Structural Characterization and Photochemical Properties of Mono- and Bimetallic Cu-Mabiq Complexes

H. Sophia Stark; Philipp J. Altmann; Stephen Sproules; Corinna R. Hess

doi:10.1021/acs.inorgchem.8b00471

Structural Characterization and Photochemical Properties of Mono- and Bimetallic Cu-Mabiq Complexes

H. Sophia Stark, Philipp J. Altmann, Stephen Sproules, Corinna R. Hess

Assistant Professorship of Bioinorganic Chemistry

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

8 Scopus citations

Abstract

We present a series of monometallic ([Cu(Mabiq)OTf] (1) and [Cu(Mabiq)] (2)) and bimetallic copper-Mabiq complexes ([Cu₂(Mabiq)(PPh₃)₂(OTf)₂] (3) and [Cu₂(Mabiq)(PPh₃)₂]PF₆ (4)). The latter compounds contain an additional Cu^I center that binds in a tetrahedral fashion to the external bipyrimidine nitrogens of the macrocyclic ligand. Compounds 3 and 4 represent the first examples of bimetallic transition metal Mabiq complexes, stable both in solution and in the solid state. The structural and electronic properties of compounds 1-4 were analyzed by means of X-ray crystallography, cyclic voltammetry, and spectroscopic methods. One-electron reduced 2 and 4 consist of a Cu^II ion coordinated by a Mabiq ligand radical, [Cu^II(Mabiq^•)]. Thus, both bimetallic compounds are mixed-valent with respect to the copper oxidation states. Complexes 2 and 4 can be generated photochemically, upon irradiation of 1 or 3 with visible light in the presence of a sacrificial electron donor.

Original language	English
Pages (from-to)	6401-6409
Number of pages	9
Journal	Inorganic Chemistry
Volume	57
Issue number	11
DOIs	https://doi.org/10.1021/acs.inorgchem.8b00471
State	Published - 4 Jun 2018

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title = "Structural Characterization and Photochemical Properties of Mono- and Bimetallic Cu-Mabiq Complexes",

abstract = "We present a series of monometallic ([Cu(Mabiq)OTf] (1) and [Cu(Mabiq)] (2)) and bimetallic copper-Mabiq complexes ([Cu2(Mabiq)(PPh3)2(OTf)2] (3) and [Cu2(Mabiq)(PPh3)2]PF6 (4)). The latter compounds contain an additional CuI center that binds in a tetrahedral fashion to the external bipyrimidine nitrogens of the macrocyclic ligand. Compounds 3 and 4 represent the first examples of bimetallic transition metal Mabiq complexes, stable both in solution and in the solid state. The structural and electronic properties of compounds 1-4 were analyzed by means of X-ray crystallography, cyclic voltammetry, and spectroscopic methods. One-electron reduced 2 and 4 consist of a CuII ion coordinated by a Mabiq ligand radical, [CuII(Mabiq•)]. Thus, both bimetallic compounds are mixed-valent with respect to the copper oxidation states. Complexes 2 and 4 can be generated photochemically, upon irradiation of 1 or 3 with visible light in the presence of a sacrificial electron donor.",

author = "Stark, {H. Sophia} and Altmann, {Philipp J.} and Stephen Sproules and Hess, {Corinna R.}",

note = "Publisher Copyright: {\textcopyright} 2018 American Chemical Society.",

year = "2018",

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doi = "10.1021/acs.inorgchem.8b00471",

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T1 - Structural Characterization and Photochemical Properties of Mono- and Bimetallic Cu-Mabiq Complexes

AU - Stark, H. Sophia

AU - Altmann, Philipp J.

AU - Sproules, Stephen

AU - Hess, Corinna R.

PY - 2018/6/4

Y1 - 2018/6/4

N2 - We present a series of monometallic ([Cu(Mabiq)OTf] (1) and [Cu(Mabiq)] (2)) and bimetallic copper-Mabiq complexes ([Cu2(Mabiq)(PPh3)2(OTf)2] (3) and [Cu2(Mabiq)(PPh3)2]PF6 (4)). The latter compounds contain an additional CuI center that binds in a tetrahedral fashion to the external bipyrimidine nitrogens of the macrocyclic ligand. Compounds 3 and 4 represent the first examples of bimetallic transition metal Mabiq complexes, stable both in solution and in the solid state. The structural and electronic properties of compounds 1-4 were analyzed by means of X-ray crystallography, cyclic voltammetry, and spectroscopic methods. One-electron reduced 2 and 4 consist of a CuII ion coordinated by a Mabiq ligand radical, [CuII(Mabiq•)]. Thus, both bimetallic compounds are mixed-valent with respect to the copper oxidation states. Complexes 2 and 4 can be generated photochemically, upon irradiation of 1 or 3 with visible light in the presence of a sacrificial electron donor.

AB - We present a series of monometallic ([Cu(Mabiq)OTf] (1) and [Cu(Mabiq)] (2)) and bimetallic copper-Mabiq complexes ([Cu2(Mabiq)(PPh3)2(OTf)2] (3) and [Cu2(Mabiq)(PPh3)2]PF6 (4)). The latter compounds contain an additional CuI center that binds in a tetrahedral fashion to the external bipyrimidine nitrogens of the macrocyclic ligand. Compounds 3 and 4 represent the first examples of bimetallic transition metal Mabiq complexes, stable both in solution and in the solid state. The structural and electronic properties of compounds 1-4 were analyzed by means of X-ray crystallography, cyclic voltammetry, and spectroscopic methods. One-electron reduced 2 and 4 consist of a CuII ion coordinated by a Mabiq ligand radical, [CuII(Mabiq•)]. Thus, both bimetallic compounds are mixed-valent with respect to the copper oxidation states. Complexes 2 and 4 can be generated photochemically, upon irradiation of 1 or 3 with visible light in the presence of a sacrificial electron donor.

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 11

ER -

Structural Characterization and Photochemical Properties of Mono- and Bimetallic Cu-Mabiq Complexes

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