Heteromultimetallic compounds based on polyfunctional carboxylate linkers

TY - JOUR

T1 - Heteromultimetallic compounds based on polyfunctional carboxylate linkers

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.

UR - https://spiral.imperial.ac.uk/handle/10044/1/66695

U2 - 10.1039/C8NJ06455E

DO - 10.1039/C8NJ06455E

M3 - Article

SN - 1144-0546

VL - 43

SP - 3199

EP - 3207

JO - NEW JOURNAL OF CHEMISTRY

JF - NEW JOURNAL OF CHEMISTRY

IS - 7

ER -