Synthesis and characterization of platinum(ii) di-ynes and poly-ynes incorporating ethylenedioxythiophene (EDOT) spacers in the backbone

Muhammad S. Khan, Mohammed K. Al-Suti, Hakkikulla H. Shah, Said Al-Humaimi, Fathiya R. Al-Battashi, Jens K. Bjernemose, Louise Male, Paul R. Raithby, Ning Zhang, Anna Köhler, John E. Warren

Research output: Contribution to journalArticle

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Abstract

A series of trimethylsilyl-protected di-alkynes incorporating 3,4-ethylenedioxythiophene (EDOT) linker groups Me3Si-CC-R-CC- SiMe3 (R = ethylenedioxythiophene-3,4-diyl 1a, 2,2′-bis-3,4- ethylenedioxythiophene-5,5′-diyl 2a, 2,2′,5′,2′′- ter-3,4-ethylenedioxythiophene-5,5′′-diyl 3a) and the corresponding terminal di-alkynes, H-CC-R-CC-H 1b-2b has been synthesized and characterized and the single crystal X-ray structure of 1a has been determined. CuI-catalyzed dehydrohalogenation reaction between trans-[(Ph)(Et3P) 2PtCl] and the terminal di-alkynes 1b-2b in iPr 2NH/CH2Cl2 (2:1 mole ratio) gives the Pt(ii) di-ynes trans-[(Et3P)2(Ph)Pt-CC-R-CC-Pt(Ph)(Et 3P)2] 1M-2M while the dehydrohalogenation polycondensation reaction between trans-[(nBu3P)2PtCl 2] and 1b-2b (1:1 mole ratio) under similar reaction conditions affords the Pt(ii) poly-ynes trans-[Pt(PnBu3) 2-CC-R-CC-]n1P-2P. The di-ynes and poly-ynes have been characterized spectroscopically and, for 1M and 2M, by single-crystal X-ray which confirms the "rigid rod" di-yne backbone. The materials possess excellent thermal stability, are soluble in common organic solvents and readily cast into thin films. Optical absorption spectroscopic measurements reveal that the EDOT spacers create stronger donor-acceptor interactions between the platinum(ii) centres and conjugated ligands along the rigid backbone of the organometallic polymers compared to the related non-fused and fused oligothiophene spacers.

Original languageEnglish
Pages (from-to)10174-10183
Number of pages10
JournalDalton Transactions
Volume40
Issue number39
DOIs
Publication statusPublished - Oct 21 2011

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Platinum
Alkynes
Single crystals
X rays
Organometallics
Polycondensation
Organic solvents
Light absorption
Polymers
Thermodynamic stability
Ligands
Thin films
3,4-ethylenedioxythiophene

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Khan, M. S., Al-Suti, M. K., Shah, H. H., Al-Humaimi, S., Al-Battashi, F. R., Bjernemose, J. K., ... Warren, J. E. (2011). Synthesis and characterization of platinum(ii) di-ynes and poly-ynes incorporating ethylenedioxythiophene (EDOT) spacers in the backbone. Dalton Transactions, 40(39), 10174-10183. https://doi.org/10.1039/c1dt11010a

Synthesis and characterization of platinum(ii) di-ynes and poly-ynes incorporating ethylenedioxythiophene (EDOT) spacers in the backbone. / Khan, Muhammad S.; Al-Suti, Mohammed K.; Shah, Hakkikulla H.; Al-Humaimi, Said; Al-Battashi, Fathiya R.; Bjernemose, Jens K.; Male, Louise; Raithby, Paul R.; Zhang, Ning; Köhler, Anna; Warren, John E.

In: Dalton Transactions, Vol. 40, No. 39, 21.10.2011, p. 10174-10183.

Research output: Contribution to journalArticle

Khan, MS, Al-Suti, MK, Shah, HH, Al-Humaimi, S, Al-Battashi, FR, Bjernemose, JK, Male, L, Raithby, PR, Zhang, N, Köhler, A & Warren, JE 2011, 'Synthesis and characterization of platinum(ii) di-ynes and poly-ynes incorporating ethylenedioxythiophene (EDOT) spacers in the backbone', Dalton Transactions, vol. 40, no. 39, pp. 10174-10183. https://doi.org/10.1039/c1dt11010a
Khan, Muhammad S. ; Al-Suti, Mohammed K. ; Shah, Hakkikulla H. ; Al-Humaimi, Said ; Al-Battashi, Fathiya R. ; Bjernemose, Jens K. ; Male, Louise ; Raithby, Paul R. ; Zhang, Ning ; Köhler, Anna ; Warren, John E. / Synthesis and characterization of platinum(ii) di-ynes and poly-ynes incorporating ethylenedioxythiophene (EDOT) spacers in the backbone. In: Dalton Transactions. 2011 ; Vol. 40, No. 39. pp. 10174-10183.
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abstract = "A series of trimethylsilyl-protected di-alkynes incorporating 3,4-ethylenedioxythiophene (EDOT) linker groups Me3Si-CC-R-CC- SiMe3 (R = ethylenedioxythiophene-3,4-diyl 1a, 2,2′-bis-3,4- ethylenedioxythiophene-5,5′-diyl 2a, 2,2′,5′,2′′- ter-3,4-ethylenedioxythiophene-5,5′′-diyl 3a) and the corresponding terminal di-alkynes, H-CC-R-CC-H 1b-2b has been synthesized and characterized and the single crystal X-ray structure of 1a has been determined. CuI-catalyzed dehydrohalogenation reaction between trans-[(Ph)(Et3P) 2PtCl] and the terminal di-alkynes 1b-2b in iPr 2NH/CH2Cl2 (2:1 mole ratio) gives the Pt(ii) di-ynes trans-[(Et3P)2(Ph)Pt-CC-R-CC-Pt(Ph)(Et 3P)2] 1M-2M while the dehydrohalogenation polycondensation reaction between trans-[(nBu3P)2PtCl 2] and 1b-2b (1:1 mole ratio) under similar reaction conditions affords the Pt(ii) poly-ynes trans-[Pt(PnBu3) 2-CC-R-CC-]n1P-2P. The di-ynes and poly-ynes have been characterized spectroscopically and, for 1M and 2M, by single-crystal X-ray which confirms the {"}rigid rod{"} di-yne backbone. The materials possess excellent thermal stability, are soluble in common organic solvents and readily cast into thin films. Optical absorption spectroscopic measurements reveal that the EDOT spacers create stronger donor-acceptor interactions between the platinum(ii) centres and conjugated ligands along the rigid backbone of the organometallic polymers compared to the related non-fused and fused oligothiophene spacers.",
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