Nickel(II) Bisporphyrin-Fused Pentacenes Exhibiting Abnormal High Stability

A series of largely π-extended multichromophoric molecules including cross-conjugated, half cross-conjugated, conjugation-interrupted and linearly conjugated systems were synthesized and characterized. These multichromophoric molecular systems revealed interesting structural-property relationships. Bisporphyrin-fused pentacenes Pen-1 b and Pen-2 a showed rich redox chemistry with 7 and 8 observable redox states, respectively. The linearly-conjugated bisporphyrin-fused pentacenes ( Pen-1 b and Pen-2 a ) possess much narrower HOMO–LUMO gaps (1.65 and 1.42 eV redox, respectively) and higher HOMO energy levels than those of their pentacene analogues (2.23 and 2.01 eV redox, respectively), similar to those of much less stable hexacenes and heptacenes. An estimated half-life of >945 h was obtained for bisporphyrin-fused pentacene Pen-2 a , which is much longer than that of its pentacene analogue ( BPE-P , half-life, 33 h).     

Towards Efficient and Photostable Red-Emitting Photonic Materials Based on Symmetric All-BODIPY-Triads, -Pentads,and -Hexads

The development of efficient and stable red and near-IR emitting materials under hard radiation doses and/or prolonged times is a sought-after task due to their widespread applications in optoelectronics and biophotonics. To this aim, novel symmetric all-BODIPY-triads, -pentads, and -hexads have been designed and synthesized as light-harvesting arrays. These photonic materials are spectrally active in the 655–730 nm region and display high molar absorption across UV–visible region. Furthermore, they provide, to the best of our knowledge, the highest lasing efficiency (up to 68 %) and the highest photostability (tolerance >1300 GJ mol⁻¹) in the near-IR spectral region ever recorded under drastic pumping conditions. Additionally, the modular synthetic strategy to access the cassettes allows the systematic study of their photonic behavior related to structural factors. Collectively, the outstanding behavior of these multichromophoric photonic materials provides the keystone for engineering multifunctional systems to expedite the next generation of effective red optical materials.