Cover Feature: Testing the Limits of the BOPHY Platform: Preparation, Characterization, and Theoretical Modeling of BOPHYs and Organometallic BOPHYs with Electron‐Withdrawing Groups at β‐Pyrrolic and Bridging Positions (Chem. Eur. J. 59/2017)

Abstract

As part of our continuing investigations into the BOPHY fluorophore, we have started to explore the cyanation of derivatives both with and without ferrocene. Upon functionalization of BOPHY with cyanide, however, extrusion of a BF2 unit is observed, resulting in a “half‐BOPHY” compound, which exhibits reduced emission. The introduction of a CN unit reduces the basicity of the bridging hydrazine. More information can be found in the Full Paper by V. N. Nemykin et al. on page 14786.

Catalytic Synthesis of Donor-Acceptor-Donor (D-A-D) and Donor-Acceptor-Acceptor (D-A-A) Pyrimidine-Ferrocenes via Acceptorless Dehydrogenative Coupling: Synthesis, Structures, and Electronic Communication

“…Instead, oxidation of both compounds is accompanied by a decrease in intensity of the far UV feature ( 2 : 355 nm, 3 : 371 nm) and a growth of a peak overlapping with the lowest energy absorption of the neutral species ( 2 : 470 nm, 3 : shoulder at ∼460 nm). Similar spectral changes were observed for oxidation of the ferrocenyl units in ferrocene-BODIPY conjugates , and related (di)­ferrocenyl-substituted D-A-D triads with conjugated cores such as bis­(difluoroboron)-1,2-bis­{(pyrrol-2-yl)­methylene}­hydrazine (BOPHY) . In those systems, oxidation results in the appearance of a band also at shorter wavelengths compared with typical ferrocenium derivatives (∼530 nm).…”

“…Similar spectral changes were observed for oxidation of the ferrocenyl units in ferrocene-BODIPY conjugates 16,46 and related (di)ferrocenylsubstituted D-A-D triads with conjugated cores such as bis(difluoroboron)-1,2-bis{(pyrrol-2-yl)methylene}hydrazine (BOPHY). 56 In those systems, oxidation results in the appearance of a band also at shorter wavelengths compared with typical ferrocenium derivatives (∼530 nm).…”