Linearly Aligned Metal Clusters: Versatile Reactivity and Bonding Nature of Tetrametal M–Mo–Mo–M Complexes (M = Pt, Pd, Ir, and Rh) Supported by 6-Diphenylphosphino-2-pyridonato Ligand

Mashima, Kazushi

doi:10.1246/bcsj.20090281

Cited by 30 publications

(6 citation statements)

References 157 publications

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“…Seventeen tetranuclear copper(I) chain complexes (88)(89)(90)(91)(92)(93)(94)(95)(96)(97)(98)(99)(100)(101)(102)(103)(104) have been documented and they are presented in ad ecreasing orderb ased on the coordination number of the Cu centers as illustrated in Figure 3. Twot etranuclearc opper complexes supported by the monoanionic tetradentate N,N'-bis(pyrimidyl-2-yl)formamidinato (PMF) ligand, [Cu 4 (pmf) 3 (SCN) 2 ] À counterbalanced by the cation [K(thf) 5 ] + (88)o r[ nBu 4 N] + (89)w ere obtained when CuSCN was the startingr eagent.…”

Section: Nitrogen-supported Tetracopper Chain Complexesmentioning

confidence: 99%

“…[80][81][82][83][84][85] In addition, EMAC complexes display interesting physical properties, such as electron-transfer processes in metal chainsa nd applications in molecular electronics. [86][87][88][89][90][91][92] Recent interesti nt he preparation of copper string complexes is due to their unique photoluminescence properties and potential applicationsi nm aterial science. [77, Ar ecent theoretical analysiss uggested that the coordination of multi-copper atomst oD NA base pairs may increaset he conductivity of DNA-based nanowires.…”

Section: Introductionmentioning

confidence: 99%

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Cuprophilic Interactions in and between Molecular Entities

Harisomayajula

Makovetskyi

Tsai

2019

Chemistry A European J

154

127

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Despite being weak attractive forces, closed‐shell metallophilic interactions play important roles in the Group 11 metal complexes on their diverse structural and physical features. A plethora of experimental and computational studies has thus been dedicated to such weak attractive d10–d10 interactions, particularly aurophilic and argentophilic interactions. Although d10–d10 CuI–CuI forces had been recognized for four decades, cuprophilic interactions are less explored and they are best evidenced by single‐crystal X‐ray crystallographic analysis on CuI complexes and aggregates thereof, by which precise information about the Cu⋅⋅⋅Cu contacts, shorter than the sum of two van der Waals radii (3.92 Å) between the copper centers concerned can be obtained. Based on recently compelling experimental and spectroscopic evidence for intra‐ and intermolecular cuprophilic interactions in copper chemistry, the present Minireview summarizes recent progress in the past three decades in the synthesis and structures of multinuclear homometallic copper complexes, whereby supported and unsupported d10–d10 CuI–CuI interactions are at work.

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Section: Nitrogen-supported Tetracopper Chain Complexesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Cuprophilic Interactions in and between Molecular Entities

Harisomayajula

Makovetskyi

Tsai

2019

Chemistry A European J

154

127

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“…DFT calculations suggest the ligand-unsupported cuprophilicity originate from weak attractive orbital interactions,a nd the strength is estimated to be 2.4 kcal mol À1 .Therecognition of linear trinuclear copper(II) and nickel(II) complexes supported by four di-2-pyridylamido ligands [1] sparked ar apid growth of the extended metal atom chain (EMAC; or metal string) complexes.T he study of EMACs focuses primarily on their physical properties,s uch as magnetic behaviors,m etal-metal interactions,a nd potential applications in molecular electronics. [2] Many tetranuclear EMACs have been characterized for the past 20 years,and are predominated by divalent Cr, Co,N i, or Ru. [2][3][4] Ac rucial factor in the construction of EMACs is the ligand design; efficacious ligands are predominated by those nitrogencontaining polydentate donors,o ligophosphines,a nd conjugated polyenes.…”

mentioning

confidence: 99%

“…[2] Many tetranuclear EMACs have been characterized for the past 20 years,and are predominated by divalent Cr, Co,N i, or Ru. [2][3][4] Ac rucial factor in the construction of EMACs is the ligand design; efficacious ligands are predominated by those nitrogencontaining polydentate donors,o ligophosphines,a nd conjugated polyenes. [2][3][4] Interests in EMACs of copper arose from their unique photoluminescence properties and potential applications in material science.…”

mentioning

confidence: 99%

“…[2][3][4] Ac rucial factor in the construction of EMACs is the ligand design; efficacious ligands are predominated by those nitrogencontaining polydentate donors,o ligophosphines,a nd conjugated polyenes. [2][3][4] Interests in EMACs of copper arose from their unique photoluminescence properties and potential applications in material science. [5][6][7] Short EMACs of copper-(I) containing 3o r4Cu atoms have been reported, [8,9] but longer EMACs of copper(I) are very rare.…”

mentioning

confidence: 99%

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Ligand‐Unsupported Cuprophilicity in the Preparation of Dodecacopper(I) Complexes and Raman Studies

