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

被引:22
作者
Al-Balushi, Rayya A. [1 ]
Haque, Ashanul [1 ]
Jayapal, Maharaja [1 ]
Al-Suti, Mohammed K. [1 ]
Husband, John [1 ]
Khan, Muhammad S. [1 ]
Skelton, Jonathan M. [2 ]
Molloy, Kieran C. [2 ]
Raithby, Paul R. [2 ]
机构
[1] Sultan Qaboos Univ, Dept Chem, POB 36, Al Khoud 123, Oman
[2] Univ Bath, Dept Chem, Bath BA2 7AY, Avon, England
基金
英国工程与自然科学研究理事会;
关键词
OPTICAL SPECTROSCOPY; CONJUGATED POLYMERS; DI-YNES; STRUCTURAL-CHARACTERIZATION; LINKER GROUPS; SOLAR-CELLS; MAIN-CHAIN; COMPLEXES; BACKBONE; STORAGE;
D O I
10.1021/acs.inorgchem.6b01509
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Trimethylsilyl-protected dialkynes incorporating azobenzene linker groups, Me3SiC equivalent to CRC equivalent to CSiMe3 (R = azobenzene-3,3'-diyl, azobenzene-4,4'-diyl, 2,5-dioctylazobenzene-4,4'-diyl), and the corresponding terminal dialkynes, HC equivalent to CRC equivalent to CH, have been synthesized and characterized. The CuI-catalyzed dehydrohalogenation reaction between trans-[Ph(Et3P)(2)PtCl] and the deprotected dialkynes in a 2:1 ratio in (Pr2NH)-Pr-i/CH2Cl2 gives the platinum(II) diynes trans-[Ph(Et3P)(2)PtC equivalent to CRC equivalent to CPt(PEt3)(2)Ph], while the dehydrohalogenation polycondensation reaction between trans-[((Bu3P)-Bu-n)(2)PtCl2] and the dialkynes in a 1:1 molar ratio under similar reaction conditions affords the platinum(II) polyynes, [-Pt((PBu3)-Bu-n)(2)-C equivalent to CRC equivalent to C-](n). 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.
引用
收藏
页码:10955 / 10967
页数:13
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