Linker Redox Mediated Control of Morphology and Properties in Semiconducting Iron-Semiquinoid Coordination Polymers.

The emergence of conductive 2D and less commonly 3D coordination polymers (CPs) and metal-organic frameworks (MOFs) promises novel applications in many fields. However, the synthetic parameters for these electronically complex materials are not thoroughly understood. Here we report a new 3D semiconducting CP Fe (C O ) , which is a fusion of 2D Fe-semiquinoid materials and 3D cubic Fe (C O ) materials, by using a different initial redox-state of the C O linker.

Steric and electronic effects of ligand substitution on redox-active FeS-based coordination polymers.

One of the notable advantages of molecular materials is the ability to precisely tune structure, properties, and function via molecular substitutions. While many studies have demonstrated this principle with classic carboxylate-based coordination polymers, there are comparatively fewer examples where systematic changes to sulfur-based coordination polymers have been investigated. Here we present such a study on 1D coordination chains of redox-active FeS clusters linked by methylated 1,4-benzene-dithiolates.

Redox-Active 1D Coordination Polymers of Iron-Sulfur Clusters.

Here we describe the combination of an archetypal redox-active metal sulfide cluster, FeS, with an organic linker, 1,4-benzenedithiolate, to prepare coordination polymers containing infinite chains of FeS clusters. The crystal structures of two solid materials have been solved from synchrotron X-ray powder diffraction data using simulated annealing and refined by a least-squares Rietveld refinement procedure. The electronic properties of these chains have also been characterized by UV-visible and Mössbauer spectroscopies.

Spin-Selective Photoreduction of a Stable Radical within a Covalent Donor-Acceptor-Radical Triad.

Controlling spin-spin interactions in multispin molecular assemblies is important for developing new approaches to quantum information processing. In this work, a covalent electron donor-acceptor-radical triad is used to probe spin-selective reduction of the stable radical to its diamagnetic anion. The molecule consists of a perylene electron donor chromophore (D) bound to a pyromellitimide acceptor (A), which is, in turn, linked to a stable α,γ-bisdiphenylene-β-phenylallyl radical (R) to produce D-A-R.

Spin Polarization Transfer from a Photogenerated Radical Ion Pair to a Stable Radical Controlled by Charge Recombination.

Photoexcitation of electron donor-acceptor molecules frequently produces radical ion pairs with well-defined initial spin-polarized states that have attracted significant interest for spintronics. Transfer of this initial spin polarization to a stable radical is predicted to depend on the rates of the radical ion pair recombination reactions, but this prediction has not been tested experimentally. In this study, a stable radical/electron donor/chromophore/electron acceptor molecule, BDPA-mPD-ANI-NDI, where BDPA is α,γ-bisdiphenylene-β-phenylallyl, mPD is m-phenylenediamine, ANI is 4-aminonaphthalene-1,8-dicarboximide, and NDI is naphthalene-1,4:5,8-bis(dicarboximide), was synthesized.

Unified model for singlet fission within a non-conjugated covalent pentacene dimer.

When molecular dimers, crystalline films or molecular aggregates absorb a photon to produce a singlet exciton, spin-allowed singlet fission may produce two triplet excitons that can be used to generate two electron-hole pairs, leading to a predicted ∼50% enhancement in maximum solar cell performance. The singlet fission mechanism is still not well understood. Here we report on the use of time-resolved optical and electron paramagnetic resonance spectroscopy to probe singlet fission in a pentacene dimer linked by a non-conjugated spacer.

Zero Quantum Coherence in a Series of Covalent Spin-Correlated Radical Pairs.

Photoinitiated subnanosecond electron transfer within covalently linked electron donor-acceptor molecules can result in the formation of a spin-correlated radical pair (SCRP) with a well-defined initial singlet spin configuration. Subsequent coherent mixing between the SCRP singlet and triplet m = 0 spin states, the so-called zero quantum coherence (ZQC), is of potential interest in quantum information processing applications because the ZQC can be probed using pulse electron paramagnetic resonance (pulse-EPR) techniques. Here, pulse-EPR spectroscopy is utilized to examine the ZQC oscillation frequencies and ZQC dephasing in three structurally well-defined D-A systems.

Electron Hopping and Charge Separation within a Naphthalene-1,4:5,8-bis(dicarboximide) Chiral Covalent Organic Cage.

We present the stereoselective synthesis of a chiral covalent organic cage consisting of three redox-active naphthalene-1,4:5,8-bis(dicarboximide) (NDI) units by dynamic imine chemistry. Single crystal X-ray diffraction analysis shows that host-guest interactions and racemic cocrystallization allow for controlling the solid state structure. Electronic interactions between the NDI units probed by absorption and circular dichroism spectroscopies, electrochemistry and theoretical calculations are shown to be weak.

Picosecond Control of Photogenerated Radical Pair Lifetimes Using a Stable Third Radical.

