Spin–Orbit Charge-Transfer Intersystem Crossing (ISC) in Compact Electron Donor–Acceptor Dyads: ISC Mechanism and Application as Novel and Potent Photodynamic Therapy Reagents

Spin–orbit charge-transfer intersystem crossing (SOCT-ISC) is useful for the preparation of heavy atom-free triplet photosensitisers (PSs). Herein, a series of perylene-Bodipy compact electron donor/acceptor dyads showing efficient SOCT-ISC is prepared. The photophysical properties of the dyads were studied with steady-state and time-resolved spectroscopies. Efficient triplet state formation (quantum yield Φ_T=60 %) was observed, with a triplet state lifetime (τ_T=436 μs) much longer than that accessed with the conventional heavy atom effect (τ_T=62 μs). The SOCT-ISC mechanism was unambiguously confirmed by direct excitation of the charge transfer (CT) absorption band by using nanosecond transient absorption spectroscopy and time-resolved electron paramagnetic resonance (TREPR) spectroscopy. The factors affecting the SOCT-ISC efficiency include the geometry, the potential energy surface of the torsion, the spin density for the atoms of the linker, solvent polarity, and the energy matching of the ¹CT/³LE states. Remarkably, these heavy atom-free triplet PSs were demonstrated as a new type of efficient photodynamic therapy (PDT) reagents (phototoxicity, EC₅₀=75 nm ), with a negligible dark toxicity (EC₅₀=78.1 μm ) compared with the conventional heavy atom PSs (dark toxicity, EC₅₀=6.0 μm, light toxicity, EC₅₀=4.0 nm ). This study provides in-depth understanding of the SOCT-ISC, unveils the design principles of triplet PSs based on SOCT-ISC, and underlines their application as a new generation of potent PDT reagents.     

Tuning the Triplet Excited State of Bis(dipyrrin) Zinc(II) Complexes: Symmetry Breaking Charge Transfer Architecture with Exceptionally Long Lived Triplet State for Upconversion

Zinc(II) bis(dipyrrin) complexes, which feature intense visible absorption and efficient symmetry breaking charge transfer (SBCT) are outstanding candidates for photovoltaics but their short lived triplet states limit applications in several areas. Herein we demonstrate that triplet excited state dynamics of bis(dipyrrin) complexes can be efficiently tuned by attaching electron donating aryl moieties at the 5,5′-position of the complexes. For the first time, a long lived triplet excited state (τ_T=296 μs) along with efficient ISC ability (Φ_Δ=71 %) was observed for zinc(II) bis(dipyrrin) complexes, formed via SBCT. The results revealed that molecular geometry and energy gap between the charge transfer (CT) state and triplet energy levels strongly control the triplet excited state properties of the complexes. An efficient triplet–triplet annihilation upconversion system was devised for the first time using a SBCT architecture as triplet photosensitizer, reaching a high upconversion quantum yield of 6.2 %. Our findings provide a blueprint for the development of triplet photosensitizers based on earth abundant metal complexes with long lived triplet state for revolutionary photochemical applications.     

On a supplementary conservation law for the energy equation in a rigid heat conductor

We consider a rigid heat conductor with specified constitutive equations and show that the internal energy equation may be written in the form of a symmetric and conservative hyperbolic system of first order quasi-linear equations for which the Cauchy problem is well-posed. Moreover, such a system is useful to study shocks. Several particular cases are examined.     

Some extremum theorems for the elastoplastic boundary value problem in the presence of large displacements

Summary The incremental boundary value problem for elastoplastic work-hardening continua, is discussed in the presence of large displacements but small strains, and allowing for distributed dislocations.Associated flow laws are assumed, as is the occurrence of interaction between yielding modes in singular points of the yield surface.Four extremum theorems are proved which reduce the problem to the optimization, under linear constraints, of convex quadratic forms (of a non linear form for the third theorem).Finally some results are specialized to small displacements and perfectly plastic (non hardening) cases.

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Sommario Si discute della soluzione incrementale del problema elastoplastico con incrudimento nel campo dei grandi spostamenti (ma con piccole deformazioni intrinseche), ed in presenza di distorsioni distribuite.Si assumono leggi costitutive del tipo associato, ammettendo la possibilità di interazione tra i modi plastici in corrispondenza dei punti singolari della superficie di snervamento.Si dimostrano quattro proprietà di minimo della soluzione; esse riconducono il problema alla ottimizzazione di funzionali convessi (quadratici tranne che nel caso del terzo teorema) vincolata da equazioni e diseguaglianze lineari.Si specializzano infine alcuni risultati al caso dei piccoli spostamenti e della elastoplasticità senza incrudimento.

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This study forms part of a research programme supported by the National (Italian) Research Council (C.N.R., Gruppo Plasticità).     

Separable geodesic action slicing in stationary spacetimes

A simple observation about the action for geodesics in a stationary spacetime with separable geodesic equations leads to a natural class of slicings of that spacetime whose orthogonal geodesic trajectories represent the world lines of freely falling fiducial observers. The time coordinate function can then be taken to be the observer proper time, leading to a unit lapse function, although the time coordinate lines still follow Killing trajectories to retain the explicitly stationary nature of the coordinate grid. This explains some of the properties of the original Painlevé-Gullstrand coordinates on the Schwarzschild spacetime and their generalization to the Kerr-Newman family of spacetimes, reproducible also locally for the Gödel spacetime. For the static spherically symmetric case the slicing can be chosen to be intrinsically flat with spherically symmetric geodesic observers, leaving all the gravitational field information in the shift vector field.