Harisomayajula

et al. 2018

Angewandte Chemie

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Synthesis and characterization of two dodecacopper(I) extended metal atom chains (EMAC) assembled by two hexadentate bis(pyridylamido)amidinate-supported hexacopper(I) string complexes (monomers) via the ligand-unsupported cuprophilicity are described. In addition to short unsupported Cu À Cu contacts,two hexacopper fragments in these two dodecacopper EMACs show abent conformation based on X-ray crystallography.C ompared with their THFbound hexacopper(I) monomers and protonated ligands,these ligand-unsupported cuprophilic interactions are shown to be weak by Raman spectroscopy. DFT calculations suggest the ligand-unsupported cuprophilicity originate from weak attractive orbital interactions,a nd the strength is estimated to be 2.4 kcal mol À1 .Therecognition of linear trinuclear copper(II) and nickel(II) complexes supported by four di-2-pyridylamido ligands [1] sparked ar apid growth of the extended metal atom chain (EMAC; or metal string) complexes.T he study of EMACs focuses primarily on their physical properties,s uch as magnetic behaviors,m etal-metal interactions,a nd potential applications in molecular electronics. [2] Many tetranuclear EMACs have been characterized for the past 20 years,and are predominated by divalent Cr, Co,N i, or Ru. [2][3][4] Ac rucial factor in the construction of EMACs is the ligand design; efficacious ligands are predominated by those nitrogencontaining polydentate donors,o ligophosphines,a nd conjugated polyenes. [2][3][4] Interests in EMACs of copper arose from their unique photoluminescence properties and potential applications in material science. [5][6][7] Short EMACs of copper-(I) containing 3o r4Cu atoms have been reported, [8,9] but longer EMACs of copper(I) are very rare. [10] Arisen from relativistic and correlation effects, [11] the term "metallophilicity" was coined to describe metal-metal interactions between two metal atoms with ac losed-shell elec-tronic configuration. Metallophilicity are often observed in Group 11 metal complexes.O ft he coinage metals,a urophilicity is the strongest metallophilic interaction with astrength of about 7-12 kcal mol À1 comparable to that of ah ydrogen bond, [12] which accounts for the characterization of al arge number of multinuclear gold complexes. [13] Whereas the cuprophilic interaction is weaker, [14] different conclusions on the existence of such aw eak interaction have been made based on spectral and theoretical investigations. [8,9,15] The ligand-unsupported cuprophilic interactions have widely been invoked to be ad riving force for the self-assembly of copper(I) aggregates, [16,17] but concrete evidence directly from crystal structural investigation remains ag reat challenge.T he unsupported cuprophilic interactions are usually accompanied by H-bonding, inter-ligand p-p/metal-ligand p interactions. [16,17] Intermolecular cuprophilicity is not observed in EMACs of copper(I), although it can be applied to extend the chain lengths.H erein, we report af amily of linear arrays of oligocopper(I) stabilized by five nitrogencontain...

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Electrically Induced Mixed Valence Increases the Conductivity of Copper Helical Metallopolymers

et al. 2021

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Controlling the flow of electrical current at the nanoscale typically requires complex top‐down approaches. Here, a bottom‐up approach is employed to demonstrate resistive switching within molecular wires that consist of double‐helical metallopolymers and are constructed by self‐assembly. When the material is exposed to an electric field, it is determined that ≈25% of the copper atoms oxidize from CuI to CuII, without rupture of the polymer chain. The ability to sustain such a high level of oxidation is unprecedented in a copper‐based molecule: it is made possible here by the double helix compressing in order to satisfy the new coordination geometry required by CuII. This mixed‐valence structure exhibits a 104‐fold increase in conductivity, which is projected to last on the order of years. The increase in conductivity is explained as being promoted by the creation, upon oxidation, of partly filled orbitals aligned along the mixed‐valence copper array; the long‐lasting nature of the change in conductivity is due to the structural rearrangement of the double‐helix, which poses an energetic barrier to re‐reduction. This work establishes helical metallopolymers as a new platform for controlling currents at the nanoscale.

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Linearly Aligned Metal Clusters: Versatile Reactivity and Bonding Nature of Tetrametal M–Mo–Mo–M Complexes (M = Pt, Pd, Ir, and Rh) Supported by 6-Diphenylphosphino-2-pyridonato Ligand

Cited by 30 publications

References 157 publications

Cuprophilic Interactions in and between Molecular Entities

Cuprophilic Interactions in and between Molecular Entities

Ligand‐Unsupported Cuprophilicity in the Preparation of Dodecacopper(I) Complexes and Raman Studies

Electrically Induced Mixed Valence Increases the Conductivity of Copper Helical Metallopolymers

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