Experimental and theoretical investigation for level of conjugation in carbazole-based precursors and their mono-,di- and polynuclear Pt(II) complexes

Paul Raithby, Kieran Molloy, Jonathan Skelton, Olivia F Koentjoro, Rayya A. Al-balushi, Ashanul Haque, Jayapal Maharaja, Mohammed K Al-Suti, John Husband, Muhammad S Khan

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Abstract

A series of trimethylsilyl-protected mono-alkynes (Me3SiC≡C−R) and bis-alkynes (Me3 SiC≡C−R−C≡CSiMe3) incorporating carbazole spacer groups (R = carbazole-2-yl, carbazole-3-yl, carbazole-2,7-diyl, N-(2-ethylhexyl)carbazole-2,7-diyl, carbazole-3,6-diyl, N-(2-ethylhexyl)carbazole-3,6-diyl), together with the corresponding terminal mono-alkynes (H−C≡C−R) and bis-alkynes (H−C≡C−R−C≡C−H), have been synthesized and characterized. The CuI-catalyzed dehydrohalogenation reaction between trans-[(Ph)(Et3P)2PtCl], trans-[(Et3P)2PtCl2] and trans-[(PnBu3)2PtCl2] and the terminal alkynes in iPr2NH/CH2Cl2 affords a series of Pt(II) mono- and di-ynes, while the dehydrohalogenation polycondensation reactions with trans-[(PnBu3)2PtCl2] under similar reaction conditions yields four Pt(II) poly-ynes of the form trans-[(PnBu3)2Pt−C≡C−R−C≡C−]n. The acetylide-functionalized carbazole ligands and the mono-, di- and poly-nuclear Pt(II) σ-acetylide complexes have been characterized spectroscopically, with a subset analysed using single-crystal X-ray diffraction. The Pt(II) mono-, di- and poly-ynes incorporating the carbazole spacers are soluble in common organic solvents, and solution absorption spectra show a consistent red-shift between the 2- and 2,7- as well as 3- and 3,6-carbazole complexes. Computational modelling is used to explain the observed spectral shifts, which are related to the enhanced electronic delocalization in the latter systems. These results also indicate that the inclusion of carbazole-2,7-diyl units into rigid-rod organometallic polymers should enhance electronic transport along the chains.
Original languageEnglish
Article numberic-2016-005239
JournalInorganic Chemistry
DOIs
Publication statusPublished - 10 Jun 2016

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carbazoles
conjugation
Alkynes
alkynes
spacers
carbazole
organometallic polymers
Organometallics
Polycondensation
electronics
red shift
Organic solvents
set theory
Absorption spectra
Polymers
rods
Single crystals
inclusions
Ligands
absorption spectra

Keywords

  • Carbazole, Conjugation, Pt(II) acteylide complexes, Solution optical absorption, TD-DFT.

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Experimental and theoretical investigation for level of conjugation in carbazole-based precursors and their mono-,di- and polynuclear Pt(II) complexes. / Raithby, Paul; Molloy, Kieran; Skelton, Jonathan; Koentjoro, Olivia F; Al-balushi, Rayya A.; Haque, Ashanul; Maharaja, Jayapal; Al-Suti, Mohammed K; Husband, John; Khan, Muhammad S.

In: Inorganic Chemistry, 10.06.2016.

Research output: Contribution to journalArticle

Raithby, Paul ; Molloy, Kieran ; Skelton, Jonathan ; Koentjoro, Olivia F ; Al-balushi, Rayya A. ; Haque, Ashanul ; Maharaja, Jayapal ; Al-Suti, Mohammed K ; Husband, John ; Khan, Muhammad S. / Experimental and theoretical investigation for level of conjugation in carbazole-based precursors and their mono-,di- and polynuclear Pt(II) complexes. In: Inorganic Chemistry. 2016.
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abstract = "A series of trimethylsilyl-protected mono-alkynes (Me3SiC≡C−R) and bis-alkynes (Me3 SiC≡C−R−C≡CSiMe3) incorporating carbazole spacer groups (R = carbazole-2-yl, carbazole-3-yl, carbazole-2,7-diyl, N-(2-ethylhexyl)carbazole-2,7-diyl, carbazole-3,6-diyl, N-(2-ethylhexyl)carbazole-3,6-diyl), together with the corresponding terminal mono-alkynes (H−C≡C−R) and bis-alkynes (H−C≡C−R−C≡C−H), have been synthesized and characterized. The CuI-catalyzed dehydrohalogenation reaction between trans-[(Ph)(Et3P)2PtCl], trans-[(Et3P)2PtCl2] and trans-[(PnBu3)2PtCl2] and the terminal alkynes in iPr2NH/CH2Cl2 affords a series of Pt(II) mono- and di-ynes, while the dehydrohalogenation polycondensation reactions with trans-[(PnBu3)2PtCl2] under similar reaction conditions yields four Pt(II) poly-ynes of the form trans-[(PnBu3)2Pt−C≡C−R−C≡C−]n. The acetylide-functionalized carbazole ligands and the mono-, di- and poly-nuclear Pt(II) σ-acetylide complexes have been characterized spectroscopically, with a subset analysed using single-crystal X-ray diffraction. The Pt(II) mono-, di- and poly-ynes incorporating the carbazole spacers are soluble in common organic solvents, and solution absorption spectra show a consistent red-shift between the 2- and 2,7- as well as 3- and 3,6-carbazole complexes. Computational modelling is used to explain the observed spectral shifts, which are related to the enhanced electronic delocalization in the latter systems. These results also indicate that the inclusion of carbazole-2,7-diyl units into rigid-rod organometallic polymers should enhance electronic transport along the chains.",
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AU - Raithby, Paul

