A new series of acetylide-functionalized ligands based on ethylenedioxythiophene (EDOT) Spacers have been synthesized and incorporated into platinum(II) di-ynes and poly-ynes. The structural, thermal and optical properties of the new dimeric and polymeric organoplatinum(II) compounds were evaluated. A new series of bis-(ferrocenylethynyl) complexes and mono (ferrocenylethyny!) complex incorporating novel conjugated heterocyclic spacers were synthesized. Structural analysis of selected complexes revealed a Fe-Fe distance of ~14 Å in the bis-(ferrocenylethynyl) complexes. Electrochemistry, spectro-electrochemistry, digital simulations, and computational analysis were used to establish the long-range intra-molecular electronic communication in bis-(ferrocenylethynyl) complexes. A new family of co-ordination-driven self-assembled ferrocenylethynylpyridyl-copper complexes was synthesized and characterized by spectroscopic and crystallographic methods. The materials undergo oxidation under mild conditions followed by electro-crystallization of the oxidation products. The electro-crystallization generated partial- and fully-oxidized materials which were investigated by Raman, SEM and EDX analysis. The structural analysis of selected ligand precursors and Pt(II) di-ynes incorporating EDOT spacers shows beneficial inter- and intra-molecular bonding. The new Pt(II) poly-ynes and di-ynes show good thermal stability and lower band gaps suitable for device application. The bis (ferrocenylethynyl) complexes exhibit long-range intra-molecular electronic communication between the two iron centres, with implications for the design and synthesis of metal-containing conjugated poly-ynes and oligo ynes. In the ferrocenylethynylpyridyl-copper complexes the structural features based on rigid rod conjugated ethynyls as well as metal cluster components potentially provides high electron-mobility and therefore these crystalline materials with partial- and fully occupied ferrocene electronic band structures will be of interest in future electronic materials and in optical components