Highly Efficient Visible-to-NIR Luminescence of Lanthanide(III) Complexes with Zwitterionic Ligands Bearing Charge-Transfer Character: Beyond Triplet Sensitization

Two zwitterionic‐type ligands featuring π–π* and intraligand charge‐transfer (ILCT) excited states, namely 1,1′‐(2,3,5,6‐tetramethyl‐1,4‐phenylene)bis(methylene)dipyridinium‐4‐olate (TMPBPO) and 1‐dodecylpyridin‐4(1 H)‐one (DOPO), have been prepared and applied to the assembly of lanthanide coordina...

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Published inChemistry : a European journal Vol. 22; no. 7; pp. 2440 - 2451
Main Authors Pan, Mei, Du, Bin-Bin, Zhu, Yi-Xuan, Yue, Mei-Qin, Wei, Zhang-Wen, Su, Cheng-Yong
Format Journal Article
LanguageEnglish
Published Germany Blackwell Publishing Ltd 12.02.2016
Wiley Subscription Services, Inc
Subjects
Charge transfer
Chemistry
Coordination compounds
Dysprosium
Energy levels
energy transfer
Excitation
Gadolinium
Lanthanides
Lanthanum
Ligands
Luminescence
Photoluminescence
Photons
Samarium
Solid solutions
Temperature dependence
Ternary systems
Tuning
White light
Zwitterions
energy transfer
zwitterions
luminescence
white light
charge transfer
lanthanides
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Abstract Two zwitterionic‐type ligands featuring π–π* and intraligand charge‐transfer (ILCT) excited states, namely 1,1′‐(2,3,5,6‐tetramethyl‐1,4‐phenylene)bis(methylene)dipyridinium‐4‐olate (TMPBPO) and 1‐dodecylpyridin‐4(1 H)‐one (DOPO), have been prepared and applied to the assembly of lanthanide coordination complexes in an effort to understand the ligand‐direction effect on the structure of the Ln complexes and the ligand sensitization effect on the luminescence of the Ln complexes. Due to the wide‐band triplet states plus additional ILCT excitation states extending into lower energy levels, broadly and strongly sensitized photoluminescence of f→f transitions from various Ln3+ ions were observed to cover the visible to near‐infrared (NIR) regions. Among which, the Pr, Sm, Dy, and Tm complexes simultaneously display both strong visible and NIR emissions. Based on the isostructural feature of the Ln complexes, color tuning and single‐component white light was achieved by preparation of solid solutions of the ternary systems Gd‐Eu‐Tb (for TMPBPO) and La‐Eu‐Tb and La‐Dy‐Sm (for DOPO). Moreover, the visible and NIR luminescence lifetimes of the Ln complexes with the TMPBPO ligand were investigated from 77 to 298 K, revealing a strong temperature dependence of the Tm3+ (3H4) and Yb3+ (2F5/2) decay dynamics, which has not been explored before for their coordination complexes. Little light: Two new types of zwitterionic ligands have been designed that show broad sensitization from both triplet and ILCT states for the whole series of LnIII ions in both the visible and the NIR region (see figure), as well as single‐phase white‐light emission.
AbstractList Two zwitterionic‐type ligands featuring π–π* and intraligand charge‐transfer (ILCT) excited states, namely 1,1′‐(2,3,5,6‐tetramethyl‐1,4‐phenylene)bis(methylene)dipyridinium‐4‐olate (TMPBPO) and 1‐dodecylpyridin‐4(1 H)‐one (DOPO), have been prepared and applied to the assembly of lanthanide coordination complexes in an effort to understand the ligand‐direction effect on the structure of the Ln complexes and the ligand sensitization effect on the luminescence of the Ln complexes. Due to the wide‐band triplet states plus additional ILCT excitation states extending into lower energy levels, broadly and strongly sensitized photoluminescence of f→f transitions from various Ln3+ ions were observed to cover the visible to near‐infrared (NIR) regions. Among which, the Pr, Sm, Dy, and Tm complexes simultaneously display both strong visible and NIR emissions. Based on the isostructural feature of the Ln complexes, color tuning and single‐component white light was achieved by preparation of solid solutions of the ternary systems Gd‐Eu‐Tb (for TMPBPO) and La‐Eu‐Tb and La‐Dy‐Sm (for DOPO). Moreover, the visible and NIR luminescence lifetimes of the Ln complexes with the TMPBPO ligand were investigated from 77 to 298 K, revealing a strong temperature dependence of the Tm3+ (3H4) and Yb3+ (2F5/2) decay dynamics, which has not been explored before for their coordination complexes. Little light: Two new types of zwitterionic ligands have been designed that show broad sensitization from both triplet and ILCT states for the whole series of LnIII ions in both the visible and the NIR region (see figure), as well as single‐phase white‐light emission.
