Hydrogen Bonding and Electron Transfer between Dimetal Paddlewheel Compounds Containing Pendant 2-Pyridone Functional Groups

Luke A. Wilkinson, Laura McNeill, Paul A. Scattergood, Nathan J. Patmore

Research output: Contribution to journalArticle

20 Citations (Scopus)

Abstract

The compounds M2(TiPB)3(HDON) (TiPB = 2,4,6-triisopropylbenzoic acid; H2DON = 2,7-dihdroxy-1,8- napthyridine; M = Mo (1a) or W (1b)) and Mo2(TiPB)2(O 2CCH2Cl)(HDON) (1c) which contain a pendant 2-pyridone functional group have been prepared. These compounds are capable of forming self-complementary hydrogen bonds, resulting in the formation of "dimers of dimers" ([1a-c]2) in CH2Cl2 solutions. Electrochemical studies reveal two successive one-electron redox processes for [1a-c]2 in CH2Cl2 solutions that correspond to successive oxidations of the dimetal core, indicating stabilization of the mixed-valence state. Only small changes in the value of Kc are observed upon changing the ancillary ligand or metal, implying that proton coupled mixed valency is responsible for the stabilization. Dimethylsulfoxide (DMSO) disrupts the hydrogen bonding interactions in these compounds, and a single oxidation process is observed in DMSO which shifts to lower potential as the number of HDON ligands increases. Further substitution of carboxylate ligands with HDON leads to the formation of Mo2(TiPB) 2(HDON)2 (2) and Mo2(HDON)4 (3), which adopt trans-1,1 and cis-2,2 regioisomers in the solid-state. 1H NMR spectroscopy indicates that there are at least two regioisomers present in solution for both compounds. The lowest energy transition in the electronic absorption spectra of these compounds corresponds to a M2-δ → HDON-π* transition. The electrochemical, spectroscopic and structural results were rationalized with the aid of density functional theory (DFT) calculations.

LanguageEnglish
Pages9683-9691
Number of pages9
JournalInorganic Chemistry
Volume52
Issue number16
Early online date19 Aug 2013
DOIs
Publication statusPublished - 19 Aug 2013
Externally publishedYes

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Functional groups
Hydrogen bonds
electron transfer
Ligands
Dimethyl Sulfoxide
Dimers
ligands
Electrons
hydrogen
Stabilization
stabilization
dimers
Oxidation
oxidation
Electron transitions
electronic spectra
carboxylates
Nuclear magnetic resonance spectroscopy
Density functional theory
Protons

Cite this

@article{4b91df900f3647bb80543fb0e847eb91,
title = "Hydrogen Bonding and Electron Transfer between Dimetal Paddlewheel Compounds Containing Pendant 2-Pyridone Functional Groups",
abstract = "The compounds M2(TiPB)3(HDON) (TiPB = 2,4,6-triisopropylbenzoic acid; H2DON = 2,7-dihdroxy-1,8- napthyridine; M = Mo (1a) or W (1b)) and Mo2(TiPB)2(O 2CCH2Cl)(HDON) (1c) which contain a pendant 2-pyridone functional group have been prepared. These compounds are capable of forming self-complementary hydrogen bonds, resulting in the formation of {"}dimers of dimers{"} ([1a-c]2) in CH2Cl2 solutions. Electrochemical studies reveal two successive one-electron redox processes for [1a-c]2 in CH2Cl2 solutions that correspond to successive oxidations of the dimetal core, indicating stabilization of the mixed-valence state. Only small changes in the value of Kc are observed upon changing the ancillary ligand or metal, implying that proton coupled mixed valency is responsible for the stabilization. Dimethylsulfoxide (DMSO) disrupts the hydrogen bonding interactions in these compounds, and a single oxidation process is observed in DMSO which shifts to lower potential as the number of HDON ligands increases. Further substitution of carboxylate ligands with HDON leads to the formation of Mo2(TiPB) 2(HDON)2 (2) and Mo2(HDON)4 (3), which adopt trans-1,1 and cis-2,2 regioisomers in the solid-state. 1H NMR spectroscopy indicates that there are at least two regioisomers present in solution for both compounds. The lowest energy transition in the electronic absorption spectra of these compounds corresponds to a M2-δ → HDON-π* transition. The electrochemical, spectroscopic and structural results were rationalized with the aid of density functional theory (DFT) calculations.",
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Hydrogen Bonding and Electron Transfer between Dimetal Paddlewheel Compounds Containing Pendant 2-Pyridone Functional Groups. / Wilkinson, Luke A.; McNeill, Laura; Scattergood, Paul A.; Patmore, Nathan J.

