Characterization of excimer relaxation via femtosecond shortwaveand mid-infrared spectroscopy

Catherine M. Mauck, Ryan M. Young, Michael R Wasielewski

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

Excimer formation plays a significant role in trapping excitons within organic molecular solids. Covalent dimers of perylene-3,4:9,10-bis- (dicarboximide) (PDI) are useful model systems for studying these processes as their intermolecular geometries can be precisely tuned. Using femtosecond visible-pump infrared-probe (fsIR) spectroscopy in the shortwave-And midinfrared regions, we characterize two PDI dimers with a cofacial and a slip-stacked geometry that are coupled through a triptycene bridge. In the mid-infrared region, fsIR spectra for the strongly coupled dimers are highly blue-shifted compared to spectra for monomeric 1∗PDI. The perylene core stretching modes provide a directly observable probe of excimer relaxation, as they are particularly sensitive to this process, which is associated with a small blue shift of these modes in both dimers. The broad Frenkel-To-CT state electronic transition of the excimer, the edge of which has previously been detected in the NIR region, is now fully resolved to be much broader and to extend well into the shortwave infrared region for both dimers and is likely a generic feature of π-extended aromatic excimers.

Original languageEnglish
Pages (from-to)784-792
Number of pages9
JournalJournal of Physical Chemistry A
Volume121
Issue number4
DOIs
Publication statusPublished - Jan 1 2017

Fingerprint

excimers
Dimers
Infrared spectroscopy
infrared spectroscopy
dimers
Perylene
Infrared radiation
Geometry
probes
Electronic states
geometry
blue shift
Stretching
slip
trapping
excitons
Pumps
Spectroscopy
pumps
electronics

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Characterization of excimer relaxation via femtosecond shortwaveand mid-infrared spectroscopy. / Mauck, Catherine M.; Young, Ryan M.; Wasielewski, Michael R.

In: Journal of Physical Chemistry A, Vol. 121, No. 4, 01.01.2017, p. 784-792.

Research output: Contribution to journalArticle

@article{3afe9d3952f94808a93e7a79b2a9846f,
title = "Characterization of excimer relaxation via femtosecond shortwaveand mid-infrared spectroscopy",
abstract = "Excimer formation plays a significant role in trapping excitons within organic molecular solids. Covalent dimers of perylene-3,4:9,10-bis- (dicarboximide) (PDI) are useful model systems for studying these processes as their intermolecular geometries can be precisely tuned. Using femtosecond visible-pump infrared-probe (fsIR) spectroscopy in the shortwave-And midinfrared regions, we characterize two PDI dimers with a cofacial and a slip-stacked geometry that are coupled through a triptycene bridge. In the mid-infrared region, fsIR spectra for the strongly coupled dimers are highly blue-shifted compared to spectra for monomeric 1∗PDI. The perylene core stretching modes provide a directly observable probe of excimer relaxation, as they are particularly sensitive to this process, which is associated with a small blue shift of these modes in both dimers. The broad Frenkel-To-CT state electronic transition of the excimer, the edge of which has previously been detected in the NIR region, is now fully resolved to be much broader and to extend well into the shortwave infrared region for both dimers and is likely a generic feature of π-extended aromatic excimers.",
author = "Mauck, {Catherine M.} and Young, {Ryan M.} and Wasielewski, {Michael R}",
year = "2017",
month = "1",
day = "1",
doi = "10.1021/acs.jpca.6b11388",
language = "English",
volume = "121",
pages = "784--792",
journal = "Journal of Physical Chemistry A",
issn = "1089-5639",
publisher = "American Chemical Society",
number = "4",

}

TY - JOUR

T1 - Characterization of excimer relaxation via femtosecond shortwaveand mid-infrared spectroscopy

AU - Mauck, Catherine M.

AU - Young, Ryan M.

AU - Wasielewski, Michael R

PY - 2017/1/1

Y1 - 2017/1/1

N2 - Excimer formation plays a significant role in trapping excitons within organic molecular solids. Covalent dimers of perylene-3,4:9,10-bis- (dicarboximide) (PDI) are useful model systems for studying these processes as their intermolecular geometries can be precisely tuned. Using femtosecond visible-pump infrared-probe (fsIR) spectroscopy in the shortwave-And midinfrared regions, we characterize two PDI dimers with a cofacial and a slip-stacked geometry that are coupled through a triptycene bridge. In the mid-infrared region, fsIR spectra for the strongly coupled dimers are highly blue-shifted compared to spectra for monomeric 1∗PDI. The perylene core stretching modes provide a directly observable probe of excimer relaxation, as they are particularly sensitive to this process, which is associated with a small blue shift of these modes in both dimers. The broad Frenkel-To-CT state electronic transition of the excimer, the edge of which has previously been detected in the NIR region, is now fully resolved to be much broader and to extend well into the shortwave infrared region for both dimers and is likely a generic feature of π-extended aromatic excimers.

AB - Excimer formation plays a significant role in trapping excitons within organic molecular solids. Covalent dimers of perylene-3,4:9,10-bis- (dicarboximide) (PDI) are useful model systems for studying these processes as their intermolecular geometries can be precisely tuned. Using femtosecond visible-pump infrared-probe (fsIR) spectroscopy in the shortwave-And midinfrared regions, we characterize two PDI dimers with a cofacial and a slip-stacked geometry that are coupled through a triptycene bridge. In the mid-infrared region, fsIR spectra for the strongly coupled dimers are highly blue-shifted compared to spectra for monomeric 1∗PDI. The perylene core stretching modes provide a directly observable probe of excimer relaxation, as they are particularly sensitive to this process, which is associated with a small blue shift of these modes in both dimers. The broad Frenkel-To-CT state electronic transition of the excimer, the edge of which has previously been detected in the NIR region, is now fully resolved to be much broader and to extend well into the shortwave infrared region for both dimers and is likely a generic feature of π-extended aromatic excimers.

UR - http://www.scopus.com/inward/record.url?scp=85027278553&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85027278553&partnerID=8YFLogxK

U2 - 10.1021/acs.jpca.6b11388

DO - 10.1021/acs.jpca.6b11388

M3 - Article

AN - SCOPUS:85027278553

VL - 121

SP - 784

EP - 792

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

IS - 4

ER -