Planar hexaphyrin-like macrocycles turning into bis-BODIPYs with box-shaped structures exhibiting excitonic coupling

Abstract

Planar carbazole based hexaphyrin-like macrocycles with bis-coordinating cores and box-shaped cyclic BODIPYs were synthesized. Solution and solid-state structure of free macrocycles indicates an inversion of two pyrrole rings resulting in...

Conformationally Distinct [26]Heterorubyrin(1.1.0.1.1.0) Macrocycles and Their Bis-BODIPYs: Synthesis, Structure, and Optical Properties

“…Herein, we adopted a modified synthetic strategy by condensing modified tripyrranes 3a , b with pentafluorobenzaldehyde to accomplish rubyrins S 2 N 4 and O 2 N 4 . Interestingly, these new heterorubyrins provided the corresponding bis-BODIPYs upon BF 2 complexation in conjunction with our recent report on cyclic-BODIPYs derived from a hexaphyrin-like macrocycle . Further, we explored their structural and photophysical properties and corroborated with DFT results.…”

“…Interestingly, these new heterorubyrins provided the corresponding bis-BODIPYs upon BF 2 complexation in conjunction with our recent report on cyclic-BODIPYs derived from a hexaphyrin-like macrocycle. 18 Further, we explored their structural and photophysical properties and corroborated with DFT results. We began our synthesis from 1a,b, which were previously reported from our group.…”

Unravelling the excited state dynamics of monofunctionalized mono- and distyryl-BODIPY and perylenediimide dyads

“…13 The efficiency of light-harvesting can be enhanced by harnessing excitonic coupling among the chromophores, which has been recently reported for cyclic BODIPY derivatives. 14 Their spectral profile can be tuned to bathochromic shifts by various structural modifications, and common strategies include functionalization at the b-position, [15][16][17] fusing aromatic rings to the pyrrole moieties 18,19 or functionalization through the C-3 and C-5 positions [20][21][22] of BODIPY to extend the conjugation. The methyl groups on the C-3 and C-5 position of BODIPY undergo facile Knoevenagel condensation reactions yielding monostyryl-BODIPY (MSBDP) and distyryl-BODIPY (DSBDP) derivatives, resulting in extension of p-conjugation and hence bathochromically shifted absorption and emission compared to core-unsubstituted BODIPY.…”

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

“…Recently, covalent arrangements of BODIPYs (BF 2 -dipyrromethenes), including oligomers and arrays, [21][22][23][24][25][26] have attracted attention as complements to simple monomeric BODIPYs. The strong exciton coupling 22,24 expected for systems containing more than one BODIPY-like subunit has made such systems of interest in the context of specic applications, including lightharvesting, uorescence-based sensor development, and photodynamic therapy (PDT). [27][28][29][30][31][32][33] Recently, Werz and co-workers prepared a series of benzene-fused oligo-BODIPYs containing up to 31 rings that exhibited intriguing NIRabsorbing and redox properties.…”

“…Recently, covalent arrangements of BODIPYs (BF 2 -dipyrromethenes), including oligomers and arrays, 21–26 have attracted attention as complements to simple monomeric BODIPYs. The strong exciton coupling 22,24 expected for systems containing more than one BODIPY-like subunit has made such systems of interest in the context of specific applications, including light-harvesting, fluorescence-based sensor development, and photodynamic therapy (PDT). 27–33 Recently, Werz and co-workers prepared a series of benzene-fused oligo-BODIPYs containing up to 31 rings that exhibited intriguing NIR-absorbing and redox properties.…”