In: Inorganic Chemistry, Vol. 52, No. 16, 19.08.2013, p. 9683-9691.

Research output: Contribution to journalArticle

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T1 - Hydrogen Bonding and Electron Transfer between Dimetal Paddlewheel Compounds Containing Pendant 2-Pyridone Functional Groups

AU - Wilkinson, Luke A.

AU - McNeill, Laura

AU - Scattergood, Paul A.

AU - Patmore, Nathan J.

PY - 2013/8/19

Y1 - 2013/8/19

N2 - The compounds M2(TiPB)3(HDON) (TiPB = 2,4,6-triisopropylbenzoic acid; H2DON = 2,7-dihdroxy-1,8- napthyridine; M = Mo (1a) or W (1b)) and Mo2(TiPB)2(O 2CCH2Cl)(HDON) (1c) which contain a pendant 2-pyridone functional group have been prepared. These compounds are capable of forming self-complementary hydrogen bonds, resulting in the formation of "dimers of dimers" ([1a-c]2) in CH2Cl2 solutions. Electrochemical studies reveal two successive one-electron redox processes for [1a-c]2 in CH2Cl2 solutions that correspond to successive oxidations of the dimetal core, indicating stabilization of the mixed-valence state. Only small changes in the value of Kc are observed upon changing the ancillary ligand or metal, implying that proton coupled mixed valency is responsible for the stabilization. Dimethylsulfoxide (DMSO) disrupts the hydrogen bonding interactions in these compounds, and a single oxidation process is observed in DMSO which shifts to lower potential as the number of HDON ligands increases. Further substitution of carboxylate ligands with HDON leads to the formation of Mo2(TiPB) 2(HDON)2 (2) and Mo2(HDON)4 (3), which adopt trans-1,1 and cis-2,2 regioisomers in the solid-state. 1H NMR spectroscopy indicates that there are at least two regioisomers present in solution for both compounds. The lowest energy transition in the electronic absorption spectra of these compounds corresponds to a M2-δ → HDON-π* transition. The electrochemical, spectroscopic and structural results were rationalized with the aid of density functional theory (DFT) calculations.

AB - The compounds M2(TiPB)3(HDON) (TiPB = 2,4,6-triisopropylbenzoic acid; H2DON = 2,7-dihdroxy-1,8- napthyridine; M = Mo (1a) or W (1b)) and Mo2(TiPB)2(O 2CCH2Cl)(HDON) (1c) which contain a pendant 2-pyridone functional group have been prepared. These compounds are capable of forming self-complementary hydrogen bonds, resulting in the formation of "dimers of dimers" ([1a-c]2) in CH2Cl2 solutions. Electrochemical studies reveal two successive one-electron redox processes for [1a-c]2 in CH2Cl2 solutions that correspond to successive oxidations of the dimetal core, indicating stabilization of the mixed-valence state. Only small changes in the value of Kc are observed upon changing the ancillary ligand or metal, implying that proton coupled mixed valency is responsible for the stabilization. Dimethylsulfoxide (DMSO) disrupts the hydrogen bonding interactions in these compounds, and a single oxidation process is observed in DMSO which shifts to lower potential as the number of HDON ligands increases. Further substitution of carboxylate ligands with HDON leads to the formation of Mo2(TiPB) 2(HDON)2 (2) and Mo2(HDON)4 (3), which adopt trans-1,1 and cis-2,2 regioisomers in the solid-state. 1H NMR spectroscopy indicates that there are at least two regioisomers present in solution for both compounds. The lowest energy transition in the electronic absorption spectra of these compounds corresponds to a M2-δ → HDON-π* transition. The electrochemical, spectroscopic and structural results were rationalized with the aid of density functional theory (DFT) calculations.

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U2 - 10.1021/ic401555g

DO - 10.1021/ic401555g

M3 - Article

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T2 - Inorganic Chemistry

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SN - 0020-1669

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