Multinuclear Ag Clusters Sandwiched by Pt Complex Units: Fluxional Behavior and Chiral‐at‐Cluster Photoluminescence

Horiuchi, Shigeo; Moon, Sangjoon; Ito, Akitaka; Tessarolo, Jacopo; Sakuda, Eri; Arikawa, Yasuhiro; Clever, Guido H.; Umakoshi, Keisuke

doi:10.1002/ange.202101460

Cited by 7 publications

(3 citation statements)

References 72 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The molecule of Ag 3 ⊂ 1 comprises three unique silver(I) cations arranged into a cluster [65] in which each metal possessed a unique coordination environment. The Ag(1), closest to the pole, is bound to the three imine nitrogens (N(im)−Ag(1): 2.260(4)−2.398(4) Å) and the bridgehead atom (2.599(4) Å), whereas Ag(2) and Ag(3) remain in the equatorial part, coordinated by two pyrrolides (2.115(4) Å and 2.125(4) Å), and a pyrrolic (2.216(4) Å) and two imine nitrogens (2.229(4) Å and 2.519(4) Å), respectively.…”

Section: Resultsmentioning

confidence: 99%

Plenates: Anion‐Dependent Self‐Assembly of the Pyrrole Cage Encapsulating Silver(I) Clusters

Sarwa

Białońska

Garbicz

et al. 2023

Chemistry A European J

View full text Add to dashboard Cite

The self-assembly of 2,5-diformylpyrrole, tris(2aminoethyl)amine, and silver(I) yielded, depending on the size and basicity of the anion, new cascade complexes or plenates, that is, cryptates incorporating Ag n n + clusters. The nature of the product was counterion-dependent, and its formation was either driven by cascade anion binding or by argentophilic interactions stabilizing the cluster within the cavity. The reaction of plenates with tetrabutylammonium halides resulted in the protonation-coupled replacement of the Ag 3 3 + with anion(s), yielding cascade cryptates.

show abstract

Section: Resultsmentioning

confidence: 99%

Plenates: Anion‐Dependent Self‐Assembly of the Pyrrole Cage Encapsulating Silver(I) Clusters

Sarwa

Białońska

Garbicz

et al. 2023

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…The Pt(II) precursors 3 and 5 on the one hand and the Pt 2 Ag 2 complexes 9 and 11 on the other revealed identical absorption (266 nm) and emission patterns (397–411 and 431–436 nm at λ ex = 352 nm). The related known PtAg complexes were shown to undergo a blueshift, a redshift, or no change in their absorption/emission spectra upon the formation of a dative Pt → Ag bond. ,,− …”

Section: Resultsmentioning

confidence: 99%

Influence of the Steric/Electronic Properties of N-Aryl Substituents in Cycloplatinated Guanidinate(1−) Complexes on the Formation of Discrete Pt → Ag Complexes and One-Dimensional Coordination Polymer

2023

View full text Add to dashboard Cite

The reactions of cycloplatinated guanidinate(1−) complexes 1−6 with AgTFA (TFA = OC(O)CF 3 ) in 1:1 and 1:2 Pt II /Ag I molar ratios afforded complexes containing three types of Pt 2 Ag 2 skeletons (7−10, 11, and 13), one 1D CP containing Pt 2 Ag 3 skeleton ( 16), and a Pt 2 Ag 4 complex (17) in 91−95% (method 1), 73−82% (method 2) (7−10), and 54−79% (11, 13, 16, and 17) yields. The reactions of 11 with 2,6-XylNC (2,6-Xyl = 2,6-Me 2 C 6 H 3 ) and 4-DMAP (4-dimethylaminopyridine) gave a neutral complex 18 and an ionic complex 19, respectively. Molecular structures of 12 complexes were unambiguously determined by single-crystal X-ray diffraction. Ten complexes contain unprecedented PtAg skeletons and are shown to contain multiple number of dative Pt → Ag bonds supported by the TFA ligand, platinated carbon of the TAG ligand, or both these ligands in conjunction with the Ag−Ag contacts stabilized by argentophilic interaction. Further, the new complexes were characterized by analytical, IR, and multinuclear NMR ( 19 F, 1 H, 13 C{ 1 H}, and 195 Pt) spectroscopies, powder X-ray diffraction, and TGA/DTA. In solution, 9 and 19 exist in more than one form as identified by multinuclear NMR, and this behavior is ascribed to the restricted (N 2 )C−N(H)Ar single-bond rotation of the TAG ligand. The photophysical properties of 9 and 11 are reported.

