Solid state photochemistry of novel composites containing luminescent metal centers and poly(2-methoxyaniline-5-sulfonic acid)

Lynn Dennany, Emmet J. O'Reilly, Peter C. Innis, Gordon G. Wallace, Robert J. Forster

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

Steady state luminescence and measurements of the luminescent lifetime as well as cyclic voltammetry have been used to elucidate the mechanism and dynamics of interaction between a luminescent ruthenium metal center and two different fractions of poly(2-methoxyaniline-5-sulfonic acid) (PMAS). The two fractions, high molecular weight (HMWT) PMAS and low molecular weight (LMWT) PMAS oligomer, showed significantly distinctive influences on the luminophore. The HMWT PMAS, confirmed to be an emeraldine salt by its characteristic redox chemistry, greatly impacted the diffusion coefficient of the Ru2+/3+ within the composite film, increasing the diffusion coefficient, D-CT, by 2 orders of magnitude. The HMWT PMAS also resulted in quenching of the ruthenium-based emission. Significantly, these results indicate that quenching involves both static and dynamic processes, with the static quenching being the dominant process, suggesting that the metal center and polymer backbone were strongly associated. In stark contrast, the LMWT PMAS did not influence the electrochemical properties of the ruthenium metal center; however, it did double the emission observed from the ruthenium metal center. The insensitivity of the luminescence lifetime does suggest that, as with the HMWT PMAS, LWMT PMAS is strongly associated with the ruthenium metal center. The enhanced luminescence may allow for many potential sensor developments based on the luminescent ruthenium metal center, while the HMWT PMAS quenching could be utilized within quenching-based strategies or electrochemical devices.

LanguageEnglish
Pages7443-7448
Number of pages6
JournalJournal of Physical Chemistry B
Volume113
Issue number21
DOIs
Publication statusPublished - 28 May 2009

Fingerprint

Photochemical reactions
sulfonic acid
Ruthenium
photochemical reactions
ruthenium
Metals
Molecular weight
molecular weight
solid state
quenching
Quenching
composite materials
Acids
Composite materials
metals
Luminescence
low molecular weights
luminescence
diffusion coefficient
life (durability)

Keywords

  • rigid-rod
  • direct electrochemiluminescence
  • electronic communications
  • sulfonated polyaniline
  • ultrathin films
  • polymers
  • complexes
  • photoluminescence

Cite this

Dennany, Lynn ; O'Reilly, Emmet J. ; Innis, Peter C. ; Wallace, Gordon G. ; Forster, Robert J. / Solid state photochemistry of novel composites containing luminescent metal centers and poly(2-methoxyaniline-5-sulfonic acid). In: Journal of Physical Chemistry B. 2009 ; Vol. 113, No. 21. pp. 7443-7448.
@article{e8a25e00148c43f5a3d987652c9bb075,
title = "Solid state photochemistry of novel composites containing luminescent metal centers and poly(2-methoxyaniline-5-sulfonic acid)",
abstract = "Steady state luminescence and measurements of the luminescent lifetime as well as cyclic voltammetry have been used to elucidate the mechanism and dynamics of interaction between a luminescent ruthenium metal center and two different fractions of poly(2-methoxyaniline-5-sulfonic acid) (PMAS). The two fractions, high molecular weight (HMWT) PMAS and low molecular weight (LMWT) PMAS oligomer, showed significantly distinctive influences on the luminophore. The HMWT PMAS, confirmed to be an emeraldine salt by its characteristic redox chemistry, greatly impacted the diffusion coefficient of the Ru2+/3+ within the composite film, increasing the diffusion coefficient, D-CT, by 2 orders of magnitude. The HMWT PMAS also resulted in quenching of the ruthenium-based emission. Significantly, these results indicate that quenching involves both static and dynamic processes, with the static quenching being the dominant process, suggesting that the metal center and polymer backbone were strongly associated. In stark contrast, the LMWT PMAS did not influence the electrochemical properties of the ruthenium metal center; however, it did double the emission observed from the ruthenium metal center. The insensitivity of the luminescence lifetime does suggest that, as with the HMWT PMAS, LWMT PMAS is strongly associated with the ruthenium metal center. The enhanced luminescence may allow for many potential sensor developments based on the luminescent ruthenium metal center, while the HMWT PMAS quenching could be utilized within quenching-based strategies or electrochemical devices.",
keywords = "rigid-rod, direct electrochemiluminescence, electronic communications, sulfonated polyaniline, ultrathin films, polymers, complexes, photoluminescence",
author = "Lynn Dennany and O'Reilly, {Emmet J.} and Innis, {Peter C.} and Wallace, {Gordon G.} and Forster, {Robert J.}",
year = "2009",
month = "5",
day = "28",
doi = "10.1021/jp901808d",
language = "English",
volume = "113",
pages = "7443--7448",
journal = "Journal of Physical Chemistry B",
issn = "1520-6106",
publisher = "American Chemical Society",
number = "21",

