Synthesis and dark state EPR properties of PDI-trityl dyads and triads.

Covalently-linked chromophore-radical systems with their unique optical and magnetic properties are useful for applications in, e. g., quantum information science. To expand the catalog of molecular systems, we synthesized and characterized six novel chromophore-radical and radical-chromophore-radical systems employing derivatives of perylene diimide (PDI) as the chromophore and trityl as the radical. The EPR properties of these compounds were evaluated in solution at cryogenic and room temperatures. In addition, the electron spin-spin coupling in the two bistrityl systems was investigated using DQC measurements. The presented results serve as a basis for further spectroscopic investigations under photoexcitation of the PDI core.

Magneto-Structural Correlations in a Mixed Porphyrin(Cu2+ )/Trityl Spin System: Magnitude, Sign, and Distribution of the Exchange Coupling Constant.

Tetrathiatriarylmethyl radicals (TAM or trityl) are receiving increasing attention in various fields of magnetic resonance such as imaging, dynamic nuclear polarization, spin labeling, and, more recently, molecular magnetism and quantum information technology. Here, a trityl radical attached via a phenyl bridge to a copper(II)tetraphenylporphyrin was synthesized, and its magnetic properties studied by multi-frequency continuous-wave electron paramagnetic resonance (EPR) spectroscopy and magnetic measurements. EPR revealed that the electron spin-spin coupling constant J between the trityl and Cu2+ spin centers is ferromagnetic with a magnitude of -2.3 GHz (-0.077 cm-1 , + J S → 1 S → 2 ${+J{\vec{S}}_{1}{\vec{S}}_{2}}$ convention) and a distribution width of 1.2 GHz (0.040 cm-1 ). With the help of density functional theory (DFT) calculations, the obtained ferromagnetic exchange coupling, which is unusual for para-substituted phenyl-bridged biradicals, could be related to the almost perpendicular orientation of the phenyl linker with respect to the porphyrin and trityl ring planes in the energy minimum, while the J distribution was rationalized by the temperature weighted rotation of the phenyl bridge about the molecular axis connecting both spin centers. This study exemplifies the importance of molecular dynamics for the homogeneity (or heterogeneity) of the magnetic properties of trityl-based systems.

Improved, Odorless Access to Benzo[1,2-d;4,5-d']- bis[1,3]dithioles and Tert-butyl Arylsulfides via C-S Cross Coupling.

Benzo[1,2-d;4,5-d']bis[1,3]dithioles are important building blocks within a range of functional materials such as fluorescent dyes, conjugated polymers, and stable trityl radicals. Access to these is usually gained via tert-butyl aryl sulfides, the synthesis of which requires the use of highly malodorous tert-butyl thiol and relies on SNAr-chemistry requiring harsh reaction conditions, while giving low yields. In the present work, S-tert-butyl isothiouronium bromide is successfully applied as an odorless surrogate for tert-butyl thiol. The C-S bond formation is carried out under palladium catalysis with the thiolate formed in situ resulting in high yields of tert-butyl aryl sulfides. The subsequent formation of benzo[1,2-d;4,5-d']bis[1,3]dithioles is here achieved with scandium(III)triflate, a less harmful reagent than the usually used Lewis acids, e.g., boron trifluoride or tetrafluoroboric acid. This enables a convenient and environmentally more compliant access to high yields of benzo[1,2-d;4,5-d']bis[1,3]dithioles.

PDI-trityl dyads as photogenerated molecular spin qubit candidates.

Owing to their potential applications in the field of quantum information science, photogenerated organic triplet-radical conjugates have attracted an increasing amount of attention recently. Typically, these compounds are composed of a chromophore appended to a stable radical. After initialisation of the system by photoexcitation, a highly spin-polarised quartet state may be generated, which serves as a molecular spin qubit candidate. Here, we investigate three perylene diimide (PDI)-based chromophore-radical systems with different phenylene linkers and radical counterparts by both optical spectroscopy and transient electron paramagnetic resonance (EPR) techniques. Femtosecond transient absorption measurements demonstrate chromophore triplet state formation on a picosecond time scale for PDI-trityl dyads, while excited state deactivation is found to be slowed down considerably in a PDI-nitroxide analogue. The subsequent investigation of the coherent spin properties by transient EPR confirms quartet state formation by triplet-doublet spin mixing for all investigated dyads and the suitability of the two studied PDI-trityl dyads as spin qubit candidates. In particular, we show that using tetrathiaryl trityl as the radical counterpart, an intense spin polarisation is observed even at room temperature and quartet state coherence times of 3.0 µs can be achieved at 80 K, which represents a considerable improvement compared to previously studied systems.

Heat management strategies for MSW landfills.

Heat is a primary byproduct of landfilling of municipal solid waste. Long-term elevated temperatures have been reported for MSW landfills under different operational conditions and climatic regions around the world. A conceptual framework is presented for management of the heat generated in MSW landfills. Three main strategies are outlined: extraction, regulation, and supplementation. Heat extraction allows for beneficial use of the excess landfill heat as an alternative energy source. Two approaches are provided for the extraction strategy: extracting all of the excess heat above baseline equilibrium conditions in a landfill and extracting only a part of the excess heat above equilibrium conditions to obtain target optimum waste temperatures for maximum gas generation. Heat regulation allows for controlling the waste temperatures to achieve uniform distribution at target levels at a landfill facility. Two approaches are provided for the regulation strategy: redistributing the excess heat across a landfill to obtain uniform target optimum waste temperatures for maximum gas generation and redistributing the excess heat across a landfill to obtain specific target temperatures. Heat supplementation allows for controlling heat generation using external thermal energy sources to achieve target waste temperatures. Two approaches are provided for the supplementation strategy: adding heat to the waste mass using an external energy source to increase waste temperatures and cooling the waste mass using an external energy source to decrease waste temperatures. For all strategies, available landfill heat energy is determined based on the difference between the waste temperatures and the target temperatures. Example analyses using data from landfill facilities with relatively low and high heat generation indicated thermal energy in the range of -48.4 to 72.4MJ/m(3) available for heat management. Further modeling and experimental analyses are needed to verify the effectiveness and feasibility of design, installation, and operation of heat management systems in MSW landfills.

Predictable implant placement with a diagnostic/surgical template and advanced radiographic imaging.

The technique described facilitates precise dental implant placement. A barium-coated template with external guide wires used in conjunction with a computed tomography scan and interactive software may provide superior presurgical diagnostics, treatment planning, and prosthetically directed implant placement. Measurements predetermined on the computed tomography scan can be transferred accurately to the diagnostic/surgical template by use of a precision milled cylinder placed into the template at the proper angulation and linear dimensions. The diagnostic/surgical template shows the surgeon the optimal position for implant placement, thus establishing greater clinical confidence when placing implants.