Exploring the Excited States of a Hexa-peri-hexabenzocoronene-Substituted Dipyridophenazine Ligand and Its Metal Complexes: Inorganic Chemistry

Joseph I. Mapley; Jordan N. Smith; Georgina E. Shillito; Sara J. Fraser-Miller; Nigel T. Lucas; Keith C. Gordon

doi:10.1021/acs.inorgchem.3c01007

Exploring the Excited States of a Hexa-peri-hexabenzocoronene-Substituted Dipyridophenazine Ligand and Its Metal Complexes: Inorganic Chemistry

Joseph I. Mapley, Jordan N. Smith, Georgina E. Shillito, Sara J. Fraser-Miller, Nigel T. Lucas, Keith C. Gordon

Research output: Contribution to journal › Article › peer-review

3 Citations (Scopus)

Abstract

A hexa-peri-hexabenzocoronene (HBC)-substituted dipyridophenazine (dppz) ligand (dppz-HBC) and its corresponding rhenium [Re(CO)3Cl] and ruthenium [Ru(bpy)2]2+ complexes were synthesized and characterized. The interplay of their various excited states was investigated using spectroscopic and computational techniques. Perturbation of the HBC was seen through a broadening and decreased intensity of the HBC absorption bands that dominate the absorption spectra. A delocalized, partial charge transfer state was shown through emission (520 nm) in the ligand and rhenium complex and is supported by time-dependent density functional theory calculations. Transient absorption measurements revealed the presence of dark states with a triplet delocalized state populated in the ligand, while in the complexes, longer-lived (2.3-2.5 μs) triplet HBC states could be accessed. The properties of the studied ligand and complexes provide insight into the future design of polyaromatic systems and add to the rich history of dppz systems. © 2023 American Chemical Society

Original language	English
Pages (from-to)	11028-11036
Number of pages	9
Journal	Inorganic Chemistry
Volume	62
Issue number	28
DOIs	https://doi.org/10.1021/acs.inorgchem.3c01007
Publication status	Published - 17 Jul 2023
Externally published	Yes

Keywords

Charge transfer
Computation theory
Density functional theory
Excited states
Metal complexes
Rhenium compounds
Synthesis (chemical)
Charge transfer state
Computational technique
Excited-states
Hexa-peri-hexabenzocoronenes
Hexabenzocoronene
Ligand complexes
Partial charge transfer
Ru(bpy)
Spectroscopic technique
Synthesised
Ligands

Access to Document

10.1021/acs.inorgchem.3c01007Licence: In Copyright

Cite this

@article{1d7aa019c9d94bf59d3c7d75cbf8994c,

title = "Exploring the Excited States of a Hexa-peri-hexabenzocoronene-Substituted Dipyridophenazine Ligand and Its Metal Complexes: Inorganic Chemistry",

abstract = "A hexa-peri-hexabenzocoronene (HBC)-substituted dipyridophenazine (dppz) ligand (dppz-HBC) and its corresponding rhenium [Re(CO)3Cl] and ruthenium [Ru(bpy)2]2+ complexes were synthesized and characterized. The interplay of their various excited states was investigated using spectroscopic and computational techniques. Perturbation of the HBC was seen through a broadening and decreased intensity of the HBC absorption bands that dominate the absorption spectra. A delocalized, partial charge transfer state was shown through emission (520 nm) in the ligand and rhenium complex and is supported by time-dependent density functional theory calculations. Transient absorption measurements revealed the presence of dark states with a triplet delocalized state populated in the ligand, while in the complexes, longer-lived (2.3-2.5 μs) triplet HBC states could be accessed. The properties of the studied ligand and complexes provide insight into the future design of polyaromatic systems and add to the rich history of dppz systems. {\textcopyright} 2023 American Chemical Society",

keywords = "Charge transfer, Computation theory, Density functional theory, Excited states, Metal complexes, Rhenium compounds, Synthesis (chemical), Charge transfer state, Computational technique, Excited-states, Hexa-peri-hexabenzocoronenes, Hexabenzocoronene, Ligand complexes, Partial charge transfer, Ru(bpy), Spectroscopic technique, Synthesised, Ligands",

author = "Mapley, {Joseph I.} and Smith, {Jordan N.} and Shillito, {Georgina E.} and Fraser-Miller, {Sara J.} and Lucas, {Nigel T.} and Gordon, {Keith C.}",

year = "2023",

month = jul,

day = "17",

doi = "10.1021/acs.inorgchem.3c01007",

language = "English",

volume = "62",

pages = "11028--11036",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "28",

