The impact of the alkyne substitution pattern and metalation on the photo-isomerization of azobenzene-based platinum(II) diynes and polyynes

Rayya A. Al-Balushi; Ashanul Haque; Maharaja Jayapal; Mohammed K. Al-Suti; John Husband; Muhammad S. Khan; Jonathan M. Skelton; Kieran C. Molloy; Paul R. Raithby

doi:10.1021/acs.inorgchem.6b01509

The impact of the alkyne substitution pattern and metalation on the photo-isomerization of azobenzene-based platinum(II) diynes and polyynes

Rayya A. Al-Balushi, Ashanul Haque, Maharaja Jayapal, Mohammed K. Al-Suti, John Husband, Muhammad S. Khan, Jonathan M. Skelton, Kieran C. Molloy, Paul R. Raithby

Department of Chemistry

Sultan Qaboos University

Research output: Contribution to journal › Article › peer-review

22 Citations (SciVal)

361 Downloads (Pure)

Abstract

Trimethylsilyl-protected di-alkynes incorporating azobenzene linker groups, Me3Si─C≡C─R─C≡C─SiMe3 (R = azobenzene-3,3’-diyl, azobenzene-4,4’-diyl, 2,5-bisoctylazobenzene-4,4’-diyl), and the corresponding terminal dialkynes, H─C≡C─R─C≡C─H, have been synthesised 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 Pt(II) di-ynes trans-[Ph(Et3P)2Pt─C≡C─R─C≡C─Pt(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 Pt(II) poly-ynes, [─Pt(PnBu3)2─C≡C─R─C≡C─]n. The materials have been characterized spectroscopically, with the di-ynes also studied using single-crystal X-ray diffraction. The Pt(II) di-ynes and poly-ynes are all soluble in common organic solvents. Optical-absorption measurements show that the compounds incorporating the para-azobenzene spacer have a higher degree of electronic delocalisation than their meta-azobenzene counterparts. Reversible photoisomerization in solution was observed spectroscopically for the alkynyl-functionalised azobenzene ligands and, to a lesser extent, for the Pt(II) complexes. Complementary quantum-chemical modelling was also used to analyse the optical properties and the isomerisation energetics.

Original language	English
Pages (from-to)	10955–10967
Number of pages	13
Journal	Inorganic Chemistry
Volume	55
Issue number	21
Early online date	18 Oct 2016
DOIs	https://doi.org/10.1021/acs.inorgchem.6b01509
Publication status	Published - 7 Nov 2016

Keywords

Azobenzene
Pt(II) acetylide complexes
Photoisomerisation
Time-dependent Density Functional Theory

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10.1021/acs.inorgchem.6b01509

IC-2016-0910S_revised
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see 10.1021/acs.inorgchem.6b01509.
Accepted author manuscript, 1.61 MB

Cite this

Al-Balushi, R. A., Haque, A., Jayapal, M., Al-Suti, M. K., Husband, J., Khan, M. S., Skelton, J. M., Molloy, K. C., & Raithby, P. R. (2016). The impact of the alkyne substitution pattern and metalation on the photo-isomerization of azobenzene-based platinum(II) diynes and polyynes. Inorganic Chemistry, 55(21), 10955–10967. https://doi.org/10.1021/acs.inorgchem.6b01509

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abstract = "Trimethylsilyl-protected di-alkynes incorporating azobenzene linker groups, Me3Si─C≡C─R─C≡C─SiMe3 (R = azobenzene-3,3{\textquoteright}-diyl, azobenzene-4,4{\textquoteright}-diyl, 2,5-bisoctylazobenzene-4,4{\textquoteright}-diyl), and the corresponding terminal dialkynes, H─C≡C─R─C≡C─H, have been synthesised 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 Pt(II) di-ynes trans-[Ph(Et3P)2Pt─C≡C─R─C≡C─Pt(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 Pt(II) poly-ynes, [─Pt(PnBu3)2─C≡C─R─C≡C─]n. The materials have been characterized spectroscopically, with the di-ynes also studied using single-crystal X-ray diffraction. The Pt(II) di-ynes and poly-ynes are all soluble in common organic solvents. Optical-absorption measurements show that the compounds incorporating the para-azobenzene spacer have a higher degree of electronic delocalisation than their meta-azobenzene counterparts. Reversible photoisomerization in solution was observed spectroscopically for the alkynyl-functionalised azobenzene ligands and, to a lesser extent, for the Pt(II) complexes. Complementary quantum-chemical modelling was also used to analyse the optical properties and the isomerisation energetics.",

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AU - Jayapal, Maharaja

AU - Al-Suti, Mohammed K.

AU - Husband, John

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AU - Skelton, Jonathan M.

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AB - Trimethylsilyl-protected di-alkynes incorporating azobenzene linker groups, Me3Si─C≡C─R─C≡C─SiMe3 (R = azobenzene-3,3’-diyl, azobenzene-4,4’-diyl, 2,5-bisoctylazobenzene-4,4’-diyl), and the corresponding terminal dialkynes, H─C≡C─R─C≡C─H, have been synthesised 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 Pt(II) di-ynes trans-[Ph(Et3P)2Pt─C≡C─R─C≡C─Pt(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 Pt(II) poly-ynes, [─Pt(PnBu3)2─C≡C─R─C≡C─]n. The materials have been characterized spectroscopically, with the di-ynes also studied using single-crystal X-ray diffraction. The Pt(II) di-ynes and poly-ynes are all soluble in common organic solvents. Optical-absorption measurements show that the compounds incorporating the para-azobenzene spacer have a higher degree of electronic delocalisation than their meta-azobenzene counterparts. Reversible photoisomerization in solution was observed spectroscopically for the alkynyl-functionalised azobenzene ligands and, to a lesser extent, for the Pt(II) complexes. Complementary quantum-chemical modelling was also used to analyse the optical properties and the isomerisation energetics.

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The impact of the alkyne substitution pattern and metalation on the photo-isomerization of azobenzene-based platinum(II) diynes and polyynes

Abstract

Keywords

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Applying Long-Lived Metastable States in Switchable Functionality via Kinetic Control of Molecular Assembly

Data for "The Impact of the Alkyne Substitution Pattern and Metallation on the Photo-isomerization of Azobenzene-based Platinum(II) Di-ynes and Poly-ynes"

Avance III 400 MHz Nuclear Magnetic Resonance (NMR) Spectrometer (9West)

Balena High Performance Computing (HPC) System

Electrospray Time-of-Flight Mass Spectrometer (Open-Access)

Cite this

The impact of the alkyne substitution pattern and metalation on the photo-isomerization of azobenzene-based platinum(II) diynes and polyynes

Abstract

Keywords

Access to Document

Other files and links

Fingerprint

Projects

Applying Long-Lived Metastable States in Switchable Functionality via Kinetic Control of Molecular Assembly

Datasets

Data for "The Impact of the Alkyne Substitution Pattern and Metallation on the Photo-isomerization of Azobenzene-based Platinum(II) Di-ynes and Poly-ynes"

Equipment

Avance III 400 MHz Nuclear Magnetic Resonance (NMR) Spectrometer (9West)

Balena High Performance Computing (HPC) System

Electrospray Time-of-Flight Mass Spectrometer (Open-Access)

Cite this