skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Ultrafast intersystem-crossing in platinum containing π-conjugated polymers with tunable spin-orbit coupling

Journal Article · · Scientific Reports
DOI:https://doi.org/10.1038/srep02653· OSTI ID:1624648
 [1];  [2];  [2];  [2];  [2];  [3];  [2]
  1. Univ. of Utah, Salt Lake City, UT (United States). Dept. of Physics and Astronomy; Nanjing Univ. of Science and Technology (China). School of Electronic and Optical Engineering
  2. Univ. of Utah, Salt Lake City, UT (United States). Dept. of Physics and Astronomy
  3. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
+ Show Author Affiliations

The development of efficient organic light-emitting diodes (OLED) and organic photovoltaic cells requires control over the dynamics of spin sensitive excitations. Embedding heavy metal atoms in p-conjugated polymer chains enhances the spin-orbit coupling (SOC), and thus facilitates intersystem crossing (ISC) from the singlet to triplet manifolds. Here we use various nonlinear optical spectroscopies such as two-photon absorption and electroabsorption in conjunction with electronic structure calculations, for studying the energies, emission bands and ultrafast dynamics of spin photoexcitations in two newly synthesized p-conjugated polymers that contain intrachain platinum (Pt) atoms separated by one (Pt-1) or three (Pt-3) organic spacer units. The controllable SOC in these polymers leads to a record ISC time of ,,1 ps in Pt-1 and ,6 ps in Pt-3. The tunable ultrafast ISC rate modulates the intensity ratio of the phosphorescence and fluorescence emission bands, with potential applications for white OLEDs.

Research Organization:
Univ. of Utah, Salt Lake City, UT (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
FG02-04ER46109
OSTI ID:
1624648
Journal Information:
Scientific Reports, Vol. 3, Issue 1; ISSN 2045-2322
Publisher:
Nature Publishing GroupCopyright Statement
Country of Publication:
United States
Language:
English

References (30)

Formation of Assemblies Comprising Ru–Polypyridine Complexes and CdSe Nanocrystals Studied by ATR-FTIR Spectroscopy and DFT Modeling journal July 2011
Spectroscopic Studies of Photoexcitations in Regioregular and Regiorandom Polythiophene Films journal September 2002
Nonlinear optical spectroscopy of excited states in polyfluorene journal March 2007
Platinum-Functionalized Random Copolymers for Use in Solution-Processible, Efficient, Near-White Organic Light-Emitting Diodes journal December 2004
What controls triplet exciton transfer in organic semiconductors? journal January 2011
Experimental determination of the charge/neutral branching ratio η in the photoexcitation of π -conjugated polymers by broadband ultrafast spectroscopy journal February 2007
The Singlet–Triplet Exchange Energy in Conjugated Polymers journal January 2004
Spatial extent of the singlet and triplet excitons in transition metal‐containing poly‐ynes journal September 1996
Polymer Triplet Energy Levels Need Not Limit Photocurrent Collection in Organic Solar Cells journal November 2012
Excitation transfer processes in a phosphor-doped poly( p -phenylene vinylene) light-emitting diode journal February 2002
Localization of Electronic Excitations in Conjugated Polymers Studied by DFT journal February 2011
Management of singlet and triplet excitons for efficient white organic light-emitting devices journal April 2006
Phosphorescence superradiance in a Pt-containing π -conjugated polymer journal November 2012
One-Dimensional Wide Energy Bands in a Polydiacetylene Revealed by Electroreflectance journal April 1981
Excited State Absorption Properties of Pt(II) Terpyridyl Complexes Bearing π-Conjugated Arylacetylides † journal November 2010
Role of the conduction band in electroabsorption, two-photon absorption, and third-harmonic generation in polydiacetylenes journal July 1993
A new mixing of Hartree–Fock and local density‐functional theories journal January 1993
Spectroscopic study of spin-dependent exciton formation rates in π -conjugated semiconductors: Comparison with electroluminescence techniques journal December 2004
Femtosecond transient photoinduced transmission measurements on a novel conjugated zinc porphyrin system journal January 1996
Optical absorption in the substituted phenylene-based conjugated polymers: Theory and experiment journal January 1997
Triplet Formation in Fullerene Multi-Adduct Blends for Organic Solar Cells and Its Influence on Device Performance journal July 2010
Spin-dependent exciton formation in π-conjugated compounds journal October 2001
Metal-containing polymers: Facile tuning of photophysical traits and emerging applications in organic electronics and photonics journal November 2011
Triplet states in a series of Pt-containing ethynylenes journal November 2000
Achieving Highly Efficient Fluorescent Blue Organic Light-Emitting Diodes Through Optimizing Molecular Structures and Device Configuration journal January 2011
A joint theoretical and experimental study of phenylene–acetylene molecular wires journal January 2005
Spectral diffusion in poly( para -phenylene)-type polymers with different energetic disorder journal March 2010
Nonlinear optical spectroscopy of excited states in disubstituted polyacetylene journal May 2010
Natural transition orbitals journal March 2003
Photophysics of excitons in quasi-one-dimensional organic semiconductors: Single-walled carbon nanotubes and π -conjugated polymers journal February 2006

Cited By (8)

Achieving yellow emission by varying the donor/acceptor units in rod-shaped fluorenyl-alkynyl based π-conjugated oligomers and their binuclear gold( i ) alkynyl complexes journal January 2017
Seven membered chelate Pt( ii ) complexes with 2,3-di(2-pyridyl)quinoxaline ligands: studies of substitution kinetics by sulfur donor nucleophiles, interactions with CT-DNA, BSA and in vitro cytotoxicity activities journal January 2019
Photosynthesis under artificial light: the shift in primary and secondary metabolism journal April 2014
Unidirectional Spin-Wave-Propagation-Induced Seebeck Voltage in a PEDOT:PSS/YIG Bilayer journal January 2018
Spin Transport in Organic Molecules journal June 2019
Inverse spin Hall effect from pulsed spin current in organic semiconductors with tunable spin–orbit coupling journal April 2016
Configuration interaction singles with spin-orbit coupling: Constructing spin-adiabatic states and their analytical nuclear gradients journal January 2019
Configuration Interaction Singles with Spin-Orbit Coupling: Constructing Spin-Adiabatic States and Their Analytical Nuclear Gradients text January 2018

Similar Records

Intersystem-crossing and phosphorescence rates in fac-Ir{sup III}(ppy){sub 3}: A theoretical study involving multi-reference configuration interaction wavefunctions
Journal Article · Sat Mar 07 00:00:00 EST 2015 · Journal of Chemical Physics · OSTI ID:1624648
Ultrafast branching in intersystem crossing dynamics revealed by coherent vibrational wavepacket motions in a bimetallic Pt($\mathrm{II}$) complex
Journal Article · Wed Jun 01 00:00:00 EDT 2022 · Faraday Discussions · OSTI ID:1624648
+4 more
Ultrafast Transient Spectroscopy of Polymer/Fullerene Blends for Organic Photovoltaic Applications
Journal Article · Fri Mar 01 00:00:00 EST 2013 · Materials · OSTI ID:1624648

Related Subjects

71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
Science & Technology - Other Topics
ORGANIC LEDS
NONLINEAR OPTICS
CHEMICAL PHYSICS
MOLECULAR ELECTRONICS