Photoinduced electron transfer reactions in organic donor-acceptor systems leading to long-lived radical ion pairs (RPs) have attracted broad interest for their potential applications in fields as diverse as solar energy conversion and spintronics. We present the photophysics and spin dynamics of an electron donor - electron acceptor - stable radical system consisting of a meta-phenylenediamine (mPD) donor covalently linked to a 4-aminonaphthalene-1,8-dicarboximide (ANI) electron-accepting chromophore as well as an α,γ-bisdiphenylene-β-phenylallyl (BDPA) stable radical. Selective photoexcitation of ANI produces the BDPA-mPD(+•)-ANI(-•) triradical in which the mPD(+•)-ANI(-•) RP spins are strongly exchange coupled.

Marked Consequences of Systematic Oligothiophene Catenation in Thieno[3,4-c]pyrrole-4,6-dione and Bithiopheneimide Photovoltaic Copolymers.

As effective building blocks for high-mobility transistor polymers, oligothiophenes are receiving attention for polymer solar cells (PSCs) because the resulting polymers can effectively suppress charge recombination. Here we investigate two series of in-chain donor-acceptor copolymers, PTPDnT and PBTInT, based on thieno[3,4-c]pyrrole-4,6-dione (TPD) or bithiopheneimide (BTI) as electron acceptor units, respectively, and oligothiophenes (nTs) as donor counits, for high-performance PSCs. Intramolecular S···O interaction leads to more planar TPD polymer backbones, however backbone torsion yields greater open-circuit voltages for BTI polymers.

Photogenerated Quartet State Formation in a Compact Ring-Fused Perylene-Nitroxide.

We report on a novel small organic molecule comprising a perylene chromophore fused to a six-membered ring containing a persistent nitroxide radical to give a perylene-nitroxide, or PerNO(•). This molecule is a robust, compact molecule in which the radical is closely bound to the chromophore but separated by saturated carbon atoms, thus limiting the electronic coupling between the chromophore and radical. We present both ultrafast transient absorption experiments and time-resolved EPR (TREPR) studies to probe the spin dynamics of photoexcited PerNO(•) and utilize X-ray crystallography to probe the molecular structure and stacking motifs of PerNO(•) in the solid state.

Fast Triplet Formation via Singlet Exciton Fission in a Covalent Perylenediimide-β-apocarotene Dyad Aggregate.

A covalent dyad was synthesized in which perylene-3,4,:9:10-bis(dicarboximide) (PDI) is linked to β-apocarotene (Car) using a biphenyl spacer. The dyad is monomeric in toluene and forms a solution aggregate in methylcyclohexane (MCH). Using femtosecond transient absorption (fsTA) spectroscopy, the monomeric dyad and its aggregates were studied both in solution and in thin films.

Tetrathiafulvalene hetero radical cation dimerization in a redox-active [2]catenane.

The electronic properties of tetrathiafulvalene (TTF) can be tuned by attaching electron-donating or electron-withdrawing substituents. An electron-rich macrocyclic polyether containing two TTF units of different constitutions, namely 4,4'-bis(hydroxymethyl)tetrathiafulvalene (OTTFO) and 4,4'-bisthiotetrathiafulvalene (STTFS), has been synthesized. On two-electron oxidation, a hetero radical dimer is formed between OTTFO(•+) and STTFS(•+).

Built-In Potential in Conjugated Polymer Diodes with Changing Anode Work Function: Interfacial States and Deviation from the Schottky-Mott Limit.

We use electroabsorption spectroscopy to measure the change in built-in potential (VBI) across the polymer photoactive layer in diodes where indium tin oxide electrodes are systematically modified using dipolar phosphonic acid self-assembled monolayers (SAMs) with various dipole moments. We find that VBI scales linearly with the work function (Φ) of the SAM-modified electrode over a wide range when using a solution-coated poly(p-phenylenevinylene) derivative as the active layer. However, we measure an interfacial parameter of S = eΔVBI/ΔΦ < 1, suggesting that these ITO/SAM/polymer interfaces deviate from the Schottky-Mott limit, in contrast to what has previously been reported for a number of ambient-processed organic-on-electrode systems.

Positionally defined, binary semiconductor nanoparticles synthesized by scanning probe block copolymer lithography.

We report the first method for synthesizing binary semiconductor materials by scanning probe block copolymer lithography (SPBCL) in desired locations on a surface. In this work, we utilize SPBCL to create polymer features containing a desired amount of Cd(2+), which is defined by the feature volume. When they are subsequently reacted in H(2)S in the vapor phase, a single CdS nanoparticle is formed in each block copolymer (BCP) feature.

Absence of photoinduced charge transfer in blends of PbSe quantum dots and conjugated polymers.

We use photoluminescence (PL) quenching and photoinduced absorption (PIA) spectroscopy to study charge transfer in bulk heterojunction blends of PbSe quantum dots with the semiconducting polymers poly-3-hexylthiophene (P3HT) and poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-para-phenylene vinylene] (MDMO-PPV). PIA spectra from the PbSe blends are compared to spectra from similar blends of the polymers with phenyl-C(61)-butyric acid methyl ester (PCBM) and blends with CdSe quantum dots. We find that the MDMO-PPV PL is quenched, and the PL lifetime is shortened upon addition of PbSe quantum dots, while the PL of the P3HT is unaffected upon blending.