Our group started a research program in acetylene chemistry in 1987; since then, an intense research effort led to a fascinating journey into acetylenic scaffolding, aimed at exploring conjugative and optoelectronic properties of acetylenic chromophores. This journey included the generation of a unique molecular construction kit for acetylenic scaffolding, consisting of (E)-1,2-diethynylethenes [DEEs, (E)-hex-3-ene-1,5-diynes], tetraethynylethenes (TEEs, 3,4-diethynylhex-3-ene-1,5-diynes), chiral 1,3-diethynylallenes (DEAs, hepta-3,4-diene-1,6-diynes), 1,4-di and 1,1,4,4-tetraethynylbutatrienes, chiral trialkynylmethanes, and 1,1,2,2-tetraethynylethanes. These building modules were subsequently applied to the synthesis of carbon-rich architectures extending into one, two, and three dimensions. They include multinanometer-long monodisperse oligomers as models for infinite acetylenic polymers, molecular switches, perethynylated dehydroannulenes, expanded radialenes, and radiaannulenes, and an octamethoxy-substituted expanded cubane with a central C56 core. Donor-substituted cyanoethynylethenes (CEEs) and 1,1,4,4-tetracyanobuta-1,3-dienes (TCBDs) were introduced as new push-pull chromophores featuring intense intramolecular charge-transfer (CT) interactions. Dendritic multivalent CT chromophores were constructed using atom-economic, "click"-like reactions, and these systems were shown to behave as "molecular batteries", featuring exceptional electron uptake and storage capacity. The research finally led to the development of an unprecedented cascade reaction for the preparation of dendritic and oligomeric donor-acceptor (D-A) molecules. New [AB]-type oligomers become accessible in domino reactions involving repetitive sequences of [2+2] cycloadditions of tetracyanoethylene (TCNE) and tetrathiafulvalene (TTF) to polyynes, followed by retro-electrocyclization
