Impact of the Alkyne Substitution Pattern and Metalation on the Photoisomerization 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

Research output: Contribution to journalArticle

7 Citations (Scopus)

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.

Original languageEnglish
Pages (from-to)10955-10967
Number of pages13
JournalInorganic Chemistry
Volume55
Issue number21
DOIs
Publication statusPublished - Nov 7 2016

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Diynes
Polyacetylenes
Photoisomerization
Alkynes
alkynes
Platinum
platinum
Substitution reactions
substitutes
Polycondensation
Isomerization
Organic solvents
spacers
Light absorption
isomerization
optical absorption
Optical properties
Single crystals
methylidyne
Ligands

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

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

In: Inorganic Chemistry, Vol. 55, No. 21, 07.11.2016, p. 10955-10967.

Research output: Contribution to journalArticle

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. / Impact of the Alkyne Substitution Pattern and Metalation on the Photoisomerization of Azobenzene-Based Platinum(II) Diynes and Polyynes. In: Inorganic Chemistry. 2016 ; Vol. 55, No. 21. pp. 10955-10967.
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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.",
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AU - Al-Balushi, Rayya A.

AU - Haque, Ashanul

AU - Jayapal, Maharaja

AU - Al-Suti, Mohammed K.

AU - Husband, John

AU - Khan, Muhammad S.

AU - Skelton, Jonathan M.

AU - Molloy, Kieran C.

AU - Raithby, Paul R.

PY - 2016/11/7

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AB - 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.

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