Dye-sensitized solar cells based on multichromophoric supramolecular light-harvesting materials.

Multichromophoric dye-sensitized solar cells (DSSCs) comprised of a supramolecular zinc-phthalocyanineperyleneimide (ZnPc···PMI) dyad convert light to electrical energy with much higher power conversion efficiency (PCE = 2.3%) and incident-photon-to-current-efficiency (IPCE = ca. 40%) than the devices made of individual dyes.

Tunable electronic interactions between anions and perylenediimide.

Over the past decade anion-π interaction has emerged as a new paradigm of supramolecular chemistry of anions. Taking advantage of the electronic nature of anion-π interaction, we have expanded its boundaries to charge-transfer (CT) and formal electron transfer (ET) events by adjusting the electron-donating and accepting abilities of anions and π-acids, respectively. To establish that ET, CT, and anion-π interactions could take place between different anions and π-acids as long as their electronic and structural properties are conducive, herein, we introduce 3,4,9,10-perylenediimide (PDI-1) that selectively undergoes thermal ET from strong Lewis basic hydroxide and fluoride anions, but remains electronically and optically silent to poor Lewis basic anions, as ET and CT events are turned OFF.

Multichromophoric dye-sensitized solar cells based on supramolecular zinc-porphyrin···perylene-imide dyads.

Multichromophoric dye-sensitized solar cells (DSCs) based on self-assembled zinc-porphyrin···peryleneimide dyads on TiO(2) films display more efficient light-to-electrical energy conversion than DSCs based on individual dyes. Higher efficiency of multichromophoric dyes can be attributed to co-sensitization as well as vectorial electron transfer that lead to better electron-hole separation in the device.

Boundaries of anion/naphthalenediimide interactions: from anion-π interactions to anion-induced charge-transfer and electron-transfer phenomena.

The recent emergence of anion-π interactions has added a new dimension to supramolecular chemistry of anions. Yet, after a decade since its inception, actual mechanisms of anion-π interactions remain highly debated. To elicit a complete and accurate understanding of how different anions interact with π-electron-deficient 1,4,5,8-naphthalenediimides (NDIs) under different conditions, we have extensively studied these interactions using powerful experimental techniques.

Electronically regulated thermally and light-gated electron transfer from anions to naphthalenediimides.

Anion-induced electron transfer (ET) to π-electron-deficient naphthalenediimides (NDIs) can be channeled through two distinct pathways by adjusting the Lewis basicity of the anion and the π-acidity of the NDI: (1) When the anion and NDI are a strong electron donor and acceptor, respectively, positioning the HOMO of the anion above the LUMO of the NDI, a thermal anion → NDI ET pathway is turned ON. (2) When the HOMO of a weakly Lewis basic anion falls below the LUMO of an NDI but still lies above its HOMO, the thermal ET is turned OFF, but light can activate an unprecedented anion → (1)*NDI photoinduced ET pathway from the anion's HOMO to the photogenerated (1)*NDI's SOMO-1. Both pathways generate NDI(•-) radical anions.