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Impact of the alkyne substitution pattern and metalation on the photoisomerization of azobenzene-based platinum(II) diynes and polyynes


Reference:

Al-Balushi, R. A., Haque, A., Jayapal, M., Al-Suti, M. K., Husband, J., Khan, M. S., Skelton, J. M., Molloy, K. C. and Raithby, P. R., 2016. Impact of the alkyne substitution pattern and metalation on the photoisomerization of azobenzene-based platinum(II) diynes and polyynes. Inorganic Chemistry, 55 (21), pp. 10955-10967.

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http://dx.doi.org/10.1021/acs.inorgchem.6b01509

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Abstract

Trimethylsilyl-protected dialkynes incorporating azobenzene linker groups, Me3SiC ≡ CRC ≡ CSiMe3 (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(Et3P)2PtCl] and the deprotected dialkynes in a 2:1 ratio in iPr2NH/CH2Cl2 gives the platinum(II) diynes trans-[Ph(Et3P)2PtC ≡ CRC ≡ CPt(PEt3)2Ph], while the dehydrohalogenation polycondensation reaction between trans-[(nBu3P)2PtCl2] and the dialkynes in a 1:1 molar ratio under similar reaction conditions affords the platinum(II) polyynes, [-Pt(PnBu3)2-C ≡ CRC ≡ 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.

Details

Item Type Articles
CreatorsAl-Balushi, R. A., Haque, A., Jayapal, M., Al-Suti, M. K., Husband, J., Khan, M. S., Skelton, J. M., Molloy, K. C. and Raithby, P. R.
DOI10.1021/acs.inorgchem.6b01509
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URLURL Type
http://www.scopus.com/inward/record.url?scp=84994491986&partnerID=8YFLogxKUNSPECIFIED
DepartmentsFaculty of Science > Chemistry
RefereedYes
StatusPublished
ID Code53368

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