Two zwitterionic-type ligands featuring pi - pi * and intraligand charge-transfer (ILCT) excited states, namely 1,1'-(2,3,5,6-tetramethyl-1,4-phenylene)bis(methylene)dipyri dinium-4-olate (TMPBPO) and 1-dodecylpyridin-4(1H)-one (DOPO), have been prepared and applied to the assembly of lanthanide coordination complexes in an effort to understand the ligand-direction effect on the structure of the Ln complexes and the ligand sensitization effect on the luminescence of the Ln complexes. Due to the wide-band triplet states plus additional ILCT excitation states extending into lower energy levels, broadly and strongly sensitized photoluminescence of f arrow right f transitions from various Ln super(3+) ions were observed to cover the visible to near-infrared (NIR) regions. Among which, the Pr, Sm, Dy, and Tm complexes simultaneously display both strong visible and NIR emissions. Based on the isostructural feature of the Ln complexes, color tuning and single-component white light was achieved by preparation of solid solutions of the ternary systems Gd-Eu-Tb (for TMPBPO) and La-Eu-Tb and La-Dy-Sm (for DOPO). Moreover, the visible and NIR luminescence lifetimes of the Ln complexes with the TMPBPO ligand were investigated from 77 to 298K, revealing a strong temperature dependence of the Tm super(3+) ( super(3)H sub(4)) and Yb super(3+) ( super(2)F sub(5/2)) decay dynamics, which has not been explored before for their coordination complexes. Little light: Two new types of zwitterionic ligands have been designed that show broad sensitization from both triplet and ILCT states for the whole series of Ln super(III) ions in both the visible and the NIR region (see figure), as well as single-phase white-light emission.
Two zwitterionic‐type ligands featuring π–π* and intraligand charge‐transfer (ILCT) excited states, namely 1,1′‐(2,3,5,6‐tetramethyl‐1,4‐phenylene)bis(methylene)dipyridinium‐4‐olate (TMPBPO) and 1‐dodecylpyridin‐4(1 H)‐one (DOPO), have been prepared and applied to the assembly of lanthanide coordination complexes in an effort to understand the ligand‐direction effect on the structure of the Ln complexes and the ligand sensitization effect on the luminescence of the Ln complexes. Due to the wide‐band triplet states plus additional ILCT excitation states extending into lower energy levels, broadly and strongly sensitized photoluminescence of f→f transitions from various Ln3+ ions were observed to cover the visible to near‐infrared (NIR) regions. Among which, the Pr, Sm, Dy, and Tm complexes simultaneously display both strong visible and NIR emissions. Based on the isostructural feature of the Ln complexes, color tuning and single‐component white light was achieved by preparation of solid solutions of the ternary systems Gd‐Eu‐Tb (for TMPBPO) and La‐Eu‐Tb and La‐Dy‐Sm (for DOPO). Moreover, the visible and NIR luminescence lifetimes of the Ln complexes with the TMPBPO ligand were investigated from 77 to 298 K, revealing a strong temperature dependence of the Tm3+ (3H4) and Yb3+ (2F5/2) decay dynamics, which has not been explored before for their coordination complexes.
