Heterometallic Cluster-Capped Tetrahedral Assemblies with Postsynthetic Modification of the Metal Cores

Julia R. Shakirova; Elena V. Grachova; Vladislav V. Gurzhiy; Senthil Kumar Thangaraj; Janne Jänis; Alexey S. Melnikov; Antti J. Karttunen; Sergey P. Tunik; Igor O. Koshevoy

doi:10.1002/anie.201809058

Heterometallic Cluster-Capped Tetrahedral Assemblies with Postsynthetic Modification of the Metal Cores

Julia R. Shakirova^*, Elena V. Grachova, Vladislav V. Gurzhiy, Senthil Kumar Thangaraj, Janne Jänis, Alexey S. Melnikov, Antti J. Karttunen, Sergey P. Tunik, Igor O. Koshevoy

^*Corresponding author for this work

Research output: Contribution to journal › Article › Scientific › peer-review

34 Citations (Scopus)

Abstract

Combining the star-shaped alkynyl ligands with low-nuclearity gold–copper triphosphane clusters produces 3D metallocage aggregates, which demonstrate room temperature phosphorescence in solution (max Φ_em=0.6). Their luminescence mainly originates from cluster-localized metal-to-ligand charge transfer excited state. These supramolecular assemblies can be easily converted into the isostructural gold-silver congeners by the direct exchange of the metal ions. Such modification of the terminal metal cores switches the emission to the intraligand (alkyne) electronic transitions of the triplet manifold, that represents an unusual optical functionality among the metallocycle/metallocage complexes.

Original language	English
Pages (from-to)	14154-14158
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	57
Issue number	43
DOIs	https://doi.org/10.1002/anie.201809058
Publication status	Published - 22 Oct 2018
MoE publication type	A1 Journal article-refereed

Keywords

alkyne ligands
cluster compounds
coinage metals
heterometallic complexes
phosphorescence

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10.1002/anie.201809058

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title = "Heterometallic Cluster-Capped Tetrahedral Assemblies with Postsynthetic Modification of the Metal Cores",

abstract = "Combining the star-shaped alkynyl ligands with low-nuclearity gold–copper triphosphane clusters produces 3D metallocage aggregates, which demonstrate room temperature phosphorescence in solution (max Φem=0.6). Their luminescence mainly originates from cluster-localized metal-to-ligand charge transfer excited state. These supramolecular assemblies can be easily converted into the isostructural gold-silver congeners by the direct exchange of the metal ions. Such modification of the terminal metal cores switches the emission to the intraligand (alkyne) electronic transitions of the triplet manifold, that represents an unusual optical functionality among the metallocycle/metallocage complexes.",

keywords = "alkyne ligands, cluster compounds, coinage metals, heterometallic complexes, phosphorescence",

author = "Shakirova, {Julia R.} and Grachova, {Elena V.} and Gurzhiy, {Vladislav V.} and Thangaraj, {Senthil Kumar} and Janne J{\"a}nis and Melnikov, {Alexey S.} and Karttunen, {Antti J.} and Tunik, {Sergey P.} and Koshevoy, {Igor O.}",

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month = oct,

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doi = "10.1002/anie.201809058",

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journal = "Angewandte Chemie - International Edition",

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T1 - Heterometallic Cluster-Capped Tetrahedral Assemblies with Postsynthetic Modification of the Metal Cores

AU - Shakirova, Julia R.

AU - Grachova, Elena V.

AU - Gurzhiy, Vladislav V.

AU - Thangaraj, Senthil Kumar

AU - Jänis, Janne

AU - Melnikov, Alexey S.

AU - Karttunen, Antti J.

AU - Tunik, Sergey P.

AU - Koshevoy, Igor O.

PY - 2018/10/22

Y1 - 2018/10/22

N2 - Combining the star-shaped alkynyl ligands with low-nuclearity gold–copper triphosphane clusters produces 3D metallocage aggregates, which demonstrate room temperature phosphorescence in solution (max Φem=0.6). Their luminescence mainly originates from cluster-localized metal-to-ligand charge transfer excited state. These supramolecular assemblies can be easily converted into the isostructural gold-silver congeners by the direct exchange of the metal ions. Such modification of the terminal metal cores switches the emission to the intraligand (alkyne) electronic transitions of the triplet manifold, that represents an unusual optical functionality among the metallocycle/metallocage complexes.

AB - Combining the star-shaped alkynyl ligands with low-nuclearity gold–copper triphosphane clusters produces 3D metallocage aggregates, which demonstrate room temperature phosphorescence in solution (max Φem=0.6). Their luminescence mainly originates from cluster-localized metal-to-ligand charge transfer excited state. These supramolecular assemblies can be easily converted into the isostructural gold-silver congeners by the direct exchange of the metal ions. Such modification of the terminal metal cores switches the emission to the intraligand (alkyne) electronic transitions of the triplet manifold, that represents an unusual optical functionality among the metallocycle/metallocage complexes.

KW - alkyne ligands

KW - cluster compounds

KW - coinage metals

KW - heterometallic complexes

KW - phosphorescence

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JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 43

ER -

Heterometallic Cluster-Capped Tetrahedral Assemblies with Postsynthetic Modification of the Metal Cores

Abstract

Keywords

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