A Guanidine-Based Superbase as Efficient Chemiluminescence Booster

Abstract

We introduce the guanidine-based superbase 1,5,7-triaza-bicyclo-[4.4.0]dec-5-ene (TBD) as efficient enabler for chemiluminescence (CL) based on luminol in a simple, ready-to-use two component system. The strong CL is generated by the superbase’s properties as peroxidase mimetic and bifunctional coreactant. The herein established concept allows for CL enabling molecules (superbases) to be readily implemented in larger molecular structures, including in polymers.

Chemiluminescent self-reporting supramolecular transformations on macromolecular scaffolds

“…Based the high reactivity of acrylate PFP-ester derivatives toward aromatic amines compared to their own methacrylate analogue, 49 the PFPA moiety reacts selectively in an orthogonal manner with luminol, while the PFPMA moiety should be substituted with the superbase derivative. Furthermore, according to the results of the previously reported small molecule study, 21 in which an excess of 5.0 eq. of superbase (i.e.…”

“…A plausible explanation for the immense difference in the CL emission between C1 and C2 lies in the structural difference of the superbase tethered to the polymer backbone. As reported in the literature, 21 the type of the superbase plays a critical role in the CL reaction of luminol, not only as catalyst but also as co-reactant. While the non-cyclic guanidine-derivative in P1/C1 is transformed to the urea functionality in the presence of an oxidant (e.g.…”

“…19,20 Recently, we successfully implemented the organic superbase 1,5,7-triaza-bicyclo-[4.4.0]dec-5-ene (TBD) into the CL reaction of luminol. 21 Without the requirement for additional additives (such as catalysts or enhancers), the CL of a luminol-TBD-mixture in organic media (DMSO) was readily triggered in the presence of hydrogen peroxide (H 2 O 2 ). Indeed, the resulting CL of the system can be observed by the naked eye.…”

A new family of liquid and solid guanidine-based n-type dopants for solution-processed perovskite solar cells

“…Although beyond the scope of this report, there may be added benefits of using superbases like the TBD series as n-type dopants with perovskite solar cells. The ability of TBD and its conjugate Lewis acid to complex, or react, with stray metal atoms, 43,44 CO 2 , 45,46 and reactive oxygen species 47,48 could further improve the stability of devices.…”

Untapped toolbox of luminol based polymers

“…80 Accordingly, a copolymer (LUM-TBD-PMMA) decorated with luminol and a superbase (i.e. 1,5,7-triazabicyclo-[4.4.0]dec-5-ene (TBD)), the latter being essential as a coreactant for the CL response of luminol, 81 was synthesized via sequential free radical polymerization of pentafluorophenyl acrylate (PFPA) and 4-vinyl benzylchloride (VBC) in the presence of methyl methacrylate (MMA), and subsequent orthogonal post-polymerization modification (Scheme 12A). While the PFPA segment reacted selectively in an orthogonal manner with luminol by virtue of the high reactivity of acrylate PFPester derivatives toward aromatic amines, 82 the VBC moiety was substituted with TBD.…”