Acetylene-Derived Strong Organic Acceptors for Planar and Nonplanar Push−Pull Chromophores

Abstract

Though investigated for decades, interest in push-pull chromophores (D-pi-A), strong electron donors (D) connected by pi-conjugating spacers to strong electron acceptors (A), continues to grow. Such chromophores are of substantial interest for optoelectronic devices such as waveguides. Also, strong donors and acceptors form bimolecular charge-transfer (CT) complexes and salts, some of which exhibit electrical conductivity and magnetic behavior. Furthermore, strong organic acceptors are increasingly explored as dopants in the fabrication of organic light-emitting diodes (OLEDs) and solar cells. This Account describes systematic efforts pursued over the past decade in our laboratory to generate new families of organic electron acceptors (A) and conjugate them via pi-spacers to electron donors (D) under formation of push-pull systems with intense intramolecular CT interactions and high third-order optical nonlinearities. First, we describe donor-acceptor-substituted tetraethynylethenes (TEEs). In these chromophores, the peripherally attached p-nitrophenyl acceptors and N,N-dimethylanilino donors behave as nearly independent redox centers. Acetylenic scaffolding using TEE building blocks produces large all-carbon sheets, such as perethynylated dehydroannulenes, expanded radialenes, and radiaannulenes with potent electron-acceptor properties. Arylated TEEs act as molecular switches allowing two-way photochemical interconversion that is not perturbed by thermal isomerization pathways. Upon sequential substitution of the acetylene moieties in TEEs, we formed another family of potent acceptors, the cyanoethynylethenes (CEEs). Donor-substituted CEEs are planar CT chromophores with very high third-order optical nonlinearities. Their high environmental stability allows for the formation of thin films by vapor-phase deposition. Through careful analysis of the physicochemical properties of CEEs, we established useful guidelines for evaluating and tuning the optical gap in strong push-pull chromophores: increasing the length of the pi-spacer in D-pi-A systems reduces ground-state D-A conjugation and lowers the HOMO-LUMO gap. By taking advantage of "click-chemistry"-type [2 + 2] cycloadditions of tetracyanoethene (TCNE) and 7,7,8,8-tetracyanoquinodimethane (TCNQ) with appropriately activated alkynes, followed by retro-electrocyclization, the formation of donor-substituted 1,1,4,4-tetracyanobuta-1,3-dienes (TCBDs), 1,1,2,4,4-pentacyanobuta-1,3-dienes (PCBDs), and novel TCNQ adducts is possible. Some of these stable, nonplanar CT chromophores form high optical quality amorphous thin films by vapor-phase deposition. Despite donor substitution, the new acceptors (TCBDs, PCBDs, and the TCNQ adducts) rival TCNE and TCNQ in their ease for reversible electron uptake. High-yielding cycloaddition/retro-electrocyclization cascades provide access to multivalent, dendritic chromophores acting as "molecular batteries" with a remarkable capacity for multiple electron uptake in a narrow potential range. Finally, we used a one-pot protocol for electronically controlled consecutive TCNE and tetrathiafulvalene (TTF) additions to end-capped polyynes to form [AB]-type oligomers with a dendralene-type backbone.