Expected and Unconventional Ag+ Binding Modes in Heteronuclear Pt,Ag Coordination Polymers Derived from trans‐[Pt(methylamine)2(pyrazole)2]2+

Brandi-Blanco, Pilar; Miguel, Pablo J. Sanz; Lippert, Bernhard

doi:10.1002/ejic.201101197

Cited by 9 publications

(5 citation statements)

References 69 publications

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“…The Ag + -pyrazolate binding motif thus is best described as η 1 or η 3 . A similar binding situation has been previously described for pyrazolate-based silver complexes containing platinum or palladium. − However, displacement of the Ag + above the pyrazolate ring seems to be facile: in [Ag 2 L] 3 (OTf) 3 , Ag6 is located almost above the center of the ring with a relatively short Ag···centroid distance which is close to a η 5 coordination, though all individual contacts are >3 Å. The η 1 or η 3 bonding interaction found for most of the outer Ag + ions is likely responsible for a bending of the S–Ag–S angles, since those Ag + ions with short Ag–C distances show smaller S–Ag–S angles.…”

Section: Resultssupporting

confidence: 66%

Crowning of Coinage Metal Pyrazolates: Double-Decker Homo- and Heteronuclear Complexes with Synergic Emissive Properties

et al. 2014

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A new pyrazole ligand with flexible thioether chelate arms was synthesized and was used to obtain an unprecedented class of hexanuclear coinage metal complexes of general formula [MM'L]3Y3 (M, M' = Cu, Ag, Au; Y = OTf, BF4). Three of them were characterized by X-ray crystallography, namely, homometallic [Ag2L]3(OTf)3 and [Ag2L]3(BF4)3 as well as heterometallic [CuAgL]3(OTf)3, revealing that the classical [M(μ-pz)]3 core is crowned by a second deck of S-bound M' ions. Depending on the solvent, these oligonuclear systems undergo rapid dynamics and show cation-anion aggregation in solution, which has been investigated by DOSY and temperature dependent NMR spectroscopy. Preliminary luminescence data for selected hexametallic [MM'L]3Y3 complexes show that the combination of ligand-directed intramolecular and supramolecular d(10) metal ion interactions in the solid state gives rise to synergic emissive properties that allow for a selective addressing of different emission wavelengths.

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Section: Resultssupporting

confidence: 66%

Crowning of Coinage Metal Pyrazolates: Double-Decker Homo- and Heteronuclear Complexes with Synergic Emissive Properties

et al. 2014

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“…The 1:1 cofacial adduct 2 adopts a similar biconcave conformation as 2 a , except that the face‐to‐face overlap in [ 1 ⋅PtOEP] is strengthened by donor–acceptor Pt–Ag metallophilic bonding. The shortest Pt–Ag and Pt–Ag 3 centroid distances in 2 are 3.040 and 2.847 Å, respectively, which fall in the range of Pt–Ag dative‐bond distances reported in the literature (2.7–3.2 Å) 13a,b. The binding energy of 2 was determined to be 67.81 kcal mol −1 by DFT calculations, which indicates that the Pt→Ag metallophilic/dative bond is strengthened by electrostatic quadrupolar interactions between 1 and PtOEP (Figure S2).…”

Section: Methodssupporting

confidence: 64%

Formation of a Fluorous/Organic Biphasic Supramolecular Octopus Assembly for Enhanced Porphyrin Phosphorescence in Air

et al. 2015

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The trinuclear triangle-shaped system [tris{3,5-bis(heptafluoropropyl)-1,2,4-triazolatosilver(I)}] (1) and the multi-armed square-shaped metalloporphyrin PtOEP or the free porphyrin base H2OEP serve as excellent octopus hosts (OEP=2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphine). Coupling of the fluorous/organic molecular octopi 1 and H2OEP or PtOEP by strong quadrupole-quadrupole and metal-π interactions affords the supramolecular assemblies [1⋅PtOEP] or [1⋅H2OEP] (2 a), which feature nanoscopic cavities surrounding the upper triangular and lower square cores. The fluorous/organic biphasic configuration of [1⋅PtOEP] leads to an increase in the phosphorescence of PtOEP under ambient conditions. Guest molecules can be included in the biphasic double-octopus assembly in three different site-selective modes.

