Synthesis,Redox and Optical Properties of Low‐Bandgap Platinum(II) Polyynes with 9‐Dicyanomethylene‐Substituted Fluorene Acceptors

In view of the strong electron‐withdrawing nature of the cyano substituent, a blue donor/acceptor‐type organometallic polymer (trans‐—Pt(PBu₃)₂—C≡C—R—C≡C—]_n (R = 9‐dicyanomethylenefluorene‐2,7‐diyl)) was prepared in good yield by CuI‐catalyzed polymerization involving the dehydrohalogenating coupling of trans‐Pt(PBu₃)₂Cl₂] and H—C≡C—R—C≡C—H. The thermal, redox and photoconducting properties of the polymer are reported. Electronic absorption studies indicate that it has a bandgap of 1.58 eV which is the lowest among any of the metal polyyne polymers reported in the literature. The derivatization of the polymer backbone with electron deficient dicyano‐substituted electron acceptor in the side chain is found to be effective to tune the bandgap of this class of materials while maintaining their solubility and processability.