Aerobic Solid State Red Phosphorescence from Benzobismole Monomers and Patternable Self‐Assembled Block Copolymers

Abstract

The synthesis of the first bismuth‐containing macromolecules that exhibit phosphorescence in the solid state and in the presence of oxygen is reported. These red emissive high molecular weight polymers (>300 kDa) feature benzobismoles appended to a hydrocarbon scaffold, and were built via an efficient ring‐opening metathesis (ROMP) protocol. Moreover, our general procedure readily allows for the formation of cross‐linked networks and block copolymers. Attaining stable red phosphorescence with non‐toxic elements remains a challenge and, thus, our new class of soluble (processable) polymeric phosphor is of great interest. Furthermore, the formation of bismuth‐rich cores within organic–inorganic block copolymer spherical micelles is possible, leading to patterned arrays of bismuth in the film state.

Self‐Assembly of Macrocyclic Boronic Esters Bearing Tellurophene Moieties and Their Guest‐Responsive Phosphorescence

“…[16] The predicted absorption spectra for homo-[2+ +2] Te and hetero-[2+ +2] Te are in agreement with the experimental UV/Vis data and in both cases, the molecular orbitals involved in the transitions with significant oscillator strength show substantial contribution from the heavy Te atom. This observation mirrors those found in previous Rivard group studies involving phosphorescent tellurophenes [3,17] and bismoles: [18] one needs orbital participation from the heavy element to gain access to ef- fective phosphorescence. The predicted gas-phase absorption spectrum of 3@hetero-[2+ +2] Te confirms the redshift observed in the experimental solutiona nd solid state absorption spectra (Figure 7).…”

Heavier pnictogens – treasures for optical electronic and reactivity tuning

“…After polymerisation, there was a 60 nm red shift in the luminescence and a decrease in intensity, attributed to increased free volume around the bismoles as well as stabilisation of singlet and triplet states. 43…”

Synthesis, Structural Characterization, and Optical Properties of Benzene-Fused Tetracyclic and Pentacyclic Stiboles

“…Arsoles, containing the homologous element, arsenic, have been reported as luminescent substances that are less likely to be oxidized than phospholes, although toxicity is a concern [7][8][9][10][11]. Antimony, another homologue located in the fifth period of group 15 elements in the periodic table, is expected to impart phosphorescence similarly to bismuth and tellurium based on the "heavy element effect", in contrast to lighter elements such as phosphorus [12][13][14][15][16]. Furthermore, since antimony compounds such as sodium stibogluconate (Pentostam) are used as first-line drugs for leishmaniasis [17] and are less toxic than bismuth compounds [18][19][20]; they have also garnered attention in the field of biology [21].…”