Molecular, electronic structure and spectroscopic properties of MM quadruply bonded units supported by trans-6-carboethoxy-2-carboxylatoazulene ligands

Brian G. Alberding, Mikhail V. Barybin, Malcolm H. Chisholm, Terry L. Gustafson, Carly R. Reed, Randall E. Robinson, Nathan J. Patmore, Namrata Singh, Claudia Turro

Research output: Contribution to journalArticle

12 Citations (Scopus)

Abstract

The reaction between M2(TiPB)4 (M = Mo, W) where TiPB = 2,4,6-triisopropylbenzoate and 6-carboethoxy-2-azulenecarboxylic acid (2 equiv.) in toluene leads to the formation of complexes M2(TiPB) 2(6-carboethoxy-2-azulenecarboxylate)2. Compound I (M = Mo) is blue and compound II (M = W) is green. Both are air sensitive, hydrocarbon soluble species that gave the corresponding molecular ions in their mass spectra (MALDI-TOF). They show metal based oxidations and ligand based reductions. Electronic structure calculations (DFT and time dependent DFT) indicate that the two azulene carboxylate π systems are coupled by their interactions with the M2δ orbitals. Their intense colors arise from M2δ to azulene π* electronic transitions. While compound I exhibits weak emission at ∼ 900 nm, no emission has been detected for II. Both I and II have been studied by fs and ns transient absorption spectroscopy. The X-ray analysis of the molecular structure of II in the solid state confirmed the paddlewheel nature of its W2(O2C) 4 core and the trans orientation of the ligands.

LanguageEnglish
Pages1979-1984
Number of pages6
JournalDalton Transactions
Volume39
Issue number8
Early online date13 Jan 2010
DOIs
Publication statusPublished - 28 Feb 2010
Externally publishedYes

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Molecular electronics
Discrete Fourier transforms
Electronic structure
Ligands
X ray analysis
Toluene
Hydrocarbons
Absorption spectroscopy
Molecular structure
Metals
Ions
Color
Oxidation
Acids
Air
azulene
M-II compound

Cite this

Alberding, B. G., Barybin, M. V., Chisholm, M. H., Gustafson, T. L., Reed, C. R., Robinson, R. E., ... Turro, C. (2010). Molecular, electronic structure and spectroscopic properties of MM quadruply bonded units supported by trans-6-carboethoxy-2-carboxylatoazulene ligands. Dalton Transactions, 39(8), 1979-1984. https://doi.org/10.1039/b919282d
Alberding, Brian G. ; Barybin, Mikhail V. ; Chisholm, Malcolm H. ; Gustafson, Terry L. ; Reed, Carly R. ; Robinson, Randall E. ; Patmore, Nathan J. ; Singh, Namrata ; Turro, Claudia. / Molecular, electronic structure and spectroscopic properties of MM quadruply bonded units supported by trans-6-carboethoxy-2-carboxylatoazulene ligands. In: Dalton Transactions. 2010 ; Vol. 39, No. 8. pp. 1979-1984.
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abstract = "The reaction between M2(TiPB)4 (M = Mo, W) where TiPB = 2,4,6-triisopropylbenzoate and 6-carboethoxy-2-azulenecarboxylic acid (2 equiv.) in toluene leads to the formation of complexes M2(TiPB) 2(6-carboethoxy-2-azulenecarboxylate)2. Compound I (M = Mo) is blue and compound II (M = W) is green. Both are air sensitive, hydrocarbon soluble species that gave the corresponding molecular ions in their mass spectra (MALDI-TOF). They show metal based oxidations and ligand based reductions. Electronic structure calculations (DFT and time dependent DFT) indicate that the two azulene carboxylate π systems are coupled by their interactions with the M2δ orbitals. Their intense colors arise from M2δ to azulene π* electronic transitions. While compound I exhibits weak emission at ∼ 900 nm, no emission has been detected for II. Both I and II have been studied by fs and ns transient absorption spectroscopy. The X-ray analysis of the molecular structure of II in the solid state confirmed the paddlewheel nature of its W2(O2C) 4 core and the trans orientation of the ligands.",
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Alberding, BG, Barybin, MV, Chisholm, MH, Gustafson, TL, Reed, CR, Robinson, RE, Patmore, NJ, Singh, N & Turro, C 2010, 'Molecular, electronic structure and spectroscopic properties of MM quadruply bonded units supported by trans-6-carboethoxy-2-carboxylatoazulene ligands', Dalton Transactions, vol. 39, no. 8, pp. 1979-1984. https://doi.org/10.1039/b919282d

