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Luminescence properties of heterodinuclear Pt–Eu complexes from unusual nonadentate ligandsElectronic supplementary information (ESI) available (8 pages): Minimum energy conformation for the [(tpy)PtL1]+system obtained from B3LYP/6-31G(d)/LanL2DZ calculations in vacuo; calculated UV-Vis absorption spectra of the species formed upon titration of Na3[(tpy)PtL1] by Eu(ClO4)3in CH2Cl2–TFA and evolution of the concentrations of the species; UV-Vis spectrophotometric titration of Na3[(tpy)PtL2] by La(OTf)3in CH2Cl2–TFA (Fig. S1–S5). Cartesian coordinates of the optimized structure of [(tpy)PtL1]+and of the lowest-energy triplet state of [(tpy)PtL1]+(Table S1 and S2). See DOI: 10.1039/b903522b

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Title: Luminescence properties of heterodinuclear Pt–Eu complexes from unusual nonadentate ligandsElectronic supplementary information (ESI) available (8 pages): Minimum energy conformation for the [(tpy)PtL1]+system obtained from B3LYP/6-31G(d)/LanL2DZ calculations in vacuo; calculated UV-Vis absorption spectra of the species formed upon titration of Na3[(tpy)PtL1] by Eu(ClO4)3in CH2Cl2–TFA and evolution of the concentrations of the species; UV-Vis spectrophotometric titration of Na3[(tpy)PtL2] by La(OTf)3in CH2Cl2–TFA (Fig. S1–S5). Cartesian coordinates of the optimized structure of [(tpy)PtL1]+and of the lowest-energy triplet state of [(tpy)PtL1]+(Table S1 and S2). See DOI: 10.1039/b903522b
Authors: Kadjane, Pascal1, Platas-Iglesias, Carlos2, Ziessel, Raymond1, Charbonnière, Loïc J.1
Source: Dalton Transactions: An International Journal of Inorganic Chemistry. Jul2009, Vol. 2009 Issue 29, p5688-5700. 13p.
Subjects: Metal complexes, Luminescence, Ligands (Chemistry), Esters, Complex compounds synthesis, Acetates, Hydrolysis, Density functionals
Abstract: The synthesis of ligand L1, based on the tetramethyl ester of [4′-ethynyl-(6,6″-bis(aminomethyl))-2,2′:6′,2″-terpyridine]tetrakisacetate, and its acidic form L2, are described. Using a Cu-assisted coupling reaction, L1was connected to the Pt atom of a [(tpy)Pt] precursor (tpy = 2,2′:6′,2″-terpyridine) to afford the [(tpy)PtL1](BF4) metallosynthon, from which a hydrolysis reaction gave Na3[(tpy)PtL2]. The photophysical properties of the metallosynthons were studied by means of absorption and steady state emission spectroscopic techniques in various solvents, which revealed a dramatic impact of the solvent polarity. DFT and TDDFT calculations (B3LYP) were used to investigate the absorption and emission properties of the [(tpy)PtL1]+system both in vacuoand in different solvents. Spectrophotometric titrations of [(tpy)PtL1]+with EuCl3·6H2O in acetonitrile revealed the formation of complicated mixtures of complexes with different [(tpyPtL1)xEuy] stoichiometries, all of which display the typical EuIIIcentred luminescence upon excitation into the Pt centred 1MLCT absorption band. The energy transfer from the Pt subunit of [(tpy)PtL2]3−to EuIIIis inefficient in polar solvents, but it is restored in a TFA–CH2Cl2mixture, together with the observation of a new emission band at 684 nm, likely arising from a charge transfer process involving reduction of EuIII. [ABSTRACT FROM AUTHOR]
Copyright of Dalton Transactions: An International Journal of Inorganic Chemistry is the property of Royal Society of Chemistry 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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  Data: Luminescence properties of heterodinuclear Pt–Eu complexes from unusual nonadentate ligandsElectronic supplementary information (ESI) available (8 pages): Minimum energy conformation for the [(tpy)PtL1]+system obtained from B3LYP/6-31G(d)/LanL2DZ calculations in vacuo; calculated UV-Vis absorption spectra of the species formed upon titration of Na3[(tpy)PtL1] by Eu(ClO4)3in CH2Cl2–TFA and evolution of the concentrations of the species; UV-Vis spectrophotometric titration of Na3[(tpy)PtL2] by La(OTf)3in CH2Cl2–TFA (Fig. S1–S5). Cartesian coordinates of the optimized structure of [(tpy)PtL1]+and of the lowest-energy triplet state of [(tpy)PtL1]+(Table S1 and S2). See DOI: 10.1039/b903522b
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  Data: The synthesis of ligand L1, based on the tetramethyl ester of [4′-ethynyl-(6,6″-bis(aminomethyl))-2,2′:6′,2″-terpyridine]tetrakisacetate, and its acidic form L2, are described. Using a Cu-assisted coupling reaction, L1was connected to the Pt atom of a [(tpy)Pt] precursor (tpy = 2,2′:6′,2″-terpyridine) to afford the [(tpy)PtL1](BF4) metallosynthon, from which a hydrolysis reaction gave Na3[(tpy)PtL2]. The photophysical properties of the metallosynthons were studied by means of absorption and steady state emission spectroscopic techniques in various solvents, which revealed a dramatic impact of the solvent polarity. DFT and TDDFT calculations (B3LYP) were used to investigate the absorption and emission properties of the [(tpy)PtL1]+system both in vacuoand in different solvents. Spectrophotometric titrations of [(tpy)PtL1]+with EuCl3·6H2O in acetonitrile revealed the formation of complicated mixtures of complexes with different [(tpyPtL1)xEuy] stoichiometries, all of which display the typical EuIIIcentred luminescence upon excitation into the Pt centred 1MLCT absorption band. The energy transfer from the Pt subunit of [(tpy)PtL2]3−to EuIIIis inefficient in polar solvents, but it is restored in a TFA–CH2Cl2mixture, together with the observation of a new emission band at 684 nm, likely arising from a charge transfer process involving reduction of EuIII. [ABSTRACT FROM AUTHOR]
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  Data: <i>Copyright of Dalton Transactions: An International Journal of Inorganic Chemistry is the property of Royal Society of Chemistry 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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        Value: 10.1039/b903522b
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        Text: English
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        PageCount: 13
        StartPage: 5688
    Subjects:
      – SubjectFull: Metal complexes
        Type: general
      – SubjectFull: Luminescence
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      – SubjectFull: Ligands (Chemistry)
        Type: general
      – SubjectFull: Esters
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      – SubjectFull: Complex compounds synthesis
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      – SubjectFull: Acetates
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      – SubjectFull: Hydrolysis
        Type: general
      – SubjectFull: Density functionals
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      – TitleFull: Luminescence properties of heterodinuclear Pt–Eu complexes from unusual nonadentate ligandsElectronic supplementary information (ESI) available (8 pages): Minimum energy conformation for the [(tpy)PtL1]+system obtained from B3LYP/6-31G(d)/LanL2DZ calculations in vacuo; calculated UV-Vis absorption spectra of the species formed upon titration of Na3[(tpy)PtL1] by Eu(ClO4)3in CH2Cl2–TFA and evolution of the concentrations of the species; UV-Vis spectrophotometric titration of Na3[(tpy)PtL2] by La(OTf)3in CH2Cl2–TFA (Fig. S1–S5). Cartesian coordinates of the optimized structure of [(tpy)PtL1]+and of the lowest-energy triplet state of [(tpy)PtL1]+(Table S1 and S2). See DOI: 10.1039/b903522b
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              Text: Jul2009
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