NTCDA–TTF first axial fusion: emergent panchromatic, NIR optical, multi-state redox and high optical contrast photooxidation

Abstract

The first synthetic entry into axially fused NTCDA/PMDA-TTF multipolar molecules demonstrates a high optical contrast photooxidation, panchromism, low HOMO-LUMO gap, generation of a stable radical cation, NIR absorption/emission beyond 2150/800 nm and theoretically calculated NLO activity.

Appending Diverse π‐Extended Acceptors with Tetrathiafulvalene/Dithiafulvalene Donors: Multistate Redox Properties, Radical Ion Generation, and Mid‐IR‐Absorbing Mixed‐Valence States

“…Scheme presents a unified synthetic scheme for the TTF/DTF‐appended D–A chromophores. Recently, we reported PMDA and NDA π‐As appended with one or two TTF/DTF units, which were restricted to anhydride‐based systems . Herein, we have expanded the scope of this molecular design to incorporate different π‐As, by altering the anhydride to an imide through pre‐ and post‐functionalization to understand its structural and electronic effects and increase the number of D units.…”

“…Recently,w er eportedP MDA and NDA p-As appendedw ith one or two TTF/DTF units, which were restricted to anhydride-based systems. [14] Herein, we have expanded the scope of this molecular design to incorporate different p-As, by alteringt he anhydride to an imide through pre-and post-functionalization to understand its structurala nd electronic effects and increase the number of D units. Herein, we report the synthesis of new chromophores belonging to classes 1-3, namely,c ompounds 3a, 3b, 4, 7, and 9-12.The design of chromophores (Scheme 1) is based on the investigation of multifaceted D-A chromophores by integrating TTF/DTF units with various p-A moieties.…”

“… Unified synthetic schemes of three classes of TTF/DTF‐appended D–A chromophores ( 1 – 12 ); the gray‐colored dashed enclosure shows molecules reported previously by our group …”

Semiconducting π‐Extended Tetrathiafulvalene Derivatives

“… TTF/dithiafulvene‐appended donor–acceptor chromophores for multistate redox properties, radical ion generation, and mid‐IR‐absorbing mixed‐valence states …”

“…Recently, Mukhopadhyay et al. reported donor–acceptor π‐extended chromophores with TTF/dithiafulvalene donors to show multistate redox properties, radical ion generation, and mid‐IR‐absorbing mixed‐valence states (Figure ) …”