic One-Dimensional Chains by Ligand Alteration and Third Metal Insertion

et al. 2020

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A heterometallic one-dimensional (1-D) chain consisting of multiple kinds of metals, Rh, Pt, and Pd, with direct metal–metal bonds was successfully obtained by mixing a Rh dinuclear complex and Pt–Pd–Pt trinuclear complex. The Pt–Pd–Pt trinuclear complex can be reversibly one-electron-oxidized or -reduced, where the electron paramagnetic resonance spectrum of the one-electron-oxidized one shows an axially symmetric signal with hyperfine splitting by two Pt and Pd, indicating that an unpaired electron is delocalized to the d z 2 orbital of Pt–Pd–Pt. Utilized with the highest occupied molecular orbital and lowest unoccupied molecular orbital interaction at the d z 2 orbital, simple mixing of the Pt–Pd–Pt trinuclear complex and Rh dinuclear complex in adequate solvents afforded heterometallic 1-D chains, which are aligned as −Rh–Rh–Pt–Pd–Pt–. Several physical measurements revealed that the metal oxidation state is +2. Diffuse reflectance spectra and theoretical calculations show that heterometallic 1-D chains have σ-type conduction and valence bands where π*(Rh2) are lying between them, whose gaps become narrower than the prototype chains aligned as −Rh–Rh–Pt–Pt–Pt–Pt–. The narrower band gaps are induced by destabilization of the σ-type valence bands and accompanied by insertion of Pd ions because the d-orbital energy level of Pd is closer in value to Rh compared with Pt. Flash-photolysis time-resolved microwave conductivity measurements exhibited an increase in the product of charge carrier mobility and its generation efficiency (8.1 × 10–5 to 4.6 × 10–4 cm2 V–1 s–1) with narrowing the band gaps, suggesting that the better conductivity is attributed to shorter metal–metal distances in 1-D chains. These results imply the possibilities of controlling band gap with ligand modification and third metal insertion in heterometallic 1-D chains to show various conductivities.

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Heterometallic one-dimensional chain with tetradeca metal repetition constructed by amidate bridged dirhodium and pivalate bridged diplatinum complexes influenced by hydrogen bonding

Cited by 12 publications

References 53 publications

Synthesis and Structural Characterization of a Series of One-Dimensional Heteronuclear Dirhodium-Silver Coordination Polymers

Synthesis and Structural Characterization of a Series of One-Dimensional Heteronuclear Dirhodium-Silver Coordination Polymers

Linear One-Dimensional Coordination Polymers Constructed by Dirhodium Paddlewheel and Tetracyanido-Metallate Building Blocks

Modulation of Band Gaps toward Varying Conductivities in Heterometallic One-Dimensional Chains by Ligand Alteration and Third Metal Insertion

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