Twofold reduction of the title molecule 5,6;11,12-di-o-phenylenetetracene (DOPT) with an excess of metallic rubidium and cesium in the presence of strongly coordinating ethers like 18-crown-6-ether (18C6) and tetraglyme results in the formation of the first Rb(i) triple-decker complex and the first Cs(i) coordination polymer of the so far only sparsely studied polyaromatic planar hydrocarbon DOPT. Both compounds are extremely sensitive towards air and water in solution as well as in the solid state. Both compounds exhibit isomerism within their crystal lattices.