Experimental and Theoretical Investigation for the Level of Conjugation in Carbazole-Based Precursors and Their Mono-, Di-, and Polynuclear Pt(II) Complexes

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

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Abstract

A series of trimethylsilyl-protected monoalkynes (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 monoalkynes (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 diynes, 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 polynuclear Pt(II) σ-acetylide complexes have been characterized spectroscopically, with a subset analyzed 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 modeling 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
Pages (from-to)6465-6480
Number of pages16
JournalInorganic Chemistry
Volume55
Issue number13
DOIs
Publication statusPublished - Jul 5 2016

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

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

Experimental and Theoretical Investigation for the Level of Conjugation in Carbazole-Based Precursors and Their Mono-, Di-, and Polynuclear Pt(II) Complexes. / Al-Balushi, Rayya A.; Haque, Ashanul; Jayapal, Maharaja; Al-Suti, Mohammed K.; Husband, John; Khan, Muhammad S.; Koentjoro, Olivia F.; Molloy, Kieran C.; Skelton, Jonathan M.; Raithby, Paul R.

In: Inorganic Chemistry, Vol. 55, No. 13, 05.07.2016, p. 6465-6480.

Research output: Contribution to journalArticle

Al-Balushi, Rayya A. ; Haque, Ashanul ; Jayapal, Maharaja ; Al-Suti, Mohammed K. ; Husband, John ; Khan, Muhammad S. ; Koentjoro, Olivia F. ; Molloy, Kieran C. ; Skelton, Jonathan M. ; Raithby, Paul R. / Experimental and Theoretical Investigation for the Level of Conjugation in Carbazole-Based Precursors and Their Mono-, Di-, and Polynuclear Pt(II) Complexes. In: Inorganic Chemistry. 2016 ; Vol. 55, No. 13. pp. 6465-6480.
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AU - Jayapal, Maharaja

AU - Al-Suti, Mohammed K.

AU - Husband, John

AU - Khan, Muhammad S.

AU - Koentjoro, Olivia F.

AU - Molloy, Kieran C.

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AU - Raithby, Paul R.

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N2 - A series of trimethylsilyl-protected monoalkynes (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 monoalkynes (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 diynes, 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 polynuclear Pt(II) σ-acetylide complexes have been characterized spectroscopically, with a subset analyzed 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 modeling 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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