Photophysics of π-conjugated metal-organic oligomers

Aryleneethynylenes that contain the (bpy)Re(CO)3Cl chromophore

K. A. Walters, K. D. Ley, C. S P Cavalaheiro, S. E. Miller, D. Gosztola, Michael R Wasielewski, A. P. Bussandri, H. Van Willigen, K. S. Schanze

Research output: Contribution to journalArticle

87 Citations (Scopus)

Abstract

A comprehensive study of a series of four monodisperse, metal-organic π-conjugated oligomers of varying length is reported. The oligomers are based on the aryleneethynylene architecture, and they contain a 2,2′-bipyridine-5,5′-diyl (bpy) metal binding unit. The photophysical properties of the free oligomers and their complexes with the (L)ReI(CO)3X chromophore (where L = the bpy-oligomer and X = Cl or NCCH3) were explored by a variety of methods including electrochemistry, UV-visible absorption, variable temperature photoluminescence (PL), transient absorption (TA), and time-resolved electron paramagnetic spectroscopy (TREPR). The absorption of the free oligomers and the metal complexes is dominated by the π,π* transitions of the π-conjugated oligomers. The free oligomers feature a strong blue fluorescence that is quenched entirely in the (L)ReI(CO)3X complexes. The metal-oligomers feature a weak, relatively long-lived red photoluminescence that is assigned to emission from both the 3π,π* manifold of the π-conjugated system and the dπ Re → π* bpy-oligomer metal-to-ligand charge transfer (3MLCT) state. On the basis of a detailed analysis of the PL, TA, and TREPR results an excited-state model is developed which indicates that the oligomer-based 3π,π* state and the 3MLCT states are in close energetic proximity. Consequently the photophysical properties reflect a composite of the properties of the two excited-state manifolds.

Original languageEnglish
Pages (from-to)8329-8342
Number of pages14
JournalJournal of the American Chemical Society
Volume123
Issue number34
DOIs
Publication statusPublished - 2001

Fingerprint

Carbon Monoxide
Chromophores
Oligomers
Metals
Spectrum Analysis
Electrons
Electrochemistry
Coordination Complexes
Photoluminescence
Excited states
Fluorescence
Ligands
Temperature
Spectroscopy
Metal complexes
Charge transfer
Composite materials

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Photophysics of π-conjugated metal-organic oligomers : Aryleneethynylenes that contain the (bpy)Re(CO)3Cl chromophore. / Walters, K. A.; Ley, K. D.; Cavalaheiro, C. S P; Miller, S. E.; Gosztola, D.; Wasielewski, Michael R; Bussandri, A. P.; Van Willigen, H.; Schanze, K. S.

In: Journal of the American Chemical Society, Vol. 123, No. 34, 2001, p. 8329-8342.

Research output: Contribution to journalArticle

Walters, KA, Ley, KD, Cavalaheiro, CSP, Miller, SE, Gosztola, D, Wasielewski, MR, Bussandri, AP, Van Willigen, H & Schanze, KS 2001, 'Photophysics of π-conjugated metal-organic oligomers: Aryleneethynylenes that contain the (bpy)Re(CO)3Cl chromophore', Journal of the American Chemical Society, vol. 123, no. 34, pp. 8329-8342. https://doi.org/10.1021/ja015813h
Walters, K. A. ; Ley, K. D. ; Cavalaheiro, C. S P ; Miller, S. E. ; Gosztola, D. ; Wasielewski, Michael R ; Bussandri, A. P. ; Van Willigen, H. ; Schanze, K. S. / Photophysics of π-conjugated metal-organic oligomers : Aryleneethynylenes that contain the (bpy)Re(CO)3Cl chromophore. In: Journal of the American Chemical Society. 2001 ; Vol. 123, No. 34. pp. 8329-8342.
@article{b5b4f2c56e7341b78e8b8315be317db9,
title = "Photophysics of π-conjugated metal-organic oligomers: Aryleneethynylenes that contain the (bpy)Re(CO)3Cl chromophore",
abstract = "A comprehensive study of a series of four monodisperse, metal-organic π-conjugated oligomers of varying length is reported. The oligomers are based on the aryleneethynylene architecture, and they contain a 2,2′-bipyridine-5,5′-diyl (bpy) metal binding unit. The photophysical properties of the free oligomers and their complexes with the (L)ReI(CO)3X chromophore (where L = the bpy-oligomer and X = Cl or NCCH3) were explored by a variety of methods including electrochemistry, UV-visible absorption, variable temperature photoluminescence (PL), transient absorption (TA), and time-resolved electron paramagnetic spectroscopy (TREPR). The absorption of the free oligomers and the metal complexes is dominated by the π,π* transitions of the π-conjugated oligomers. The free oligomers feature a strong blue fluorescence that is quenched entirely in the (L)ReI(CO)3X complexes. The metal-oligomers feature a weak, relatively long-lived red photoluminescence that is assigned to emission from both the 3π,π* manifold of the π-conjugated system and the dπ Re → π* bpy-oligomer metal-to-ligand charge transfer (3MLCT) state. On the basis of a detailed analysis of the PL, TA, and TREPR results an excited-state model is developed which indicates that the oligomer-based 3π,π* state and the 3MLCT states are in close energetic proximity. Consequently the photophysical properties reflect a composite of the properties of the two excited-state manifolds.",
author = "Walters, {K. A.} and Ley, {K. D.} and Cavalaheiro, {C. S P} and Miller, {S. E.} and D. Gosztola and Wasielewski, {Michael R} and Bussandri, {A. P.} and {Van Willigen}, H. and Schanze, {K. S.}",
year = "2001",
doi = "10.1021/ja015813h",
language = "English",
volume = "123",
pages = "8329--8342",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "34",