Two zwitterionic‐type ligands featuring π–π* and intraligand charge‐transfer (ILCT) excited states, namely 1,1′‐(2,3,5,6‐tetramethyl‐1,4‐phenylene)bis(methylene)dipyridinium‐4‐olate (TMPBPO) and 1‐dodecylpyridin‐4(1  H )‐one (DOPO), have been prepared and applied to the assembly of lanthanide coordination complexes in an effort to understand the ligand‐direction effect on the structure of the Ln complexes and the ligand sensitization effect on the luminescence of the Ln complexes. Due to the wide‐band triplet states plus additional ILCT excitation states extending into lower energy levels, broadly and strongly sensitized photoluminescence of f→f transitions from various Ln 3+ ions were observed to cover the visible to near‐infrared (NIR) regions. Among which, the Pr, Sm, Dy, and Tm complexes simultaneously display both strong visible and NIR emissions. Based on the isostructural feature of the Ln complexes, color tuning and single‐component white light was achieved by preparation of solid solutions of the ternary systems Gd‐Eu‐Tb (for TMPBPO) and La‐Eu‐Tb and La‐Dy‐Sm (for DOPO). Moreover, the visible and NIR luminescence lifetimes of the Ln complexes with the TMPBPO ligand were investigated from 77 to 298 K, revealing a strong temperature dependence of the Tm 3+ ( 3 H 4 ) and Yb 3+ ( 2 F 5/2 ) decay dynamics, which has not been explored before for their coordination complexes.
Two zwitterionic-type ligands featuring π-π* and intraligand charge-transfer (ILCT) excited states, namely 1,1'-(2,3,5,6-tetramethyl-1,4-phenylene)bis(methylene)dipyridinium-4-olate (TMPBPO) and 1-dodecylpyridin-4(1 H)-one (DOPO), have been prepared and applied to the assembly of lanthanide coordination complexes in an effort to understand the ligand-direction effect on the structure of the Ln complexes and the ligand sensitization effect on the luminescence of the Ln complexes. Due to the wide-band triplet states plus additional ILCT excitation states extending into lower energy levels, broadly and strongly sensitized photoluminescence of f→f transitions from various Ln(3+) ions were observed to cover the visible to near-infrared (NIR) regions. Among which, the Pr, Sm, Dy, and Tm complexes simultaneously display both strong visible and NIR emissions. Based on the isostructural feature of the Ln complexes, color tuning and single-component white light was achieved by preparation of solid solutions of the ternary systems Gd-Eu-Tb (for TMPBPO) and La-Eu-Tb and La-Dy-Sm (for DOPO). Moreover, the visible and NIR luminescence lifetimes of the Ln complexes with the TMPBPO ligand were investigated from 77 to 298 K, revealing a strong temperature dependence of the Tm(3+) ((3) H4 ) and Yb(3+) ((2) F5/2 ) decay dynamics, which has not been explored before for their coordination complexes.
Two zwitterionic-type ligands featuring π-π* and intraligand charge-transfer (ILCT) excited states, namely 1,1'-(2,3,5,6-tetramethyl-1,4-phenylene)bis(methylene)dipyridinium-4-olate (TMPBPO) and 1-dodecylpyridin-4(1H)-one (DOPO), have been prepared and applied to the assembly of lanthanide coordination complexes in an effort to understand the ligand-direction effect on the structure of the Ln complexes and the ligand sensitization effect on the luminescence of the Ln complexes. Due to the wide-band triplet states plus additional ILCT excitation states extending into lower energy levels, broadly and strongly sensitized photoluminescence of f[arrow right]f transitions from various Ln3+ ions were observed to cover the visible to near-infrared (NIR) regions. Among which, the Pr, Sm, Dy, and Tm complexes simultaneously display both strong visible and NIR emissions. Based on the isostructural feature of the Ln complexes, color tuning and single-component white light was achieved by preparation of solid solutions of the ternary systems Gd-Eu-Tb (for TMPBPO) and La-Eu-Tb and La-Dy-Sm (for DOPO). Moreover, the visible and NIR luminescence lifetimes of the Ln complexes with the TMPBPO ligand were investigated from 77 to 298K, revealing a strong temperature dependence of the Tm3+ (3H4) and Yb3+ (2F5/2) decay dynamics, which has not been explored before for their coordination complexes.
