Heteromultimetallic compounds based on polyfunctional carboxylate linkers

Khairil Jantan; James McArdle; Lorenzo Mognon; Valentina Fiorini; Luke Alexander Wilkinson; Andrew White; Stefano Stagni; Nicholas Long; James Wilton-Ely

doi:10.1039/C8NJ06455E

Heteromultimetallic compounds based on polyfunctional carboxylate linkers

Khairil Jantan, James McArdle, Lorenzo Mognon, Valentina Fiorini, Luke Alexander Wilkinson, Andrew White, Stefano Stagni, Nicholas Long, James Wilton-Ely

Chemistry

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

Abstract

A series of homo- and hetero-nuclear, bi- and trimetallic compounds are accessible using polyfunctional linkers with carboxylic acid and alkynyl or pyridyl donor combinations. This versatile approach affords reaction at a specific donor site in each case, to accommodate both ruthenium(II) or osmium(II) units and also rhenium and gold centres. Due to the orientation of the nitrogen donors of the bipyridyl moiety in 2,2′-bipyridine-4,4′-dicarboxylic acid, the metal addition must be performed in a certain sequence due to steric considerations. One example was investigated crystallographically to add to the spectroscopic and analytical characterisation performed for all complexes. Photophysical investigations reveal the effect of incorporating second or third row transition metal centres. This approach was expanded through the use of a linker bearing both carboxylic acid and alkynyl functionalities, 1,1′-ethynylferrocene carboxylic acid. This allows initial coordination of the carboxylate donors to be followed by the formation of either an acetylide or a vinyl bridge to another metal, providing access to heterotrimetallic (FeRuOs and FeRuAu) compounds as well as a heteroheptametallic Fe3Ru2Au2 example. Preliminary electrochemical studies were performed on the latter compound.

Original language	English
Pages (from-to)	3199-3207
Journal	NEW JOURNAL OF CHEMISTRY
Volume	43
Issue number	7
Early online date	22 Jan 2019
DOIs	https://doi.org/10.1039/C8NJ06455E
Publication status	Published - 21 Feb 2019

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10.1039/C8NJ06455E

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title = "Heteromultimetallic compounds based on polyfunctional carboxylate linkers",

abstract = "A series of homo- and hetero-nuclear, bi- and trimetallic compounds are accessible using polyfunctional linkers with carboxylic acid and alkynyl or pyridyl donor combinations. This versatile approach affords reaction at a specific donor site in each case, to accommodate both ruthenium(II) or osmium(II) units and also rhenium and gold centres. Due to the orientation of the nitrogen donors of the bipyridyl moiety in 2,2′-bipyridine-4,4′-dicarboxylic acid, the metal addition must be performed in a certain sequence due to steric considerations. One example was investigated crystallographically to add to the spectroscopic and analytical characterisation performed for all complexes. Photophysical investigations reveal the effect of incorporating second or third row transition metal centres. This approach was expanded through the use of a linker bearing both carboxylic acid and alkynyl functionalities, 1,1′-ethynylferrocene carboxylic acid. This allows initial coordination of the carboxylate donors to be followed by the formation of either an acetylide or a vinyl bridge to another metal, providing access to heterotrimetallic (FeRuOs and FeRuAu) compounds as well as a heteroheptametallic Fe3Ru2Au2 example. Preliminary electrochemical studies were performed on the latter compound.",

author = "Khairil Jantan and James McArdle and Lorenzo Mognon and Valentina Fiorini and Wilkinson, {Luke Alexander} and Andrew White and Stefano Stagni and Nicholas Long and James Wilton-Ely",

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AU - Jantan, Khairil

AU - McArdle, James

AU - Mognon, Lorenzo

AU - Fiorini, Valentina

AU - Wilkinson, Luke Alexander

AU - White, Andrew

AU - Stagni, Stefano

AU - Long, Nicholas

AU - Wilton-Ely, James

PY - 2019/2/21

Y1 - 2019/2/21

N2 - A series of homo- and hetero-nuclear, bi- and trimetallic compounds are accessible using polyfunctional linkers with carboxylic acid and alkynyl or pyridyl donor combinations. This versatile approach affords reaction at a specific donor site in each case, to accommodate both ruthenium(II) or osmium(II) units and also rhenium and gold centres. Due to the orientation of the nitrogen donors of the bipyridyl moiety in 2,2′-bipyridine-4,4′-dicarboxylic acid, the metal addition must be performed in a certain sequence due to steric considerations. One example was investigated crystallographically to add to the spectroscopic and analytical characterisation performed for all complexes. Photophysical investigations reveal the effect of incorporating second or third row transition metal centres. This approach was expanded through the use of a linker bearing both carboxylic acid and alkynyl functionalities, 1,1′-ethynylferrocene carboxylic acid. This allows initial coordination of the carboxylate donors to be followed by the formation of either an acetylide or a vinyl bridge to another metal, providing access to heterotrimetallic (FeRuOs and FeRuAu) compounds as well as a heteroheptametallic Fe3Ru2Au2 example. Preliminary electrochemical studies were performed on the latter compound.

AB - A series of homo- and hetero-nuclear, bi- and trimetallic compounds are accessible using polyfunctional linkers with carboxylic acid and alkynyl or pyridyl donor combinations. This versatile approach affords reaction at a specific donor site in each case, to accommodate both ruthenium(II) or osmium(II) units and also rhenium and gold centres. Due to the orientation of the nitrogen donors of the bipyridyl moiety in 2,2′-bipyridine-4,4′-dicarboxylic acid, the metal addition must be performed in a certain sequence due to steric considerations. One example was investigated crystallographically to add to the spectroscopic and analytical characterisation performed for all complexes. Photophysical investigations reveal the effect of incorporating second or third row transition metal centres. This approach was expanded through the use of a linker bearing both carboxylic acid and alkynyl functionalities, 1,1′-ethynylferrocene carboxylic acid. This allows initial coordination of the carboxylate donors to be followed by the formation of either an acetylide or a vinyl bridge to another metal, providing access to heterotrimetallic (FeRuOs and FeRuAu) compounds as well as a heteroheptametallic Fe3Ru2Au2 example. Preliminary electrochemical studies were performed on the latter compound.

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DO - 10.1039/C8NJ06455E

M3 - Article

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JO - NEW JOURNAL OF CHEMISTRY

JF - NEW JOURNAL OF CHEMISTRY

SN - 1144-0546

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ER -

Heteromultimetallic compounds based on polyfunctional carboxylate linkers

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