}

TY - JOUR

T1 - Photophysics of π-conjugated metal-organic oligomers

T2 - Aryleneethynylenes that contain the (bpy)Re(CO)3Cl chromophore

AU - Walters, K. A.

AU - Ley, K. D.

AU - Cavalaheiro, C. S P

AU - Miller, S. E.

AU - Gosztola, D.

AU - Wasielewski, Michael R

AU - Bussandri, A. P.

AU - Van Willigen, H.

AU - Schanze, K. S.

PY - 2001

Y1 - 2001

N2 - A comprehensive study of a series of four monodisperse, metal-organic π-conjugated oligomers of varying length is reported. The oligomers are based on the aryleneethynylene architecture, and they contain a 2,2′-bipyridine-5,5′-diyl (bpy) metal binding unit. The photophysical properties of the free oligomers and their complexes with the (L)ReI(CO)3X chromophore (where L = the bpy-oligomer and X = Cl or NCCH3) were explored by a variety of methods including electrochemistry, UV-visible absorption, variable temperature photoluminescence (PL), transient absorption (TA), and time-resolved electron paramagnetic spectroscopy (TREPR). The absorption of the free oligomers and the metal complexes is dominated by the π,π* transitions of the π-conjugated oligomers. The free oligomers feature a strong blue fluorescence that is quenched entirely in the (L)ReI(CO)3X complexes. The metal-oligomers feature a weak, relatively long-lived red photoluminescence that is assigned to emission from both the 3π,π* manifold of the π-conjugated system and the dπ Re → π* bpy-oligomer metal-to-ligand charge transfer (3MLCT) state. On the basis of a detailed analysis of the PL, TA, and TREPR results an excited-state model is developed which indicates that the oligomer-based 3π,π* state and the 3MLCT states are in close energetic proximity. Consequently the photophysical properties reflect a composite of the properties of the two excited-state manifolds.

AB - A comprehensive study of a series of four monodisperse, metal-organic π-conjugated oligomers of varying length is reported. The oligomers are based on the aryleneethynylene architecture, and they contain a 2,2′-bipyridine-5,5′-diyl (bpy) metal binding unit. The photophysical properties of the free oligomers and their complexes with the (L)ReI(CO)3X chromophore (where L = the bpy-oligomer and X = Cl or NCCH3) were explored by a variety of methods including electrochemistry, UV-visible absorption, variable temperature photoluminescence (PL), transient absorption (TA), and time-resolved electron paramagnetic spectroscopy (TREPR). The absorption of the free oligomers and the metal complexes is dominated by the π,π* transitions of the π-conjugated oligomers. The free oligomers feature a strong blue fluorescence that is quenched entirely in the (L)ReI(CO)3X complexes. The metal-oligomers feature a weak, relatively long-lived red photoluminescence that is assigned to emission from both the 3π,π* manifold of the π-conjugated system and the dπ Re → π* bpy-oligomer metal-to-ligand charge transfer (3MLCT) state. On the basis of a detailed analysis of the PL, TA, and TREPR results an excited-state model is developed which indicates that the oligomer-based 3π,π* state and the 3MLCT states are in close energetic proximity. Consequently the photophysical properties reflect a composite of the properties of the two excited-state manifolds.

UR - http://www.scopus.com/inward/record.url?scp=0034814381&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0034814381&partnerID=8YFLogxK

U2 - 10.1021/ja015813h

DO - 10.1021/ja015813h

M3 - Article

VL - 123

SP - 8329

EP - 8342

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 34

ER -