Correlating structure and photophysical properties in thiazolo[5,4-d]thiazole crystal derivatives for use in solid-state photonic and fluorescence-based optical devices.

There is a growing demand for new fluorescent small molecule dyes for solid state applications in the photonics and optoelectronics industry. Thiazolo[5,4-d]thiazole (TTz) is an organic heterocycle moiety which has previously shown remarkable properties as a conjugated polymer and in solution-based studies. For TTz-based small molecules to be incorporated in solid-state fluorescence-based optical devices, a thorough elucidation of their structure-photophysical properties needs to be established. Herein, we have studied four TTz-based materials functionalized with alkyl appendages of varying carbon chain lengths. We report the single crystal structures of the TTz derivatives, three of which were previously unknown. The packing modes of the crystals reveal that molecular arrangements are largely governed by a chorus of synergistic intermolecular non-covalent interactions. Three crystals packed in herringbone mode and one crystal packed in slipped stacks proving that alkyl appendages modulate structural organization in TTz-based materials. Steady state and time-resolved photophysical properties of these crystals were studied via diffuse-reflectance, micro-Raman, and photoluminescence spectroscopy. The crystals fluoresce from orange-red to blue spanning through the whole gamut of the visible spectrum. We have established that photophysical properties are a function of crystal packing in symmetrically substituted TTz-based materials. This correlation was then utilized to fabricate crystalline blends. We demonstrate, for the first time, that symmetrically substituted donor-acceptor-donor TTz-based materials can be used for phosphor-converted color-tuning and white-light emission. Given the cost effectiveness, ease of synthesis and now a structure-photophysics correlation, we present a compelling case for the adoption of TTz-based materials in solid-state photonic and fluorescence-based optical devices.

Advanced Polymeric Nanocomposite Membranes for Water and Wastewater Treatment: A Comprehensive Review.

Nanomaterials have been extensively used in polymer nanocomposite membranes due to the inclusion of unique features that enhance water and wastewater treatment performance. Compared to the pristine membranes, the incorporation of nanomodifiers not only improves membrane performance (water permeability, salt rejection, contaminant removal, selectivity), but also the intrinsic properties (hydrophilicity, porosity, antifouling properties, antimicrobial properties, mechanical, thermal, and chemical stability) of these membranes. This review focuses on applications of different types of nanomaterials: zero-dimensional (metal/metal oxide nanoparticles), one-dimensional (carbon nanotubes), two-dimensional (graphene and associated structures), and three-dimensional (zeolites and associated frameworks) nanomaterials combined with polymers towards novel polymeric nanocomposites for water and wastewater treatment applications. This review will show that combinations of nanomaterials and polymers impart enhanced features into the pristine membrane; however, the underlying issues associated with the modification processes and environmental impact of these membranes are less obvious. This review also highlights the utility of computational methods toward understanding the structural and functional properties of the membranes. Here, we highlight the fabrication methods, advantages, challenges, environmental impact, and future scope of these advanced polymeric nanocomposite membrane based systems for water and wastewater treatment applications.

Self-Assembly-Directed Exciton Diffusion in Solution-Processable Metalloporphyrin Thin Films.

The study of excited-state energy diffusion has had an important impact in the development and optimization of organic electronics. For instance, optimizing excited-state energy migration in the photoactive layer in an organic solar cell device has been shown to yield efficient solar energy conversion. Despite the crucial role that energy migration plays in molecular electronic device physics, there is still a great deal to be explored to establish how molecular orientation impacts energy diffusion mechanisms. In this work, we have synthesized a new library of solution-processable, Zn (alkoxycarbonyl)phenylporphyrins containing butyl (ZnTCB4PP), hexyl (ZnTCH4PP), 2-ethylhexyl (ZnTCEH4PP), and octyl (ZnTCO4PP) alkoxycarbonyl groups. We establish that, by varying the length of the peripheral alkyl chains on the metalloporphyrin macrocycle, preferential orientation and molecular self-assembly is observed in solution-processed thin films. The resultant arrangement of molecules consequently affects the electronic and photophysical characteristics of the metalloporphyrin thin films. The various molecular arrangements in the porphyrin thin films and their resultant impact were determined using UV-Vis absorption spectroscopy, steady-state and time-resolved fluorescence emission lifetimes, and X-ray diffraction in thin films. The films were doped with C60 quencher molecules and the change in fluorescence was measured to derive a relative quenching efficiency. Using emission decay, relative quenching efficiency, and dopant volume fraction as input, insights on exciton diffusion coefficient and exciton diffusion lengths were obtained from a Monte Carlo simulation. The octyl derivative (ZnTCO4PP) showed the strongest relative fluorescence quenching and, therefore, the highest exciton diffusion coefficient (5.29 × 10-3 cm2 s-1) and longest exciton diffusion length (~81 nm). The octyl derivative also showed the strongest out-of-plane stacking among the metalloporphyrins studied. This work demonstrates how molecular self-assembly can be used to modulate and direct exciton diffusion in solution-processable metalloporphyrin thin films engineered for optoelectronic and photonic applications.