Molecular, electronic structure and spectroscopic properties of MM quadruply bonded units supported by trans-6-carboethoxy-2-carboxylatoazulene ligands. / Alberding, Brian G.; Barybin, Mikhail V.; Chisholm, Malcolm H.; Gustafson, Terry L.; Reed, Carly R.; Robinson, Randall E.; Patmore, Nathan J.; Singh, Namrata; Turro, Claudia.

In: Dalton Transactions, Vol. 39, No. 8, 28.02.2010, p. 1979-1984.

Research output: Contribution to journalArticle

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T1 - Molecular, electronic structure and spectroscopic properties of MM quadruply bonded units supported by trans-6-carboethoxy-2-carboxylatoazulene ligands

AU - Alberding, Brian G.

AU - Barybin, Mikhail V.

AU - Chisholm, Malcolm H.

AU - Gustafson, Terry L.

AU - Reed, Carly R.

AU - Robinson, Randall E.

AU - Patmore, Nathan J.

AU - Singh, Namrata

AU - Turro, Claudia

PY - 2010/2/28

Y1 - 2010/2/28

N2 - The reaction between M2(TiPB)4 (M = Mo, W) where TiPB = 2,4,6-triisopropylbenzoate and 6-carboethoxy-2-azulenecarboxylic acid (2 equiv.) in toluene leads to the formation of complexes M2(TiPB) 2(6-carboethoxy-2-azulenecarboxylate)2. Compound I (M = Mo) is blue and compound II (M = W) is green. Both are air sensitive, hydrocarbon soluble species that gave the corresponding molecular ions in their mass spectra (MALDI-TOF). They show metal based oxidations and ligand based reductions. Electronic structure calculations (DFT and time dependent DFT) indicate that the two azulene carboxylate π systems are coupled by their interactions with the M2δ orbitals. Their intense colors arise from M2δ to azulene π* electronic transitions. While compound I exhibits weak emission at ∼ 900 nm, no emission has been detected for II. Both I and II have been studied by fs and ns transient absorption spectroscopy. The X-ray analysis of the molecular structure of II in the solid state confirmed the paddlewheel nature of its W2(O2C) 4 core and the trans orientation of the ligands.

AB - The reaction between M2(TiPB)4 (M = Mo, W) where TiPB = 2,4,6-triisopropylbenzoate and 6-carboethoxy-2-azulenecarboxylic acid (2 equiv.) in toluene leads to the formation of complexes M2(TiPB) 2(6-carboethoxy-2-azulenecarboxylate)2. Compound I (M = Mo) is blue and compound II (M = W) is green. Both are air sensitive, hydrocarbon soluble species that gave the corresponding molecular ions in their mass spectra (MALDI-TOF). They show metal based oxidations and ligand based reductions. Electronic structure calculations (DFT and time dependent DFT) indicate that the two azulene carboxylate π systems are coupled by their interactions with the M2δ orbitals. Their intense colors arise from M2δ to azulene π* electronic transitions. While compound I exhibits weak emission at ∼ 900 nm, no emission has been detected for II. Both I and II have been studied by fs and ns transient absorption spectroscopy. The X-ray analysis of the molecular structure of II in the solid state confirmed the paddlewheel nature of its W2(O2C) 4 core and the trans orientation of the ligands.

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DO - 10.1039/b919282d

M3 - Article

VL - 39

SP - 1979

EP - 1984

JO - Dalton Transactions

T2 - Dalton Transactions

JF - Dalton Transactions

SN - 1477-9226

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