The field of chemical sensing is becoming ever more dependent upon novel materials. Polymers, crystals, glasses, particles, and nanostructures have made a profound impact and have endowed modern sensory systems with superior performance. Electronic polymers have emerged as one of the most important classes of transduction materials; they readily transform a chemical signal into an easily measured electrical or optical event. Although our group reviewed this field in 2000,1 the high levels of activity and the impact of these methods now justify a subsequent review as part of this special issue. In this review we restrict our discussions to purely fluorescence-based methods using conjugated polymers (CPs). We further confine our detailed coverage to articles published since our previous review and will only detail earlier research in this Introduction to illustrate fundamental concepts and terminology that underpin the recent literature.

Chemical sensors based on amplifying fluorescent conjugated polymers.

A review was presented to demonstrate a historical description of the synthesis of light-emitting conjugated polymers for applications in electroluminescent devices. Electroluminescence (EL) was first reported in poly(para-phenylene vinylene) (PPV) in 1990 and researchers continued to make significant efforts to develop conjugated materials as the active units in light-emitting devices (LED) to be used in display applications. Conjugated oligomers were used as luminescent materials and as models for conjugated polymers in the review. Oligomers were used to demonstrate a structure and property relationship to determine a key polymer property or to demonstrate a technique that was to be applied to polymers. The review focused on demonstrating the way polymer structures were made and the way their properties were controlled by intelligent and rational and synthetic design.

Synthesis of Light-Emitting Conjugated Polymers for Applications in Electroluminescent Devices

WOLEDs offer new design opportunities in practical solid-state lighting and could play a significant role in reducing global energy consumption. Obtaining white light from organic LEDs is a considerable challenge. Alongside the development of new materials with improved color stability and balanced charge transport properties, major issues involve the fabrication of large-area devices and the development of low-cost manufacturing technology. This Review will describe the types of materials (small molecules and polymers) that have been used to fabricate WOLEDs. A range of device architectures are presented and appraised.

Recent advances in white organic light-emitting materials and devices (WOLEDs).

The Hamiltonian Heff of an open quantum system consists formally of a first-order interaction term describing the closed (isolated) system with discrete states and a second-order term caused by the interaction of the discrete states via the common continuum of scattering states. Under certain conditions, the last term may be dominant. Due to this term, Heff is non-Hermitian. Using the Feshbach projection operator formalism, the solution ΨEc of the Schrodinger equation in the whole function space (with discrete as well as scattering states, and the Hermitian Hamilton operator H) can be represented in the interior of the localized part of the system in the set of eigenfunctions λ of Heff. Hence, the characteristics of the eigenvalues and eigenfunctions of the non-Hermitian operator Heff are contained in observable quantities. Controlling the characteristics by means of external parameters, quantum systems can be manipulated. This holds, in particular, for small quantum systems coupled to a small number of channels. The paper consists of three parts. In the first part, the eigenvalues and eigenfunctions of non-Hermitian operators are considered. Most important are the true and avoided crossings of the eigenvalue trajectories. In approaching them, the phases of the λ lose their rigidity and the values of observables may be enhanced. Here the second-order term of Heff determines decisively the dynamics of the system. The time evolution operator is related to the non-Hermiticity of Heff. In the second part of the paper, the solution ΨEc and the S matrix are derived by using the Feshbach projection operator formalism. The regime of overlapping resonances is characterized by non-rigid phases of the ΨEc (expressed quantitatively by the phase rigidity ρ). They determine the internal impurity of an open quantum system. Here, level repulsion passes into width bifurcation (resonance trapping): a dynamical phase transition takes place which is caused by the feedback between environment and system. In the third part, the internal impurity of open quantum systems is considered by means of concrete examples. Bound states in the continuum appearing at certain parameter values can be used in order to stabilize open quantum systems. Of special interest are the consequences of the non-rigidity of the phases of λ not only for the problem of dephasing, but also for the dynamical phase transitions and questions related to them such as phase lapses and enhancement of observables.

https://iopscience.iop.org/article/10.1088/1751-8113/42/15/153001/pdf

A non-Hermitian Hamilton operator and the physics of open quantum systems

https://www.bose.res.in/~skpal/papers/biological%20water_2011.pdf

Biological water: A critique

First-principles quantum mechanical calculations show that the exponential-decay law for any metastable state is only an approximation and predict an asymptotically algebraic contribution to the decay for sufficiently long times. In this Letter, we measure the luminescence decays of many dissolved organic materials after pulsed laser excitation over more than 20 lifetimes and obtain the first experimental proof of the turnover into the nonexponential decay regime. As theoretically expected, the strength of the nonexponential contributions scales with the energetic width of the excited state density distribution whereas the slope indicates the broadening mechanism.

