Electrical Behaviour of Heterobimetallic [MM′(EtCS2)4] (MM′=NiPd, NiPt, PdPt) and MM′X‐Chain Polymers [PtM(EtCS2)4I] (M=Ni, Pd)

Givaja, Gonzalo; Castillo, Óscar; Mateo, Eva M.; Gallego, Almudena; Gómez‐García, Carlos J.; Calzolari, Arrigo; Felice, Rosa Di; Zamora, Félix

doi:10.1002/chem.201200995

Cited by 19 publications

(13 citation statements)

References 47 publications

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“…Additionally, the subunits that are separated from each other by a bridging halogen are beneficial not only for the full substitution of Pt with Ni, 109,110 but also for the partial substitution of Pt to afford heterobimetallic subunits PtM (M = Ni and Pd). 111 Such a replacement while maintaining the basic structure is not simply possible in (TMTTF)2X, in which the columnar assembly of TMTTF molecules is achieved mainly by the weak π-π interactions.…”

Section: Outlook and Conclusionmentioning

confidence: 99%

One-dimensional electronic systems: metal-chain complexes and organic conductors

Yoshida

Kitagawa

2020

Chem. Commun.

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Section: Outlook and Conclusionmentioning

confidence: 99%

One-dimensional electronic systems: metal-chain complexes and organic conductors

Yoshida

Kitagawa

2020

Chem. Commun.

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“…In contrast to the synthetic methods for these finite chains, crystals of an infinite one-dimensional (1-D) chain are generally obtained by the oxidation of d8 square-planar metals connecting to other metals at the d z 2 orbital, resulting in partially oxidized d z 2 bands showing metallic chains. , Infinite 1-D chains with metal–metal bonds, such as K 2 [Pt(CN) 4 ]Br 0.3 ·3H 2 O (KCP) and Magnus’ green salt, extend from end-to-end in the crystal and have been treated as target compounds with solid physical properties. , In a similar manner to the appearance of HMSCs, in infinite 1-D chains, several heterometallic chains in which different kinds of metal are regularly aligned with metal–metal bonds have been synthesized; − the construction methodologies were: the HOMO–LUMO interaction at the d z 2 orbital (σ-type) orbitals between two kinds of complex were discovered . The significant feature for these heterometallic 1-D chains is the modulation of their electronic structures; in the chains composed of a single kind of metal, σ-type orbitals become HOMO (valence band), but in heterometallic chains, a π-type , and a δ-type − ,, orbitals can be either HOMO or a singly occupied molecular orbital.…”

Section: Introductionmentioning

confidence: 99%

Paramagnetic One-Dimensional Chain Complex Consisting of Three Kinds of Metallic Species Showing Magnetic Interaction through Metal–Metal Bonds

Uemura

Miyake

2019

Inorg. Chem.

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A heterometallic and paramagnetic one-dimensional (1-D) chain (3) aligned as −Rh(+2)−Rh(+2)− Pt(+2)−Co(+2)−Pt(+2)− with direct metal−metal bonds was obtained by HOMO−LUMO interactions at the σ* (d z 2 ) orbital between two kinds of complexes. The 1-D chains in 3 have relatively straight backbones because the raw material complexes, [Rh 2 (O 2 CCH 3 ) 4 ] and [Pt 2 Co(piam) 4 (NH 3 ) 4 ], are connected and stacked in a face-to-face fashion, where Co---Co are separated by about 13.3 Å with four different metals.Physical measurements revealed that 3 has a band gap between the σ-type conduction and valence bands, where dorbitals of the Co ion with three unpaired electrons are laid among them. The magnetic behavior of 3 was investigated and found to be consistent with a complex interaction involving both zero-field splitting and Pauli paramagnetism attributed to band formation superimposed on relatively strong exchange coupling (zJ = −22.2 cm −1 ) between two high-spin Co(+2) ions separated by the diamagnetic Pt−Rh−Rh−Pt.

