Synthesis and Physical Properties of a Perylene Diimide-Embedded Chiral Conjugated Macrocycle

Abstract

Herein, we report the facile synthesis and properties of a chiral perylene diimide (PDI)-embedded conjugated macrocycle (cyclo[6]paraphenylene-1,7-perylene diimide, [6]CPP-PDI 1,7 ) by Pd-catalyzed Suzuki coupling and a subsequent reductive aromatization reaction in two steps. The PDI-embedded conjugated macrocycle showed a significant redshift (>110 nm for absorption) compared to the PDI molecule. Moreover, efficient resolution of chiral enantiomers with (P)/(M)-[6]CPP-PDI 1,7 was achieved by high-performance liquid chromatography, and their chiral properties were investigated by circular dichroism spectroscopy. The realization of [6]CPP-PDI 1,7 expands the scope of the precise synthesis of PDI-embedded chiral conjugated macrocycles and explores its unique physical properties.

Investigating the diastereoselective synthesis of a macrocycle under Curtin–Hammett control

“…Notes and references ‡ Throughout, we use the chiral nomenclature of P/M for PDIs, which is based on the Cahn-Ingold-Prelog priority rules for molecules with axial chirality. 23,46 This ensures clear comparisons against the axial chirality of BINOL (P/M). § Since this hydrogen bond involves a triazole heterocycle which is formed during the ring-closing of the macrocycle it is less likely to contribute towards differences in stability of the macrocyclisation transition state (Fig.…”

“…15 This is because PDIs may be twisted through substitution at their bay positions (1, 6, 7, 12) to generate atropisomers ( P or M )‡‡Throughout, we use the chiral nomenclature of P / M for PDIs, which is based on the Cahn–Ingold–Prelog priority rules for molecules with axial chirality. 23,46 This ensures clear comparisons against the axial chirality of BINOL ( P / M ). with distinct chiroptical spectra, 16 while their potential for π–π aromatic stacking interactions, 17 including with complementary π-donors, 18 gives rise to an extensive supramolecular chemistry. 15 Alongside functional complexes, 19 cages, 20 and polymers, 21 macrocycles containing twisted PDIs have been developed to explore homo- and heterochirality.…”

Perylene-diimide for organic solar cells: current scenario and prospects in molecular geometric, functionalization, and optoelectronic properties

“…59,60 There has been a recent trend in the scientic literature that seems to show that expanding the number of PDIs attached from the core can lead to an increase in PCE. [61][62][63][64][65][66][67][68][69] In addition, PDI, a commercial pigment, is widely available in enormous numbers and at a low cost. Therefore, the amount of PDI moiety present in acceptors signicantly affects the photovoltaic performance of these acceptors, which in turn inuences spectrum absorption, molecular structure twisting, active layer shape, exciton dissociation, and carrier movement, as well as overall power conversion efficiency (PCE).…”

A Chirally Locked Bis-perylene Diimide Macrocycle: Consequences for Chiral Self-Assembly and Circularly Polarized Luminescence

“…Importantly, the organic dye must be configurationally stable to assess the impact of optical purity on π–π-directed self-assembly (i.e., to compare racemic and enantiopure materials). Of the handful of configurationally stable disubstituted PDIs reported (Δ G ⧧ > 117 kJ mol –1 ), ,, π–π self-assembly is limited to the formation of H-type dimers. , This is because macrocyclic strapping via the 1,7 bay positions, a necessity for preventing atropisomer interconversion, restricts π–π interactions to only one of the π-surfaces of the mono-PDI macrocycle (Figure a).…”