Al-Balushi Rayya A, Haque Ashanul, Jayapal Maharaja, Al-Suti Mohammed K, Husband John, Khan Muhammad S, Skelton Jonathan M, Molloy Kieran C, Raithby Paul R
Department of Chemistry, Sultan Qaboos University , P.O. Box 36, Al Khod 123, Sultanate of Oman.
Department of Chemistry, University of Bath , Claverton Down, Bath BA2 7AY, U.K.
Inorg Chem. 2016 Nov 7;55(21):10955-10967. doi: 10.1021/acs.inorgchem.6b01509. Epub 2016 Oct 18.
Trimethylsilyl-protected dialkynes incorporating azobenzene linker groups, MeSiC≡CRC≡CSiMe (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 trans-[Ph(EtP)PtCl] and the deprotected dialkynes in a 2:1 ratio in PrNH/CHCl gives the platinum(II) diynes trans-[Ph(EtP)PtC≡CRC≡CPt(PEt)Ph], while the dehydrohalogenation polycondensation reaction between trans-[(BuP)PtCl] and the dialkynes in a 1:1 molar ratio under similar reaction conditions affords the platinum(II) polyynes, [-Pt(PBu)-C≡CRC≡C-]. 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 para-alkynylazobenzene spacers have a higher degree of electronic delocalisation than their meta-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.
含有偶氮苯连接基团的三甲基硅烷基保护的二炔烃，MeSiC≡CRC≡CSiMe（R = 偶氮苯-3,3'-二基、偶氮苯-4,4'-二基、2,5-二辛基偶氮苯-4,4'-二基），以及相应的末端二炔烃，HC≡CRC≡CH，已被合成并表征。在PrNH/CHCl中，反式-[Ph(EtP)PtCl]与脱保护的二炔烃以2:1的比例进行CuI催化的脱卤化氢反应，得到铂(II)二炔烃反式-[Ph(EtP)PtC≡CRC≡CPt(PEt)Ph]，而在类似反应条件下，反式-[(BuP)PtCl]与二炔烃以1:1的摩尔比进行脱卤化氢缩聚反应，得到铂(II)多炔烃，[-Pt(PBu)-C≡CRC≡C-]。这些材料已通过光谱进行了表征，二炔烃也使用单晶X射线衍射进行了研究。铂(II)二炔烃和多炔烃都可溶于常见的有机溶剂。光吸收测量表明，含有对-炔基偶氮苯间隔基的化合物比其间-炔基偶氮苯对应物具有更高程度的电子离域。通过光谱观察到炔基官能化的偶氮苯配体在溶液中发生可逆光异构化，并且在较小程度上，铂(II)配合物也发生可逆光异构化。还使用互补的量子化学建模来分析光学性质和异构化能量学。