AU - Molloy, Kieran

AU - Skelton, Jonathan

AU - Koentjoro, Olivia F

AU - Al-balushi, Rayya A.

AU - Haque, Ashanul

AU - Maharaja, Jayapal

AU - Al-Suti, Mohammed K

AU - Husband, John

AU - Khan, Muhammad S

PY - 2016/6/10

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N2 - A series of trimethylsilyl-protected mono-alkynes (Me3SiC≡C−R) and bis-alkynes (Me3 SiC≡C−R−C≡CSiMe3) incorporating carbazole spacer groups (R = carbazole-2-yl, carbazole-3-yl, carbazole-2,7-diyl, N-(2-ethylhexyl)carbazole-2,7-diyl, carbazole-3,6-diyl, N-(2-ethylhexyl)carbazole-3,6-diyl), together with the corresponding terminal mono-alkynes (H−C≡C−R) and bis-alkynes (H−C≡C−R−C≡C−H), have been synthesized and characterized. The CuI-catalyzed dehydrohalogenation reaction between trans-[(Ph)(Et3P)2PtCl], trans-[(Et3P)2PtCl2] and trans-[(PnBu3)2PtCl2] and the terminal alkynes in iPr2NH/CH2Cl2 affords a series of Pt(II) mono- and di-ynes, while the dehydrohalogenation polycondensation reactions with trans-[(PnBu3)2PtCl2] under similar reaction conditions yields four Pt(II) poly-ynes of the form trans-[(PnBu3)2Pt−C≡C−R−C≡C−]n. The acetylide-functionalized carbazole ligands and the mono-, di- and poly-nuclear Pt(II) σ-acetylide complexes have been characterized spectroscopically, with a subset analysed using single-crystal X-ray diffraction. The Pt(II) mono-, di- and poly-ynes incorporating the carbazole spacers are soluble in common organic solvents, and solution absorption spectra show a consistent red-shift between the 2- and 2,7- as well as 3- and 3,6-carbazole complexes. Computational modelling is used to explain the observed spectral shifts, which are related to the enhanced electronic delocalization in the latter systems. These results also indicate that the inclusion of carbazole-2,7-diyl units into rigid-rod organometallic polymers should enhance electronic transport along the chains.

AB - A series of trimethylsilyl-protected mono-alkynes (Me3SiC≡C−R) and bis-alkynes (Me3 SiC≡C−R−C≡CSiMe3) incorporating carbazole spacer groups (R = carbazole-2-yl, carbazole-3-yl, carbazole-2,7-diyl, N-(2-ethylhexyl)carbazole-2,7-diyl, carbazole-3,6-diyl, N-(2-ethylhexyl)carbazole-3,6-diyl), together with the corresponding terminal mono-alkynes (H−C≡C−R) and bis-alkynes (H−C≡C−R−C≡C−H), have been synthesized and characterized. The CuI-catalyzed dehydrohalogenation reaction between trans-[(Ph)(Et3P)2PtCl], trans-[(Et3P)2PtCl2] and trans-[(PnBu3)2PtCl2] and the terminal alkynes in iPr2NH/CH2Cl2 affords a series of Pt(II) mono- and di-ynes, while the dehydrohalogenation polycondensation reactions with trans-[(PnBu3)2PtCl2] under similar reaction conditions yields four Pt(II) poly-ynes of the form trans-[(PnBu3)2Pt−C≡C−R−C≡C−]n. The acetylide-functionalized carbazole ligands and the mono-, di- and poly-nuclear Pt(II) σ-acetylide complexes have been characterized spectroscopically, with a subset analysed using single-crystal X-ray diffraction. The Pt(II) mono-, di- and poly-ynes incorporating the carbazole spacers are soluble in common organic solvents, and solution absorption spectra show a consistent red-shift between the 2- and 2,7- as well as 3- and 3,6-carbazole complexes. Computational modelling is used to explain the observed spectral shifts, which are related to the enhanced electronic delocalization in the latter systems. These results also indicate that the inclusion of carbazole-2,7-diyl units into rigid-rod organometallic polymers should enhance electronic transport along the chains.

KW - Carbazole, Conjugation, Pt(II) acteylide complexes, Solution optical absorption, TD-DFT.

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M3 - Article

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

M1 - ic-2016-005239

ER -