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Electrochemical, spectroscopic, and (1)O2 sensitization characteristics of 10,10-dimethylbiladiene complexes of zinc and copper.

ABSTRACT: The synthesis, electrochemistry, and photophysical characterization of a 10,10-dimethylbiladiene tetrapyrrole bearing ancillary pentafluorophenyl groups at the 5- and 15-meso positions (DMBil1) is presented. This nonmacrocyclic tetrapyrrole platform is robust and can serve as an excellent ligand scaffold for Zn(2+) and Cu(2+) centers. X-ray diffraction studies conducted for DMBil1 along with the corresponding Zn[DMBil1] and Cu[DMBil1] complexes show that this ligand scaffold binds a single metal ion within the tetrapyrrole core. Additionally, electrochemical experiments revealed that all three of the aforementioned compounds display an interesting redox chemistry as the DMBil1 framework can be both oxidized and reduced by two electrons. Spectroscopic and photophysical experiments carried out for DMBil1, Zn[DMBil1], and Cu[DMBil1] provide a basic picture of the electronic properties of these platforms. All three biladiene derivatives strongly absorb light in the visible region and are weakly emissive. The ability of these compounds to sensitize the formation of (1)O2 at wavelengths longer than 500 nm was probed. Both the free base and Zn(2+) 10,10-dimethylbiladiene architectures show modest efficiencies for (1)O2 sensitization. The combination of structural, electrochemical, and photophysical data detailed herein provides a basis for the design of additional biladiene constructs for the activation of O2 and other small molecules.

SUBMITTER: Pistner AJ

PROVIDER: S-EPMC4234430 | biostudies-literature | 2014 Nov

REPOSITORIES: biostudies-literature

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Electrochemical, spectroscopic, and (1)O2 sensitization characteristics of 10,10-dimethylbiladiene complexes of zinc and copper.

Pistner Allen J AJ Pupillo Rachel C RC Yap Glenn P A GP Lutterman Daniel A DA Ma Ying-Zhong YZ Rosenthal Joel J

The journal of physical chemistry. A 20141007 45

The synthesis, electrochemistry, and photophysical characterization of a 10,10-dimethylbiladiene tetrapyrrole bearing ancillary pentafluorophenyl groups at the 5- and 15-meso positions (DMBil1) is presented. This nonmacrocyclic tetrapyrrole platform is robust and can serve as an excellent ligand scaffold for Zn(2+) and Cu(2+) centers. X-ray diffraction studies conducted for DMBil1 along with the corresponding Zn[DMBil1] and Cu[DMBil1] complexes show that this ligand scaffold binds a single metal ...[more]

PMID: 25187099

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Project description:Two brominated 10,10-dimethylisocorrole (10-DMIC) derivatives containing Pd(II) centers have been prepared and characterized. These compounds were prepared via bromination of 10,10-dimethylbiladiene-based oligotetrapyrroles. Bromination of free base 10,10-dimethylbiladiene (DMBil1) followed by metalation with Pd(OAc)2, as well as bromination of the corresponding Pd(II) dimethylbiladiene complex (Pd[DMBil1]) provide routes to Pd(II) hexabromo-10,10-dimethyl-5,15-bis(pentafluorophenyl)-isocorrole (Pd[10-DMIC-Br6]) and Pd(II) octabromo-10,10-dimethyl-5,15-bis(pentafluorophenyl)-isocorrole (Pd[10-DMIC-Br8]). The solid-state structures of the two brominated isocorrole complexes are presented, as is that for a new decabrominated dimethylbiladiene derivative (DMBil-Br10). The electronic and spectroscopic properties of the brominated biladiene and isocorrole derivatives were probed using a combination of voltammetric methods and steady-state UV-vis absorption and emission experiments. Data obtained from these experiments allow the properties of the brominated biladiene and isocorrole derivatives to be compared to previously studied biladiene derivatives (i.e., DMBil1 and Pd[DMBil1]). CV and DPV experiments demonstrate that Pd[10-DMIC-Br6] and Pd[10-DMIC-Br8] support well-behaved multielectron redox chemistry, similar to that which has been observed for other nonaromatic tetrapyrroles containing sp3-hybridized meso-carbons. Spectroscopic experiments reveal that bromination of the dimethylbiladiene core shifts this system's UV-vis absorption profile to lower energy and that the dimethylisocorrole complexes support panchromatic absorption profiles that extend across the UV-vis and into the near-IR region. Photosensitization experiments demonstrate that unlike previously studied Pd(II) biladiene constructs, DMBil-Br10, Pd[10-DMIC-Br6], and Pd[10-DMIC-Br8] support limited triplet excited state chemistry with O2, indicating that the novel nonaromatic tetrapyrrole derivatives described in this work may be best suited for applications other than singlet oxygen sensitization.

Dataset Information

Electrochemical, spectroscopic, and (1)O2 sensitization characteristics of 10,10-dimethylbiladiene complexes of zinc and copper.

Publications

Electrochemical, spectroscopic, and (1)O2 sensitization characteristics of 10,10-dimethylbiladiene complexes of zinc and copper.

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