show abstract

“…Therefore, a mixed-valence Pt 2 (II,IV) formulation with the metals linked by a Pt II → Pt IV donor−acceptor bond seems to be the most likely for 3a′ in MeCN solution, which is also compatible with the observed metal−metal coupling. 47 According to that, we observed that compound 3a′ reacted with MeI in acetonitrile to give 2a′. Keeping in mind the small energy barrier for the transformation of Int-R into Int′-R, the free energy difference between the species Pt 2 (III,III) (4a or 5a) and Pt 2 (II,IV) (Int′-Me, Int′-Bn) seems to determine the nature of the compounds obtained at r.t.…”

Section: Synthesis Of [{Pt(c^c* a )Bn(μ-pz)} 2 (μ-Br)]br (6a)mentioning

confidence: 79%

High-Valent Pyrazolate-Bridged Platinum Complexes: A Joint Experimental and Theoretical Study

et al. 2022

View full text Add to dashboard Cite

Complexes [{Pt(C^C*)(μ-pz)} 2 ] (HC^C* A = 1-(4-(ethoxycarbonyl)phenyl)-3-methyl-1 H -imidazol-2-ylidene 1a , HC^C* B = 1-phenyl-3-methyl-1 H -imidazol-2-ylidene 1b ) react with methyl iodide (MeI) at room temperature in the dark to give compounds [{Pt IV (C^C*)Me(μ-pz)} 2 (μ-I)]I (C^C* A 2a , C^C* B 2b ). The reaction of 1a with benzyl bromide (BnBr) in the same conditions afforded [Br(C^C* A )Pt III (μ-pz) 2 Pt III (C^C* A )Bn] ( 5a ), which by heating in BnBr(l) became [{Pt IV (C^C* A )Bn(μ-pz)} 2 (μ-Br)]Br ( 6a ). Experimental investigations and density functional theory (DFT) calculations on the mechanisms of these reactions from 1a revealed that they follow a S N 2 pathway in the two steps of the double oxidative addition (OA). Based on the DFT investigations, species such as [(C^C* A )Pt III (μ-pz) 2 Pt III (C^C* A )R]X (RX = MeI Int-Me , BnBr Int-Bn ) and [(C^C* A )Pt II (μ-pz) 2 Pt IV (C^C* A )(R)X] (RX = MeI Int′-Me , BnBr Int′-Bn ) were proposed as intermediates for the first and the second OA reactions, respectively. In order to put the mechanisms on firmer grounds, Int-Me was prepared as [(C^C* A )Pt III (μ-pz) 2 Pt III (C^C* A )Me]BF 4 ( 3a′ ) and used to get [I(C^C* A )Pt III (μ-pz) 2 Pt III (C^C* A )Me]( 4a ), [(C^C* A )Pt II (μ-pz) 2 Pt IV (C^C* A )(Me)I]( Int′-Me ), and [{Pt IV (C^C*)Me(μ-pz)} 2 (μ-I)]BF 4 ( 2a′ ). The single-crystal X-ray structures of 2a , 2b , 3a′ , and 5a along with the mono- and bi-dimensional 1 H and 195 ...

show abstract

Multinuclear Ag Clusters Sandwiched by Pt Complex Units: Fluxional Behavior and Chiral‐at‐Cluster Photoluminescence

Cited by 7 publications

References 72 publications

Plenates: Anion‐Dependent Self‐Assembly of the Pyrrole Cage Encapsulating Silver(I) Clusters

Plenates: Anion‐Dependent Self‐Assembly of the Pyrrole Cage Encapsulating Silver(I) Clusters

Influence of the Steric/Electronic Properties of N-Aryl Substituents in Cycloplatinated Guanidinate(1−) Complexes on the Formation of Discrete Pt → Ag Complexes and One-Dimensional Coordination Polymer

High-Valent Pyrazolate-Bridged Platinum Complexes: A Joint Experimental and Theoretical Study

Contact Info

Product

Resources

About