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DFT/TD-DFT analysis of structural, electrochemical and optical data from mononuclear osmium and heterobinuclear osmium–ruthenium alkynyl complexes.

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Title: DFT/TD-DFT analysis of structural, electrochemical and optical data from mononuclear osmium and heterobinuclear osmium–ruthenium alkynyl complexes.
Authors: Kulasekera, Erandi1, Petrie, Simon1, Stranger, Rob1 Rob.Stranger@anu.edu.au, Cifuentes, Marie P.1, Humphrey, Mark G.1 Mark.Humphrey@anu.edu.au
Source: Journal of Organometallic Chemistry. Dec2013, Vol. 748, p21-28. 8p.
Subjects: Osmium, Ruthenium, Molecular structure, Metal-organic frameworks, Electrochemistry, Density functional theory, Light absorption, Hydrogen bonding
Abstract: Abstract: Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations of the molecular structures, optical absorption spectra, and spectroelectrochemical behavior of the complexes trans-[Os(C CC6H4-4-C CH)Cl(dppe)2] (1), trans,trans-[(dppe)2ClOs(C CC6H4-4-C C)RuCl(dppe)2] (2), trans,trans-[(dppe)2ClOs(C CC6H4-4-C C)Ru(C CC6H4-4-C CH)(dppe)2] (3), trans-[Os(C CC6H4-4-C CC6H4-4-C CH)Cl(dppe)2] (4), and trans,trans-[(dppe)2ClOs(C CC6H4-4-C CC6H4-4-C C)RuCl(dppe)2] (5) were undertaken. The calculated structures for the mononuclear osmium complexes 1 and 4 are in good agreement with the X-ray data, a 0.3 Å lengthening of the Os–Cl bond in proceeding from the theoretical model for 4 to the experimental structure being rationalized on the basis of intermolecular H-bonding effects for the latter. For the non-oxidized forms of these five complexes, the lowest-energy bands are assigned to MLCT transitions along the main molecular axis from orbitals with mostly Os d, Cl p and alkynyl character to orbitals on the alkynyl backbone. The calculations indicate that the heterobimetallic complexes 2, 3 and 5 do not undergo metal-centred oxidation. Instead, the electron is lost from an orbital that is delocalized across the bridge and both metal centres. The mono-oxidized and di-oxidized species show new bands in the low-energy region arising from LMCT transitions, primarily corresponding to transitions from the dppe ligands to metal- and alkynyl-based orbitals. For structures involving two or more phenylethynyl units along the main axis of the molecule, the TD-DFT calculations are in significantly better agreement with the observed spectra when the phenyl groups adopt a non-coplanar conformation. [Copyright &y& Elsevier]
Copyright of Journal of Organometallic Chemistry is the property of Elsevier B.V. and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
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  Label: Title
  Group: Ti
  Data: DFT/TD-DFT analysis of structural, electrochemical and optical data from mononuclear osmium and heterobinuclear osmium–ruthenium alkynyl complexes.
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  Data: <searchLink fieldCode="AR" term="%22Kulasekera%2C+Erandi%22">Kulasekera, Erandi</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Petrie%2C+Simon%22">Petrie, Simon</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Stranger%2C+Rob%22">Stranger, Rob</searchLink><relatesTo>1</relatesTo><i> Rob.Stranger@anu.edu.au</i><br /><searchLink fieldCode="AR" term="%22Cifuentes%2C+Marie+P%2E%22">Cifuentes, Marie P.</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Humphrey%2C+Mark+G%2E%22">Humphrey, Mark G.</searchLink><relatesTo>1</relatesTo><i> Mark.Humphrey@anu.edu.au</i>
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  Data: <searchLink fieldCode="JN" term="%22Journal+of+Organometallic+Chemistry%22">Journal of Organometallic Chemistry</searchLink>. Dec2013, Vol. 748, p21-28. 8p.