}

TY - JOUR

T1 - Exploring the Excited States of a Hexa-peri-hexabenzocoronene-Substituted Dipyridophenazine Ligand and Its Metal Complexes

T2 - Inorganic Chemistry

AU - Mapley, Joseph I.

AU - Smith, Jordan N.

AU - Shillito, Georgina E.

AU - Fraser-Miller, Sara J.

AU - Lucas, Nigel T.

AU - Gordon, Keith C.

PY - 2023/7/17

Y1 - 2023/7/17

N2 - A hexa-peri-hexabenzocoronene (HBC)-substituted dipyridophenazine (dppz) ligand (dppz-HBC) and its corresponding rhenium [Re(CO)3Cl] and ruthenium [Ru(bpy)2]2+ complexes were synthesized and characterized. The interplay of their various excited states was investigated using spectroscopic and computational techniques. Perturbation of the HBC was seen through a broadening and decreased intensity of the HBC absorption bands that dominate the absorption spectra. A delocalized, partial charge transfer state was shown through emission (520 nm) in the ligand and rhenium complex and is supported by time-dependent density functional theory calculations. Transient absorption measurements revealed the presence of dark states with a triplet delocalized state populated in the ligand, while in the complexes, longer-lived (2.3-2.5 μs) triplet HBC states could be accessed. The properties of the studied ligand and complexes provide insight into the future design of polyaromatic systems and add to the rich history of dppz systems. © 2023 American Chemical Society

AB - A hexa-peri-hexabenzocoronene (HBC)-substituted dipyridophenazine (dppz) ligand (dppz-HBC) and its corresponding rhenium [Re(CO)3Cl] and ruthenium [Ru(bpy)2]2+ complexes were synthesized and characterized. The interplay of their various excited states was investigated using spectroscopic and computational techniques. Perturbation of the HBC was seen through a broadening and decreased intensity of the HBC absorption bands that dominate the absorption spectra. A delocalized, partial charge transfer state was shown through emission (520 nm) in the ligand and rhenium complex and is supported by time-dependent density functional theory calculations. Transient absorption measurements revealed the presence of dark states with a triplet delocalized state populated in the ligand, while in the complexes, longer-lived (2.3-2.5 μs) triplet HBC states could be accessed. The properties of the studied ligand and complexes provide insight into the future design of polyaromatic systems and add to the rich history of dppz systems. © 2023 American Chemical Society

KW - Charge transfer

KW - Computation theory

KW - Density functional theory

KW - Excited states

KW - Metal complexes

KW - Rhenium compounds

KW - Synthesis (chemical)

KW - Charge transfer state

KW - Computational technique

KW - Excited-states

KW - Hexa-peri-hexabenzocoronenes

KW - Hexabenzocoronene

KW - Ligand complexes

KW - Partial charge transfer

KW - Ru(bpy)

KW - Spectroscopic technique

KW - Synthesised

KW - Ligands

UR - http://www.scopus.com/inward/record.url?scp=85164711722&partnerID=8YFLogxK

U2 - 10.1021/acs.inorgchem.3c01007

DO - 10.1021/acs.inorgchem.3c01007

M3 - Article

SN - 0020-1669

VL - 62

SP - 11028

EP - 11036

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 28

ER -

Exploring the Excited States of a Hexa-peri-hexabenzocoronene-Substituted Dipyridophenazine Ligand and Its Metal Complexes: Inorganic Chemistry

Abstract

Keywords

Access to Document

Other files and links

Fingerprint

Cite this