Structural and Photochemical Properties of Zn(II) Phenanthroline-Derived Complexes: From Mononuclear to Bimetallic and Circular-Trimetallic Helicates

Levín, Pedro; Escudero, Dayra; Díaz, Nicolás; Oliver, Allen; Lappin, A. Graham; Ferraudi, Guillermo; Lemus, Luis

doi:10.1021/acs.inorgchem.9b02773

Title: Structural and Photochemical Properties of Zn(II) Phenanthroline-Derived Complexes: From Mononuclear to Bimetallic and Circular-Trimetallic Helicates

Journal Article · 12 January 2020 · Inorganic Chemistry

DOI: https://doi.org/10.1021/acs.inorgchem.9b02773 · OSTI ID:1799649

^[1]; Escudero, Dayra ^[1]; Díaz, Nicolás ^[1]; Oliver, Allen ^[2]; Lappin, A. Graham ^[2]; Ferraudi, Guillermo ^[2];

^[1]

Universidad de Santiago de Chile (Chile)
Univ. of Notre Dame, IN (United States)

In the design of self-assembled compounds, small variations in the linkers connecting the coordinating moieties can produce large differences in the obtained structures. In this paper, we report three novel zinc(II) complexes with phenanthroline-derived ligands as building blocks (L¹–L³): A mononuclear complex, a bimetallic helicate, and a trimetallic circular helicate. The even-number spacer in L² promotes the formation of a bimetallic helicate stabilized by π-π interactions of adjacent phenanthrolines. The addition of an extra methylene in L³ increases the distance between where the phenanthrolines can stack, and CH-π noncovalent interactions give stability to the circular helicate. When irradiated at 308 nm in acetonitrile, long-lived excited states are formed with all three complexes, which are able to participate in oxidation of 2-propanol and in reduction of methylviologen, MV²⁺. While the overall behavior of the three complexes is similar, the bimetallic helicate is able to form a ground-state adduct with MV²⁺, while the trimer reaches the excited state to form an exciplex with MV²⁺.

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Research Organization:: University of California, Oakland, CA (United States); University of Notre Dame, IN (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: AC02-05CH11231; FC02-04ER15533

OSTI ID:: 1799649

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 3 Vol. 59; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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CCDC 1953327: Experimental Crystal Structure Determination Pedro, Levín,; Dayra, Escudero,; Nicolás, Díaz, https://doi.org/10.5517/ccdc.csd.cc23klkv The current record is supplemented by this dataset	dataset	January 2020
CCDC 1953328: Experimental Crystal Structure Determination Pedro, Levín,; Dayra, Escudero,; Nicolás, Díaz, https://doi.org/10.5517/ccdc.csd.cc23kllw The current record is supplemented by this dataset	dataset	January 2020
CCDC 1953329: Experimental Crystal Structure Determination Pedro, Levín,; Dayra, Escudero,; Nicolás, Díaz, https://doi.org/10.5517/ccdc.csd.cc23klmx The current record is supplemented by this dataset	dataset	January 2020

Title: Structural and Photochemical Properties of Zn(II) Phenanthroline-Derived Complexes: From Mononuclear to Bimetallic and Circular-Trimetallic Helicates

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