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  Label: Subjects
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  Data: <searchLink fieldCode="DE" term="%22Osmium%22">Osmium</searchLink><br /><searchLink fieldCode="DE" term="%22Ruthenium%22">Ruthenium</searchLink><br /><searchLink fieldCode="DE" term="%22Molecular+structure%22">Molecular structure</searchLink><br /><searchLink fieldCode="DE" term="%22Metal-organic+frameworks%22">Metal-organic frameworks</searchLink><br /><searchLink fieldCode="DE" term="%22Electrochemistry%22">Electrochemistry</searchLink><br /><searchLink fieldCode="DE" term="%22Density+functional+theory%22">Density functional theory</searchLink><br /><searchLink fieldCode="DE" term="%22Light+absorption%22">Light absorption</searchLink><br /><searchLink fieldCode="DE" term="%22Hydrogen+bonding%22">Hydrogen bonding</searchLink>
– Name: Abstract
  Label: Abstract
  Group: Ab
  Data: Abstract: Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations of the molecular structures, optical absorption spectra, and spectroelectrochemical behavior of the complexes trans-[Os(C CC6H4-4-C CH)Cl(dppe)2] (1), trans,trans-[(dppe)2ClOs(C CC6H4-4-C C)RuCl(dppe)2] (2), trans,trans-[(dppe)2ClOs(C CC6H4-4-C C)Ru(C CC6H4-4-C CH)(dppe)2] (3), trans-[Os(C CC6H4-4-C CC6H4-4-C CH)Cl(dppe)2] (4), and trans,trans-[(dppe)2ClOs(C CC6H4-4-C CC6H4-4-C C)RuCl(dppe)2] (5) were undertaken. The calculated structures for the mononuclear osmium complexes 1 and 4 are in good agreement with the X-ray data, a 0.3 Å lengthening of the Os–Cl bond in proceeding from the theoretical model for 4 to the experimental structure being rationalized on the basis of intermolecular H-bonding effects for the latter. For the non-oxidized forms of these five complexes, the lowest-energy bands are assigned to MLCT transitions along the main molecular axis from orbitals with mostly Os d, Cl p and alkynyl character to orbitals on the alkynyl backbone. The calculations indicate that the heterobimetallic complexes 2, 3 and 5 do not undergo metal-centred oxidation. Instead, the electron is lost from an orbital that is delocalized across the bridge and both metal centres. The mono-oxidized and di-oxidized species show new bands in the low-energy region arising from LMCT transitions, primarily corresponding to transitions from the dppe ligands to metal- and alkynyl-based orbitals. For structures involving two or more phenylethynyl units along the main axis of the molecule, the TD-DFT calculations are in significantly better agreement with the observed spectra when the phenyl groups adopt a non-coplanar conformation. [Copyright &y& Elsevier]
– Name: AbstractSuppliedCopyright
  Label:
  Group: Ab
  Data: <i>Copyright of Journal of Organometallic Chemistry is the property of Elsevier B.V. and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
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RecordInfo BibRecord:
  BibEntity:
    Identifiers:
      – Type: doi
        Value: 10.1016/j.jorganchem.2013.07.010
    Languages:
      – Code: eng
        Text: English
    PhysicalDescription:
      Pagination:
        PageCount: 8
        StartPage: 21
    Subjects:
      – SubjectFull: Osmium
        Type: general
      – SubjectFull: Ruthenium
        Type: general
      – SubjectFull: Molecular structure
        Type: general
      – SubjectFull: Metal-organic frameworks
        Type: general
      – SubjectFull: Electrochemistry
        Type: general
      – SubjectFull: Density functional theory
        Type: general
      – SubjectFull: Light absorption
        Type: general
      – SubjectFull: Hydrogen bonding
        Type: general
    Titles:
      – TitleFull: DFT/TD-DFT analysis of structural, electrochemical and optical data from mononuclear osmium and heterobinuclear osmium–ruthenium alkynyl complexes.
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            NameFull: Kulasekera, Erandi
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            NameFull: Petrie, Simon
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            NameFull: Stranger, Rob
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            NameFull: Cifuentes, Marie P.
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            NameFull: Humphrey, Mark G.
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            – D: 15
              M: 12
              Text: Dec2013
              Type: published
              Y: 2013
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              Value: 748
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            – TitleFull: Journal of Organometallic Chemistry
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