/pdf/violation-of-the-exponential-decay-law-at-long-times-rhrn4awuus.pdf

Violation of the exponential-decay law at long times.

Using time-resolved and steady-state photoluminescence techniques, fluorene/fluorenone copolymers have been studied to investigate the role of keto defects in degraded polyfluorene. Keto sites can be populated via migration from polyfluorene singlets, thereby quenching the polyfluorene fluorescence, and via direct photon absorption. In the former case, the migration process dominates all thermal and interchain variability in the efficiency of quenching. No annihilation process of fluorenone triplets and no interchain processes such as excimer formation participate in the defect emission itself.

Population and decay of keto states in conjugated polymers

In order to disentangle the relaxation effects of exciton migration and conformational rearrangement, a comparative study of a polyfluorene derivative and short oligofluorenes is carried out. We probe their long-time time-dependent relaxation in dilute solution using picosecond single photon counting and streak camera techniques. Conformational relaxation is found in oligo- and polyfluorenes. Oligofluorene relaxation is purely conformational: time scales vary between 10 and $300\phantom{\rule{0.3em}{0ex}}\mathrm{ps}$ becoming faster with decreasing chain length and solvent viscosity or increasing temperature. While a rigid ladder-type polymer in solution does not show any picosecond relaxation, polyfluorene in solution exhibits fluorescence dynamics indicating both, conformational relaxation and exciton migration.

Dynamics of conformational relaxation in photoexcited oligofluorenes and polyfluorene

The quenching process of fluorescence emission in polyfluorene (PF) due to the presence of intramolecular 9-fluorenone (9FL) moieties is studied in dilute toluene solution as a function of 9FL content in eight copolymers containing both fluorene and fluorenone units (PF/FLx). The absorption spectrum of PF/FLx copolymers clearly shows a new absorption band, redshifted relatively to the PF and 9-fluorenone absorption, which increases in intensity when the fluorenone fraction increases and also decreases with solvent polarity. Fluorescence emission spectra of PF/FLx show that this redshifted and unstructured emission does not coincide with the 9-fluorenone emission and, with increasing solvent polarity, it further redshifts and decreases in intensity. An isoemissive point is clearly observed on the fluorescence emission spectra of PF/FLx as a function of fluorenone content, showing that the new emission band is formed at the expense of PF. We propose the formation of an intramolecular charge transfer complex...

Intramolecular fluorescence quenching in luminescent copolymers containing fluorenone and fluorene units: a direct measurement of intrachain exciton hopping rate.

In this study, we report on the unusual fluorescence decay of an alkoxy-substituted polyspirobifluorene. Excited state behavior has been probed as a function of time, using femtosecond photobleaching, single photon counting, and streak camera techniques. Unusually complex decay kinetics are observed, which strongly depend on solvent viscosity and polarity, featuring decay components in both the tens of picoseconds and in the nanosecond time domain. These findings are explained by the consequences of spiroconjugation in combination with excited-state conformational relaxation. We propose that exciton wave function delocalization into the spiro units effectively traps the exciton, allowing it to relax further into a highly emissive state with a very long lifetime as compared to non-spiroconjugated polymer analogues. Frontier molecular orbitals and exciton orbitals have been calculated using a first principles density functional theory (DFT) approach. These results confirm the importance of spiroconjugation as both the highest occupied molecular orbital (HOMO) and the (lowest) exciton level are not localized on the polymer backbone but strongly extend into the side fluorene groups of the spirobifluorene units. The results of our calculations are very sensitive to the substitution pattern on the spirobifluorene units, in particular when oxygen is included. This finding may lead to new materials of this kind with optimized charge carrier transport properties and high luminescence quantum yields.

The complex excited-state behavior of a polyspirobifluorene derivative: the role of spiroconjugation and mixed charge transfer character on excited-state stabilization and radiative lifetime.

S.I. Hintschich

Papers

Violation of the exponential-decay law at long times.

Population and decay of keto states in conjugated polymers

Dynamics of conformational relaxation in photoexcited oligofluorenes and polyfluorene

Intramolecular fluorescence quenching in luminescent copolymers containing fluorenone and fluorene units: a direct measurement of intrachain exciton hopping rate.

The complex excited-state behavior of a polyspirobifluorene derivative: the role of spiroconjugation and mixed charge transfer character on excited-state stabilization and radiative lifetime.