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Difluoroboron avobenzone (BF(2)AVB), a simple boron complex of a commercial sunscreen product, exhibits morphology-dependent emission and mechanochromic luminescence in the solid state. When scratched, smeared, or even gently touched, the emission color of BF(2)AVB films is significantly red-shifted under UV excitation. In the rubbed regions, the fluorescence recovers slowly at room temperature or much faster with heating, resulting in a simple rewritable "scratch the surface" ink of potential commercial use.

Boron difluoride compounds are light emitting materials with impressive optical properties. Though their strong one- and two-photon absorption and intense fluorescence are well-known and exploited in molecular probes, lasers, and photosensitizers, phosphorescence, in contrast, is typically observed only at low temperatures. Here, we report that unusual room-temperature phosphorescence is achieved by combining a classic boron dye, difluoroboron dibenzoylmethane, BF2dbm, with poly(lactic acid) (PLA), a common biopolymer, resulting in a highly sensitive single-component oxygen sensor. Fluorescence quantum yields are enhanced, and temperature-sensitive delayed fluorescence is also observed. Multi-emissive BF2dbmPLA biomaterials show great promise as multifunctional molecular probes and sensors.

The synthesis of a series of polymeric Eu(III) complexes with polyester ligands, along with supporting emission spectra, luminescence lifetimes, and, for a Eu block copolymer film, atomic force microscopy (AFM) data, is presented. Dibenzoylmethane was derivatized with a hydroxyl initiator site (dbmOH, 1) for tin octoate catalyzed ring opening polymerization of dl-lactide. The resulting poly(lactic acid) macroligand, dbmPLA (2), was combined with EuCl3 to generate Eu(dbmPLA)3 (3). Chelation of both dbmPLA and a polycaprolactone-functionalized bipyridine ligand (bpyPCL2) led to the Eu(III)-centered heteroarm star Eu(dbmPLA)3(bpyPCL2) (4). Unpolarized emission spectra and luminescence lifetimes were recorded for the Eu polymers in CH2Cl2 and for Eu(dbmPLA)3, as a film. Solution data for Eu(dbm)3 and Eu(dbm)3(bpy) were collected for comparison. For Eu tris(dbm) complexes, data were fit to a double exponential decay, indicating the presence of multiple species. Relative amounts of the longer lifetime component increase in the series Eu(dbm)3 solutions to Eu(dbmPLA)3 solutions to Eu(dbmPLA)3 films, perhaps suggesting benefits of the "polymer shell effect" and the diminishment of aquo adducts known to shorten lifetimes. As with the nonpolymeric analogue, data for Eu(dbmPLA)3(bpyPCL2) fit to a single-exponential decay. The sharpness of the feature at 579.7 nm, attributable to the 5D0 --> 7F0 transition in the emission spectrum of 4, lends further support for a homogeneous sample. AFM studies of "as cast" thin films of 4 reveal a lamellar structure with a 17.5 nm repeat. These microstructures, inferred to contain Eu luminophores at the glassy PLA-crystalline PCL domain interfaces, are modified by thermal treatment.

Poly(lactic acid) (PLA)-supported dibenzoylmethane (dbm) and corresponding metal complexes have potential applications as biomaterials and catalysts. Using hydroxyl-functionalized dbm (i.e., dbmOH) as the initiator and Sn(oct)2 as the catalyst, lactide ring-opening polymerizations were unexpectedly slow (6 h), and PDIs broadened when molecular weights10 000 were targeted. Because interactions between the dbm ligand and Sn(oct)2 may be responsible for the diminished catalyst activity and molecular weight control, iron(III) was employed as a protecting group to form Fe(dbmOH)3. Shorter reaction times (10 min) were noted with this trifunctional metalloinitiator and Sn(oct)2, and higher molecular weights were achievable. Moreover, it was discovered that Fe(dbmOH)3 serves not only as an initiator but also as a catalyst and activating group for the polymerization. Even without the tin catalyst, iron-centered polymers with low PDIs (1.1) were obtained within 10 min ( approximately 70% monomer conversion). The resulting Fe(dbmPLA)3 stars were demetalated by acid treatment to generate dbmPLA for subsequent coordination to other metals. To explore the scope of iron beta-diketonate complexes as catalysts, additional studies were performed with dbmOH and benzyl alcohol initiators using either iron tris(dbm) or iron tris(acac) (acac = acetylacetonate) as the catalyst. Here too, PLA products were obtained, and the iron catalysts were readily separated by treatment with aqueous HCl.