Promoting photocatalytic CO₂ reduction through facile electronic modification of N-annulated perylene diimide rhenium bipyridine dyads

Abstract

The development of CO2 conversion catalysts has become paramount in the effort to close the carbon loop. Herein, we report the synthesis, characterization, and photocatalytic CO2 reduction performance for a...

Development of Tetrameric N‐Annulated Perylene Diimides Using “Click” Chemistry

“…While the molecular geometry of sbfNPDI 4 and pyrNPDI 4 may be associated with the small phase separated domains and the poor fill factors, we envision that some combination of spacer core and alkyl tether length could promote better domain growth and phase separation, which could ultimately improve charge transport [23] . Moreover, electronic substituents may be functionalized at the opposite bay‐position of NPDI to tune the optoelectronics and energy levels of the multicomponent material to better match the selected electron donor material [20] …”

“…[23] Moreover, electronic substituents may be functionalized at the opposite bay-position of NPDI to tune the optoelectronics and energy levels of the multicomponent material to better match the selected electron donor material. [20]…”

“…Perylene diimides (PDIs) are a class of organic chromophore renowned for having strong molar absorptivity, high electron affinity, as well as excellent thermal, redox, and photo‐ stabilities [1,2] . This combination of desirable chemical and physical properties has made PDI‐based materials ideally suited for a number of applications, including: chemical sensing, [3,4] bioimaging, [5,6] magnetics, [7] charge storage, [8,9] charge transport, [10–12] charge extraction, [13–15] light emission, [16,17] and even small molecule catalysis [18–21] . Depending on the target application, the proclivity for PDI to π‐π stack and form large aggregates in the solid‐state may need to be circumvented to enable high performance [22,23] .…”

“…[1,2] This combination of desirable chemical and physical properties has made PDI-based materials ideally suited for a number of applications, including: chemical sensing, [3,4] bioimaging, [5,6] magnetics, [7] charge storage, [8,9] charge transport, [10][11][12] charge extraction, [13][14][15] light emission, [16,17] and even small molecule catalysis. [18][19][20][21] Depending on the target application, the proclivity for PDI to π-π stack and form large aggregates in the solid-state may need to be circumvented to enable high performance. [22,23] Thus, to prevent PDI overaggregation in the solid-state, it is possible to synthetically introduce a spacer core in between two or more PDI units.…”

“…[44,45] Our lab has also applied "click" chemistry to NPDI, where instead the pyrrolic nitrogen was utilized for "click" chemistry to leave the imide and bay positions available for further functionalization. [19,20,25,26] Herein we report two new NPDI tetramer materials, where "click" chemistry was employed to append four NPDI units to either a spirobifluorene (sbfNPDI 4 ) or a pyrene (pyrNPDI 4 ) core. The influence of spacer core geometry (twisted vs. planar) on the optoelectronic properties was investigated and organic photovoltaic (OPV) devices were fabricated to demonstrate their utility towards optoelectronic applications.…”