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

doi:10.1039/b919282d

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 journal › Article › peer-review

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.

Original language	English
Pages (from-to)	1979-1984
Number of pages	6
Journal	Dalton Transactions
Volume	39
Issue number	8
Early online date	13 Jan 2010
DOIs	https://doi.org/10.1039/b919282d
Publication status	Published - 28 Feb 2010
Externally published	Yes

Access to Document

10.1039/b919282dLicence: Unspecified

Cite this

Alberding, B. G., Barybin, M. V., Chisholm, M. H., Gustafson, T. L., Reed, C. R., Robinson, R. E., Patmore, N. J., 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, 39(8), 1979-1984. https://doi.org/10.1039/b919282d

@article{bdbeb299787444c9aaad38b30e244cc9,

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

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.",

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

year = "2010",

month = feb,

day = "28",

doi = "10.1039/b919282d",

language = "English",

volume = "39",

pages = "1979--1984",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "8",

}

TY - JOUR

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.

UR - http://www.scopus.com/inward/record.url?scp=76749133140&partnerID=8YFLogxK

U2 - 10.1039/b919282d

DO - 10.1039/b919282d

M3 - Article

AN - SCOPUS:76749133140

VL - 39

SP - 1979

EP - 1984

JO - Dalton Transactions

JF - Dalton Transactions

SN - 1477-9226

IS - 8

ER -

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

Abstract

Access to Document

Other files and links

Fingerprint

Cite this