Dipolar Photosystems: Engineering Oriented Push–Pull Components into Double‐ and Triple‐Channel Surface Architectures

Abstract

Push-pull aromatics are not popular as optoelectronic materials because their supramolecular organization is difficult to control. However, recent progress with synthetic methods has suggested that the directional integration of push-pull components into multicomponent photosystems should become possible. In this study, we report the design, synthesis, and evaluation of double- or triple-channel architectures that contain π stacks with push-pull components in parallel or mixed orientation. Moreover, the parallel push-pull stacks were uniformly oriented with regard to co-axial stacks, either with inward or outward oriented push-pull dipoles. Hole-transporting (p) aminoperylenemonoimides (APIs) and aminonaphthalimides (ANIs) are explored for ordered push-pull stacks. For the co-axial electron-transporting (n) stacks, naphthalenediimides (NDIs) are used. In double-channel photosystems, mixed push-pull stacks are overall less active than parallel push-pull stacks. The orientation of the parallel push-pull stacks with regard to the co-axial NDI stacks has little influence on activity. In triple-channel photosystems, outward-directed dipoles in bridging stacks between peripheral p and central n channels show higher activity than inward-directed dipolar stacks. Higher activities in response to direct irradiation of outward-directed parallel stacks reveal the occurrence of quite remarkable optical gating.

Sidechain Engineering in Cell‐Penetrating Poly(disulfide)s

“…However, the availability of reloaded CPDs such as 10 was also of practical interest because increasing uptake activity of monomers 3 – 5 with increasing tension suggested that similar increases in activity could be achieved on the level of the intrinsically much more active polymers. Because of much experience with orthogonal dynamic covalent chemistry in different contexts,[15][17] hydrazone exchange was initially envisioned for sidechain modification of CPDs. However, the results were not convincing (not shown).…”

“…Sidechain modification of polymers is of general interest to avoid tedious optimization of polymerization conditions with every structural modification and to produce comparable functional systems with identical scaffold [4 – 6][12] [15 – 21]. Synthetic strategies that in part have been applied previously to synthetic transport systems include the formation of hydrazones,[4][15][16] sulfonium cations,[6] boronate esters,[17] amides,[12] thioesters,[18] disulfides,[19] diselenides,[20] triazoles,[5][21] and so on. In the following, we introduce a general method for sidechain modification of CPDs to secure synthetic access to comparable systems.…”

Engineering pH-responsive switching of donor–π–acceptor chromophore alignments along a peptide nanotube scaffold

“…2 Another useful point of D-p-A molecules is the large dipole moment generated in the molecule, which can be used to facilitate a charge separation process upon molecular excitation by resisting against the large exciton binding energy. 3,4 A p-type organic semiconductor showing a carrier mobility up to 20 cm 2 V À1 s À1 has been attained by polymer carrying D and A substituents, and an n-type organic semiconductor of nearly 10 cm 2 V À1 s À1 as well. 5 The performances of those organic semiconductors are determined mainly by two factors of organic molecules themselves and their mutual arrangement in the nm-size devices.…”

Perylene Monoimide Dimers Enhance Ternary Organic Solar Cells Efficiency by Induced D–A Crystallinity

“…PMI recently appeared as an important dye and a versatile building block for organic electronics. − Its sister molecule perylene diimides (PDI) already successfully was used as NF acceptors for OSCs. − However, using PMI for NF acceptors are rarely reported presumably due to the difficulty of large-scale synthesis. , But PMI also possesses strong light absorption ability and good photostability; in particular, it has a higher-lying lowest unoccupied molecular orbital (LUMO) compared to PDI, which could be good for high V oc of OSCs. , For PMI NF candidates, the linker group between two PMI greatly tailor the comprehensive properties of NF acceptors. Regular bridge units such as thiophene or benzyl or other aryl group-linked A–D–A type (A = PMI) NF shows poor photovoltaic performance .…”