Abstract Reaction of the PhSe− anion with 1,8-bis(2-bromoethoxy)anthracene-9,10-dione, 1,5-bis(2-bromoethoxy)anthracene-9,10-dione, 1,8-bis(2-bromoethylethyleneoxy)anthracene-9,10-dione in 1:1 ratio generates 1,8-bis(2-phenylselenoethoxy)anthracene-9,10-dione (2), 1,5-bis(2-phenylselenoethoxy)anthracene-9,10-dione (3) and 1,8-bis(2-phenylselenoethylethyleneoxy)anthracene-9,10-dione (4). The reaction of 2 with a methanolic solution of Ag(CH3CN)4BF4 and Cu(CH3CN)4BF4, yielded metal complexes 5 and 6, respectively. 3 formed a 1D coordination polymer (7) with Ag(CH3CN)4BF4 in a 1:2 ratio. The anthraquinone in 3 exhibits π–π interactions with distances in a range of 3.512–3.840Å. 2 acts as a chemodosimeter for Cu2+ and Fe3+ as it undergoes an aryl ether cleavage with Cu2+ and Fe3+, and produces the luminescent 1-hydroxy-8-(2-phenylselenoethoxy)anthracene-9,10-dione (8). Intramolecular hydrogen bonding in 8 is responsible for the red–orange (λmax 595nm) emission. The X-ray structures of 5, 6, 7, and 8 are reported along with cyclic voltammetric analyses of new organoselenium compounds.