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Title: Design of porphyrin-based ligands for the assembly of [d-block metal : calcium] bimetallic centers

Abstract

The association of different metals in stable, well-defined molecular assemblies remains a great challenge of supramolecular chemistry. In such constructs, the emergence of synergism, or cooperative effects between the different metal centers is particularly intriguing. These effects can lead to uncommon reactivity or remarkable physico-chemical properties that are not otherwise achievable. For example, the association of alkaline or alkaline-earth cations and transition metals is pivotal for the activity of several biomolecules and human-made catalysts that carry out fundamental redox transformations (water oxidation, nitrogen reduction, water–gas shift reaction, etc.). In many cases the precise nature of the interactions between the alkaline-earth cations and the redox-active transition metals remains elusive due to the difficulty of building stable molecular heterometallic assemblies that associate transition metals and alkaline or alkaline-earth cations in a controlled way. In this work we present the rational design of porphyrin-based ligands possessing a second binding site for alkaline-earth cations above the porphyrin macrocycle primary complexation site. We demonstrate that by using a combination of crown ether and carboxylic acid substituents suitably positioned on the periphery of the porphyrin, bitopic ligands can be obtained. The binding of calcium, a typical alkaline-earth cation, by the newly prepared ligands has been studiedmore » in detail and we show that a moderately large binding constant can be achieved in protic media using ligands that possess some degree of structural flexibility. The formation of Zn–Ca assemblies discussed in this work is viewed as a stepping stone towards the assembly of well defined molecular transition metal-alkaline earth bimetallic centers using a versatile organic scaffold.« less

Authors:
ORCiD logo; ; ; ORCiD logo; ; ; ;
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Bio-Inspired Solar Fuel Production (BISfuel)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1397163
DOE Contract Number:  
SC0001016
Resource Type:
Journal Article
Journal Name:
Dalton Transactions
Additional Journal Information:
Journal Volume: 46; Journal Issue: 13; Related Information: BISfuel partners with Arizona State University.; Journal ID: ISSN 1477-9226
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Koepf, Matthieu, Bergkamp, Jesse J., Teillout, Anne-Lucie, Llansola-Portoles, Manuel J., Kodis, Gerdenis, Moore, Ana L., Gust, Devens, and Moore, Thomas A. Design of porphyrin-based ligands for the assembly of [d-block metal : calcium] bimetallic centers. United States: N. p., 2017. Web. doi:10.1039/c6dt04647a.
Koepf, Matthieu, Bergkamp, Jesse J., Teillout, Anne-Lucie, Llansola-Portoles, Manuel J., Kodis, Gerdenis, Moore, Ana L., Gust, Devens, & Moore, Thomas A. Design of porphyrin-based ligands for the assembly of [d-block metal : calcium] bimetallic centers. United States. doi:10.1039/c6dt04647a.
Koepf, Matthieu, Bergkamp, Jesse J., Teillout, Anne-Lucie, Llansola-Portoles, Manuel J., Kodis, Gerdenis, Moore, Ana L., Gust, Devens, and Moore, Thomas A. Sun . "Design of porphyrin-based ligands for the assembly of [d-block metal : calcium] bimetallic centers". United States. doi:10.1039/c6dt04647a.
@article{osti_1397163,
title = {Design of porphyrin-based ligands for the assembly of [d-block metal : calcium] bimetallic centers},
author = {Koepf, Matthieu and Bergkamp, Jesse J. and Teillout, Anne-Lucie and Llansola-Portoles, Manuel J. and Kodis, Gerdenis and Moore, Ana L. and Gust, Devens and Moore, Thomas A.},
abstractNote = {The association of different metals in stable, well-defined molecular assemblies remains a great challenge of supramolecular chemistry. In such constructs, the emergence of synergism, or cooperative effects between the different metal centers is particularly intriguing. These effects can lead to uncommon reactivity or remarkable physico-chemical properties that are not otherwise achievable. For example, the association of alkaline or alkaline-earth cations and transition metals is pivotal for the activity of several biomolecules and human-made catalysts that carry out fundamental redox transformations (water oxidation, nitrogen reduction, water–gas shift reaction, etc.). In many cases the precise nature of the interactions between the alkaline-earth cations and the redox-active transition metals remains elusive due to the difficulty of building stable molecular heterometallic assemblies that associate transition metals and alkaline or alkaline-earth cations in a controlled way. In this work we present the rational design of porphyrin-based ligands possessing a second binding site for alkaline-earth cations above the porphyrin macrocycle primary complexation site. We demonstrate that by using a combination of crown ether and carboxylic acid substituents suitably positioned on the periphery of the porphyrin, bitopic ligands can be obtained. The binding of calcium, a typical alkaline-earth cation, by the newly prepared ligands has been studied in detail and we show that a moderately large binding constant can be achieved in protic media using ligands that possess some degree of structural flexibility. The formation of Zn–Ca assemblies discussed in this work is viewed as a stepping stone towards the assembly of well defined molecular transition metal-alkaline earth bimetallic centers using a versatile organic scaffold.},
doi = {10.1039/c6dt04647a},
journal = {Dalton Transactions},
issn = {1477-9226},
number = 13,
volume = 46,
place = {United States},
year = {2017},
month = {1}
}

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