The synthesis and investigation of new types of poly(paraphenyleneethynylene)s, PPEs, is presented. PPEs which are Jacketed are there by shielded from electronic and plararization effects in the solid state. Other PPEs contain pendent groups which may functionalized before or after polymerization to afford two versitle routes to newly functionalized polymeric materials. Based on the PPE structure, metals may be introduced and these polymers may be used as precursors for other types of materials such as ceramics.