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“…Metallophilic interactions have attracted the interest of many researchers because they can lead to the formation of supramolecular assemblies of metal complexes, as dimers, oligomers, chains, or sheets, showing useful properties [1][2][3][4][5][6][7][8][9][10]. These M···M interactions, which can be as strong as hydrogen bonds, can lead to M-M distances shorter than the sum of the van der Waals radii, facilitating the electronic communication between heavy metal atoms.…”

Section: Introductionmentioning

confidence: 99%

Taking Advantage of the Coordinative Behavior of a Tridentate Schiff Base Ligand towards Pd2+ and Cu2+

et al. 2019

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We have explored the suitability of an O,N,N-donor Schiff base (H 2 SB) for obtaining dinuclear complexes with heavy metal ions such as Cu 2+ , Zn 2+ , Ni 2+ , and Co 2+ (borderline acids) as well as Pd 2+ and Cd 2+ (soft acids). Spectroscopic studies demonstrated that the complexation of H 2 SB and Cu 2+ , Zn 2+ , Ni 2+ , Co 2+ , Pd 2+ , and Cd 2+ occurred at a 1:1 stoichiometry. We have found two square planar centers with Pd-N-Pd angles of 93.08(11) • and a Pd-Pd distance of 3.0102(4) Å in Pd 2 (SB) 2 ·Me 2 CO. This Pd-Pd distance is 30% shorter than the sum of the van der Waals radii, which is in accordance with a strong palladophilic interaction. Fluorescence studies on H 2 SB-M 2+ interaction showed that H 2 SB can detect Cu 2+ ions in a sample matrix containing various metal ions (hard, soft, or borderline acids) without interference. Determination of binding constants showed that H 2 SB has a greater affinity for borderline acids than for soft acids.Crystals 2019, 9, 407 2 of 15 obtaining dinuclear complexes with heavy metal ions such as Cu 2+ , Zn 2+ , Ni 2+ , and Co 2+ (borderline acids) as well as Pd 2+ and Cd 2+ (soft acids) through a double µ 2 -N sulphonamido bridge (Figure 1 , right). Spectroscopic studies demonstrated that the complexation of H 2 SB and Cu 2+ , Zn 2+ , Ni 2+ , Co 2+ , Pd 2+ , and Cd 2+ occurred at a 1:1 stoichiometry. The crystal structure of Pd 2 (SB) 2 ·Me 2 CO, which has been elucidated by using single crystal X-ray diffraction techniques, has shown a Pd-Pd distance of 3.0102(4) Å, which is sensibly shorter than the sum of the van der Waals radii (4.30 Å). This latter value corresponds to that deduced from recent statistical analyses of intermolecular contacts in deposited X-ray crystal structures, paying also special attention to homoatomic contacts involving Pd, Pt, Cu, Ag, and Au [26]. Fluorescence studies on the interaction of H 2 SB towards heavy metal ions such as Cu 2+ , Zn 2+ , Ni 2+ , Co 2+ , Cd 2+ , and Pd 2+ revealed the ability of H 2 SB to detect Cu 2+ in aqueous solutions containing various metal ions (hard, soft, or borderline acids) without interference. Determination of binding constants showed that H 2 SB has a greater affinity for borderline acids than for soft acids.Crystals 2019, 9, x FOR PEER REVIEW 2 of 15 dinuclear complexes with heavy metal ions such as Cu 2+ , Zn 2+ , Ni 2+ , and Co 2+ (borderline acids) as well as Pd 2+ and Cd 2+ (soft acids) through a double μ2-Nsulphonamido bridge (Figure 1, right). Spectroscopic studies demonstrated that the complexation of H2SB and Cu 2+ , Zn 2+ , Ni 2+ , Co 2+ , Pd 2+ , and Cd 2+ occurred at a 1:1 stoichiometry. The crystal structure of Pd2(SB)2·Me2CO, which has been elucidated by using single crystal X-ray diffraction techniques, has shown a Pd-Pd distance of 3.0102(4) Å, which is sensibly shorter than the sum of the van der Waals radii (4.30 Å). This latter value corresponds to that deduced from recent statistical analyses of intermolecular contacts in deposited X-ray crystal structures, paying also special a...

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Electrical Behaviour of Heterobimetallic [MM′(EtCS₂)₄] (MM′=NiPd, NiPt, PdPt) and MM′X‐Chain Polymers [PtM(EtCS₂)₄I] (M=Ni, Pd)

Cited by 19 publications

References 47 publications

One-dimensional electronic systems: metal-chain complexes and organic conductors

One-dimensional electronic systems: metal-chain complexes and organic conductors

Paramagnetic One-Dimensional Chain Complex Consisting of Three Kinds of Metallic Species Showing Magnetic Interaction through Metal–Metal Bonds

Taking Advantage of the Coordinative Behavior of a Tridentate Schiff Base Ligand towards Pd2+ and Cu2+

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