}

Solid state photochemistry of novel composites containing luminescent metal centers and poly(2-methoxyaniline-5-sulfonic acid). / Dennany, Lynn; O'Reilly, Emmet J.; Innis, Peter C.; Wallace, Gordon G.; Forster, Robert J.

In: Journal of Physical Chemistry B, Vol. 113, No. 21, 28.05.2009, p. 7443-7448.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Solid state photochemistry of novel composites containing luminescent metal centers and poly(2-methoxyaniline-5-sulfonic acid)

AU - Dennany, Lynn

AU - O'Reilly, Emmet J.

AU - Innis, Peter C.

AU - Wallace, Gordon G.

AU - Forster, Robert J.

PY - 2009/5/28

Y1 - 2009/5/28

N2 - Steady state luminescence and measurements of the luminescent lifetime as well as cyclic voltammetry have been used to elucidate the mechanism and dynamics of interaction between a luminescent ruthenium metal center and two different fractions of poly(2-methoxyaniline-5-sulfonic acid) (PMAS). The two fractions, high molecular weight (HMWT) PMAS and low molecular weight (LMWT) PMAS oligomer, showed significantly distinctive influences on the luminophore. The HMWT PMAS, confirmed to be an emeraldine salt by its characteristic redox chemistry, greatly impacted the diffusion coefficient of the Ru2+/3+ within the composite film, increasing the diffusion coefficient, D-CT, by 2 orders of magnitude. The HMWT PMAS also resulted in quenching of the ruthenium-based emission. Significantly, these results indicate that quenching involves both static and dynamic processes, with the static quenching being the dominant process, suggesting that the metal center and polymer backbone were strongly associated. In stark contrast, the LMWT PMAS did not influence the electrochemical properties of the ruthenium metal center; however, it did double the emission observed from the ruthenium metal center. The insensitivity of the luminescence lifetime does suggest that, as with the HMWT PMAS, LWMT PMAS is strongly associated with the ruthenium metal center. The enhanced luminescence may allow for many potential sensor developments based on the luminescent ruthenium metal center, while the HMWT PMAS quenching could be utilized within quenching-based strategies or electrochemical devices.

AB - Steady state luminescence and measurements of the luminescent lifetime as well as cyclic voltammetry have been used to elucidate the mechanism and dynamics of interaction between a luminescent ruthenium metal center and two different fractions of poly(2-methoxyaniline-5-sulfonic acid) (PMAS). The two fractions, high molecular weight (HMWT) PMAS and low molecular weight (LMWT) PMAS oligomer, showed significantly distinctive influences on the luminophore. The HMWT PMAS, confirmed to be an emeraldine salt by its characteristic redox chemistry, greatly impacted the diffusion coefficient of the Ru2+/3+ within the composite film, increasing the diffusion coefficient, D-CT, by 2 orders of magnitude. The HMWT PMAS also resulted in quenching of the ruthenium-based emission. Significantly, these results indicate that quenching involves both static and dynamic processes, with the static quenching being the dominant process, suggesting that the metal center and polymer backbone were strongly associated. In stark contrast, the LMWT PMAS did not influence the electrochemical properties of the ruthenium metal center; however, it did double the emission observed from the ruthenium metal center. The insensitivity of the luminescence lifetime does suggest that, as with the HMWT PMAS, LWMT PMAS is strongly associated with the ruthenium metal center. The enhanced luminescence may allow for many potential sensor developments based on the luminescent ruthenium metal center, while the HMWT PMAS quenching could be utilized within quenching-based strategies or electrochemical devices.

KW - rigid-rod

KW - direct electrochemiluminescence

KW - electronic communications

KW - sulfonated polyaniline

KW - ultrathin films

KW - polymers

KW - complexes

KW - photoluminescence

U2 - 10.1021/jp901808d

DO - 10.1021/jp901808d

M3 - Article

VL - 113

SP - 7443

EP - 7448

JO - Journal of Physical Chemistry B

T2 - Journal of Physical Chemistry B

JF - Journal of Physical Chemistry B

SN - 1520-6106

IS - 21

ER -