Author Du, Bin-Bin
Su, Cheng-Yong
Pan, Mei
Yue, Mei-Qin
Zhu, Yi-Xuan
Wei, Zhang-Wen
Author_xml – sequence: 1
  givenname: Mei
  surname: Pan
  fullname: Pan, Mei
  email: panm@mail.sysu.edu.cn
  organization: MOE Laboratory of Bioinorganic and Synthetic Chemistry, State Key Laboratory of Optoelectronic Materials and Technologies, Lehn Institute of Functional Materials, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, 510275, Guangzhou, P. R. China
– sequence: 2
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  surname: Du
  fullname: Du, Bin-Bin
  organization: MOE Laboratory of Bioinorganic and Synthetic Chemistry, State Key Laboratory of Optoelectronic Materials and Technologies, Lehn Institute of Functional Materials, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, 510275, Guangzhou, P. R. China
– sequence: 3
  givenname: Yi-Xuan
  surname: Zhu
  fullname: Zhu, Yi-Xuan
  organization: MOE Laboratory of Bioinorganic and Synthetic Chemistry, State Key Laboratory of Optoelectronic Materials and Technologies, Lehn Institute of Functional Materials, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, 510275, Guangzhou, P. R. China
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  surname: Yue
  fullname: Yue, Mei-Qin
  organization: MOE Laboratory of Bioinorganic and Synthetic Chemistry, State Key Laboratory of Optoelectronic Materials and Technologies, Lehn Institute of Functional Materials, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, 510275, Guangzhou, P. R. China
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  givenname: Zhang-Wen
  surname: Wei
  fullname: Wei, Zhang-Wen
  organization: MOE Laboratory of Bioinorganic and Synthetic Chemistry, State Key Laboratory of Optoelectronic Materials and Technologies, Lehn Institute of Functional Materials, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, 510275, Guangzhou, P. R. China
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  givenname: Cheng-Yong
  surname: Su
  fullname: Su, Cheng-Yong
  email: cesscy@mail.sysu.edu.cn
  organization: MOE Laboratory of Bioinorganic and Synthetic Chemistry, State Key Laboratory of Optoelectronic Materials and Technologies, Lehn Institute of Functional Materials, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, 510275, Guangzhou, P. R. China
BackLink https://www.ncbi.nlm.nih.gov/pubmed/26784018$$D View this record in MEDLINE/PubMed
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ContentType Journal Article
Copyright 2016 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim
2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Copyright_xml – notice: 2016 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim
– notice: 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
– notice: 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Issue 7
Keywords energy transfer
zwitterions
luminescence
white light
charge transfer
lanthanides
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2007; 31
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2009; 48
2013 2013; 52 125
2012; 51
2014; 20
2013; 19
2012; 134
2012; 256
2002; 102
2010; 114
2012 2012; 51 124
2015; 85
2007; 251
2013; 117
2014; 16
2005 2005; 44 117
2007; 7
2011; 21
2014; 50
2012; 22
2005; 34
2009; 15
2012; 20
2015; 284
2015; 15
2004 2004; 43 116
2013; 49
2011
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2015; 51
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2013; 42
2015; 54
2013 2013; 125 52
2007
2008; 10
2009; 131
2007; 10
2014; 273
2011; 255
2014; 114
2007; 13
2014; 43
2011; 131
2010; 46
1997; 75
2007; 111
2007 2007; 46 119
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Snippet Two zwitterionic‐type ligands featuring π–π* and intraligand charge‐transfer (ILCT) excited states, namely...
Two zwitterionic-type ligands featuring π-π* and intraligand charge-transfer (ILCT) excited states, namely...
Two zwitterionic-type ligands featuring pi - pi * and intraligand charge-transfer (ILCT) excited states, namely...
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SubjectTerms Charge transfer
Chemistry
Coordination compounds
Dysprosium
Energy levels
energy transfer
Excitation
Gadolinium
Lanthanides
Lanthanum
Ligands
Luminescence
Photoluminescence
Photons
Samarium
Solid solutions
Temperature dependence
Ternary systems
Tuning
White light
Zwitterions
Title Highly Efficient Visible-to-NIR Luminescence of Lanthanide(III) Complexes with Zwitterionic Ligands Bearing Charge-Transfer Character: Beyond Triplet Sensitization
URI https://api.istex.fr/ark:/67375/WNG-V0CB7NBS-J/fulltext.pdf
https://onlinelibrary.wiley.com/doi/abs/10.1002%2Fchem.201504344
https://www.ncbi.nlm.nih.gov/pubmed/26784018
https://www.proquest.com/docview/1761831956
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Volume 22
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