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“…Complexes containing C-4-donor pyrazolyl groups are very rare . They have been prepared by ruthenium-promoted cyclization of alkynyl(tosyl) hydrazone, gold-mediated triazole-yne 5-endo-dig cyclization, and reaction between [AuCl 4 ] and 1-phenylpyrazole …”

Section: Resultsmentioning

confidence: 99%

Preparation of Phosphorescent Osmium(IV) Complexes with N,N′,C- and C,N,C′-Pincer Ligands

et al. 2017

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Four different pincer ligands, which prove that the disposition of the donor atoms in pincer ligands allows them to develop a marked ability to form less common coordination polyhedra and to favor unusual metal oxidation states, have been generated starting from OsH6(PiPr3)2 and 2-phenyl-6-(1H-pyrazol-3-yl)pyridine (Hpz-py-Ph) in order to stabilize phosphorescent, pentagonal-bipyramidal osmium(IV) emitters. Complex 1 reacts with the disubstituted heterocycle to give OsH2{κ3-N,N′,C-(pz-py-C6H4)}(PiPr3)2 (2), as a result of the activation of a phenyl o-CH bond and the pyrazolyl NH of the pyridine substituents. The addition of methyl trifluoromethanesulfonate (MeOTf) to 2 produces the methylation of the free N atom of the pz group and the formation of the salt [OsH2{κ3-N,N′,C-(Mepz-py-C6H4)}(PiPr3)2]OTf (3), which undergoes deprotonation of the metal center in the presence of KOtBu. The resulting monohydride OsH{κ3-N,N′,C-(Mepz-py-C6H4)}(PiPr3)2 (4) is unstable and evolves into OsH2{κ3-C,N,C′-(Mepz-py-C6H4)}(PiPr3)2 (5) as a consequence of the oxidative addition of the C–H bond at position 4 of the Mepz group to the osmium atom of 4. The addition of MeOTf to 5 produces the methylation of the free N atom of the Mepz group, which is converted into a remote N-heterocyclic carbene, to form [OsH2{κ3-C,N,C′-(Me2pz-py-C6H4)}(PiPr3)2]OTf (6). Complex 1 also reacts with 2-(1H-pyrazol-3-yl)pyridine (Hpz-py). The reaction gives rise to the trihydride derivative OsH3{κ2-N,N-(pz-py)}(PiPr3)2 (7), which leads to the salt [OsH3{κ2-N,N-(Mepz-py)}(PiPr3)2]OTf (8) by addition of MeOTf. The deprotonation of 8 affords the osmium(II) dihydride OsH2{κ2-N,N-(Mepz-py)}(PiPr3)2 (9), which is stable, in contrast to 4. Complexes 2, 3, 5, 7, and 8 are emissive in the green to red region upon photoexcitation.

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Expected and Unconventional Ag⁺ Binding Modes in Heteronuclear Pt,Ag Coordination Polymers Derived from trans‐[Pt(methylamine)₂(pyrazole)₂]²⁺

Cited by 9 publications

References 69 publications

Crowning of Coinage Metal Pyrazolates: Double-Decker Homo- and Heteronuclear Complexes with Synergic Emissive Properties

Crowning of Coinage Metal Pyrazolates: Double-Decker Homo- and Heteronuclear Complexes with Synergic Emissive Properties

Formation of a Fluorous/Organic Biphasic Supramolecular Octopus Assembly for Enhanced Porphyrin Phosphorescence in Air

Preparation of Phosphorescent Osmium(IV) Complexes with N,N′,C- and C,N,C′-Pincer Ligands

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