Controlled assembly of a bicyclic porphyrinoid and its 3-dimensional boron difluoride arrays

Abstract

A fully conjugated cryptand-like bicyclic porphyrinoid ligand 4, incorporating three carbazole linkages and four dipyrrin moieties, was prepared via the acid-catalysed condensation of an extended 2,2′-bipyrrole analogue containing a central carbazole moiety and 3,4-diethyl-2,5-diformylpyrrole in 79% isolated yield. This new cryptand-like system acts as an effective ligand and allows for complexation of BF₂ (boron difluoride) subunits. Three BODIPY arrays, containing two, three, and four BF₂ subunits, namely 4·2BF₂, 4·3BF₂ and 4·4BF₂, could thus be isolated from the reaction of 4 with BF₃·Et₂O in the presence of triethylamine at 110 °C, albeit in relatively low yield. As prepared, bicycle 4 is characterized by a rigid C₂ symmetric structure as inferred from VT NMR spectroscopic analyses. In contrast, the three BODIPY-like arrays produced as the result of BF₂ complexation are conformationally flexible and unsymmetric in nature as deduced from similar analyses. All four products, namely 4, 4·2BF₂, 4·3BF₂ and 4·4BF₂, were characterized by means of single crystal X-ray diffraction analyses. Tetramer 4·4BF₂ gives rise to a higher extinction coefficient (by 2.5 times) relative to the bis- and tris-BODIPY arrays 4·2BF₂ and 4·3BF₂. This was taken as evidence for stronger excitonic coupling in the case of 4·4BF₂. All three BODIPY-like arrays proved nearly non-fluorescent, as expected given their conformationally mobile nature. The efficiency of reactive oxygen species (ROS) generation was also determined for the new BODIPY arrays of this study.