Impact of the Alkyne Substitution Pattern and Metalation on the Photoisomerization of Azobenzene-Based Platinum(II) Diynes and Polyynes

Trimethylsilyl-protected dialkynes incorporating azobenzene linker groups, Me<sub>3</sub>SiCCRCCSiMe<sub>3</sub> (R = azobenzene-3,3′-diyl, azobenzene-4,4′-diyl, 2,5-dioctylazobenzene-4,4′-diyl), and the corresponding terminal dialkynes, HCCRCCH, have been synthesized and characterized. The CuI-catalyzed dehydrohalogenation reaction between <i>trans</i>-[Ph­(Et<sub>3</sub>P)<sub>2</sub>PtCl] and the deprotected dialkynes in a 2:1 ratio in <sup>i</sup>Pr<sub>2</sub>NH/CH<sub>2</sub>Cl<sub>2</sub> gives the platinum­(II) diynes <i>trans</i>-[Ph­(Et<sub>3</sub>P)<sub>2</sub>PtCCRCCPt­(PEt<sub>3</sub>)<sub>2</sub>Ph], while the dehydrohalogenation polycondensation reaction between <i>trans</i>-[(<sup>n</sup>Bu<sub>3</sub>P)<sub>2</sub>PtCl<sub>2</sub>] and the dialkynes in a 1:1 molar ratio under similar reaction conditions affords the platinum­(II) polyynes, [−Pt­(P<sup>n</sup>Bu<sub>3</sub>)<sub>2</sub>–CCRCC−]<sub><i>n</i></sub>. The materials have been characterized spectroscopically, with the diynes also studied using single-crystal X-ray diffraction. The platinum­(II) diynes and polyynes are all soluble in common organic solvents. Optical-absorption measurements show that the compounds incorporating the <i>para</i>-alkynylazobenzene spacers have a higher degree of electronic delocalisation than their <i>meta</i>-alkynylazobenzene counterparts. Reversible photoisomerization in solution was observed spectroscopically for the alkynyl-functionalized azobenzene ligands and, to a lesser extent, for the platinum­(II) complexes. Complementary quantum-chemical modeling was also used to analyze the optical properties and isomerization energetics.