Excitonic transitions in organic semiconductors are associated with large oscillator strength that limits the excited-state lifetime and can in turn impede long-range exciton migration. We present perylene-based emissive H-aggregate nanowires where the lowest energy state is only weakly coupled to the ground state, thus dramatically enhancing lifetime. Exciton migration occurs by thermally activated hopping, leading to luminescence quenching on topological wire defects. An atomic force microscope tip can introduce local topological quenchers by distorting the H-aggregate structure, demonstrating long-range exciton migration at room temperature and offering a potential route to writing fluorescent "nanobarcodes" and excitonic circuits.

With organic light-emitting diodes (OLEDs) emerging in ever more applications, such as smart phones, televisions, and lighting, it is easy to forget that the present technology is based on a brilliantly simple patch to an inherent problem of fluorescent hydrocarbons: three quarters of the electrically generated energy is dissipated as heat by triplet excitons. Radiative decay from the triplet state via phosphorescence is generally very weak, and has only been resolved in transient spectroscopy at low temperatures in select organic semiconductors. [1] The solution to this problem has been to incorporate metal-organic emitters in OLEDs, [2] which mix spin by enhancing intersystem crossing through spin-orbit coupling: the heavy-atom effect. As this approach relies on the longevity of triplet excitons and the associated diffusion lengths, it is highly effective: in a suitably homogeneous environment even ppm concentrations of covalently bound metal atoms are sufficient to activate electrophosphorescence. [3] The second conceivable approach to harvesting energy from triplets is based on endothermic conversion [4] to a fluorescent singlet by reverse intersystem crossing. [5] This method necessitates control not only over spin-orbit coupling, requiring a heavy atom or a carefully engineered charge-transfer state, but also over the singlet-triplet exchange gap, which can be tuned by excitonic confinement. [6] Although progress has been made recently, conceptually it parallels the former approach: all excitations are converted to either triplets or singlets, thereby losing information on the underlying spin correlations of charge carriers. Evidence is emerging, however, that spin correlations in excitonic electron-hole precursor pairs can be used for exquisitely sensitive measurements of magnetic fields [7] and possibly even for quantum coherence phenomenology, [7b] with analogies to avian radical-pair photomagnetosensory processes. [8] To quantify such spin correlations, it is desirable to develop materials without heavy-atom spin mixing that show both intrinsic fluorescence and phosphorescence.The third approach to triplet harvesting has not been explored previously: tuning spin-orbit coupling without heavy atoms such that non-radiative internal conversion from the triplet excited state to the singlet ground state is suppressed and phosphorescence is the only remaining relaxation mechanism. Even in low-atomic-order-number compounds such as hydrocarbons, the orbital component of the wavefunction can give rise to substantial magnetic moments, leading to non-negligible spin-orbit energy terms. The effect is well-studied in carbon nanotubes and graphene, where zero-field splitting correlates with nanoscale curva

We report the synthesis, electrical characterization and ammonia gas sensing with single nanowire of conducting polypyrrole. Three hundred nanometer in diameter and 50 to 60 mm long polypyrrole nanowires were synthesized by chemical polymerization inside SiO 2 coated alumina membranes. Temperature dependent electrical resistance studies established that the chemically synthesized nanowires were more ordered compared to electrochemically synthesized nanowires. We further demonstrated that gas sensors based on single polypyrrole nanowire exhibited good sensitivity towards ammonia, and provided a reliable detection at concentration as low as approximately 40 ppm.

Long-lived excitons in H-aggregates hold great promise for efficient transport of excitation energy, provided they are not scavenged by structurallly relaxed excimers. We report solution self-assembly of a perylene bisimide (PBI) folda-dimer that exhibits two distinct kinetic stages: an initial fast assembly leads to metastable aggregates with large excimer contribution that is followed by a slower growth of stable, extended H-aggregates free of excimers. Mechanistic investigations reveal an interplay of two competing aggregation pathways, where suppression of excimers is directly linked to the crossover from an isodesmic to cooperative aggregation. How the comeptition between two self-assembly pathways is influenced by the conformational flexibility of the folda-dimer is also discussed.

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