Synthesis, characterisation and optical spectroscopy of platinum(ii) di-ynes and poly-ynes incorporating condensed aromatic spacers in the backbone

Muhammad S. Khan, Muna R.A. Al-Mandhary, Mohammed K. Al-Suti, Fathiya R. Al-Battashi, Sultan Al-Saadi, Birte Ahrens, Jens K. Bjernemose, Mary F. Mahon, Paul R. Raithby, Muhammad Younus, Nazia Chawdhury, Anna Köhler, Elizabeth A. Marseglia, Emilio Tedesco, Neil Feeder, Simon J. Teat

Research output: Contribution to journalArticle

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Abstract

A series of protected and terminal dialkynes with extended π-conjugation through a condensed aromatic linker unit in the backbone, 1,4-bis(trimethylsilylethynyl)naphthalene, 2a, 1,4-bis(ethynyl)naphthalene, 2b, 9,10-bis(trimethylsilylethynyl)anthracene 3a, 9,10-bis(ethynyl)anthracene 3b, have been synthesized and characterized spectroscopically. The solid-state structures of 2a and 3a have been confirmed by single crystal X-ray diffraction studies. Reaction of two equivalents of the complex trans-[Ph(Et3P)2PtCl] with an equivalent of the terminal dialkynes 1,4-bis(ethynyl)benzene 1b and 2b–3b, in iPr2NH–CH2Cl2, in the presence of CuI, at room temperature, afforded the platinum(ii) di-ynes trans-[Ph(Et3P)2Pt–C≡C–R–C≡C–Pt(PEt3)2Ph] (R = benzene-1,4-diyl 1c; naphthalene-1,4-diyl 2c and anthracene-9,10-diyl 3c) while reactions between equimolar quantities of trans-[(nBu3P)2PtCl2] and 2b–3b under similar conditions readily afforded the platinum(ii) poly-ynes trans-[–(nBu3P)2Pt–C≡C–R–C≡C–]n(R = naphthalene-1,4-diyl 2d and anthracene-9,10-diyl 3d). The Pt(ii) diynes and poly-ynes have been characterized by analytical and spectroscopic methods, and the single crystal X-ray structures of 1c and 2c have been determined. These structures confirm the trans-square planar geometry at the platinum centres and the linear nature of the molecules. The di-ynes and poly-ynes are soluble in organic solvents and readily cast into thin films. Optical spectroscopic measurements reveal that the electron-rich naphthalene and anthracene spacers create strong donor–acceptor interactions between the Pt(ii) centres and conjugated ligands along the rigid backbone of the organometallic polymers. Thermogravimetry shows that the di-ynes possess a somewhat higher thermal stability than the corresponding poly-ynes. Both the Pt(ii) di-ynes and the poly-ynes exhibit increasing thermal stability along the series of spacers from phenylene through naphthalene to anthracene.

Original languageEnglish
Pages (from-to)23772377-23852385
Number of pages80009
JournalJournal of the Chemical Society. Dalton Transactions
Volume40
Issue number1515
DOIs
Publication statusPublished - Jul 26 2004

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Platinum
Benzene
Diynes
Thermodynamic stability
Single crystals
Organometallics
Organic solvents
Thermogravimetric analysis
anthracene
Optical spectroscopy
naphthalene
Polymers
Ligands
X ray diffraction
X rays
Thin films
Molecules
Geometry
Electrons
Temperature

Keywords

  • Coordination chemistry
  • Fluorescence
  • Luminescence
  • Polymers
  • X-ray diffraction
  • X-ray powder diffraction

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Synthesis, characterisation and optical spectroscopy of platinum(ii) di-ynes and poly-ynes incorporating condensed aromatic spacers in the backbone. / Khan, Muhammad S.; Al-Mandhary, Muna R.A.; Al-Suti, Mohammed K.; Al-Battashi, Fathiya R.; Al-Saadi, Sultan; Ahrens, Birte; Bjernemose, Jens K.; Mahon, Mary F.; Raithby, Paul R.; Younus, Muhammad; Chawdhury, Nazia; Köhler, Anna; Marseglia, Elizabeth A.; Tedesco, Emilio; Feeder, Neil; Teat, Simon J.

In: Journal of the Chemical Society. Dalton Transactions, Vol. 40, No. 1515, 26.07.2004, p. 23772377-23852385.

Research output: Contribution to journalArticle

Khan, MS, Al-Mandhary, MRA, Al-Suti, MK, Al-Battashi, FR, Al-Saadi, S, Ahrens, B, Bjernemose, JK, Mahon, MF, Raithby, PR, Younus, M, Chawdhury, N, Köhler, A, Marseglia, EA, Tedesco, E, Feeder, N & Teat, SJ 2004, 'Synthesis, characterisation and optical spectroscopy of platinum(ii) di-ynes and poly-ynes incorporating condensed aromatic spacers in the backbone', Journal of the Chemical Society. Dalton Transactions, vol. 40, no. 1515, pp. 23772377-23852385. https://doi.org/10.1039/B405070C
Khan, Muhammad S. ; Al-Mandhary, Muna R.A. ; Al-Suti, Mohammed K. ; Al-Battashi, Fathiya R. ; Al-Saadi, Sultan ; Ahrens, Birte ; Bjernemose, Jens K. ; Mahon, Mary F. ; Raithby, Paul R. ; Younus, Muhammad ; Chawdhury, Nazia ; Köhler, Anna ; Marseglia, Elizabeth A. ; Tedesco, Emilio ; Feeder, Neil ; Teat, Simon J. / Synthesis, characterisation and optical spectroscopy of platinum(ii) di-ynes and poly-ynes incorporating condensed aromatic spacers in the backbone. In: Journal of the Chemical Society. Dalton Transactions. 2004 ; Vol. 40, No. 1515. pp. 23772377-23852385.
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abstract = "A series of protected and terminal dialkynes with extended π-conjugation through a condensed aromatic linker unit in the backbone, 1,4-bis(trimethylsilylethynyl)naphthalene, 2a, 1,4-bis(ethynyl)naphthalene, 2b, 9,10-bis(trimethylsilylethynyl)anthracene 3a, 9,10-bis(ethynyl)anthracene 3b, have been synthesized and characterized spectroscopically. The solid-state structures of 2a and 3a have been confirmed by single crystal X-ray diffraction studies. Reaction of two equivalents of the complex trans-[Ph(Et3P)2PtCl] with an equivalent of the terminal dialkynes 1,4-bis(ethynyl)benzene 1b and 2b–3b, in iPr2NH–CH2Cl2, in the presence of CuI, at room temperature, afforded the platinum(ii) di-ynes trans-[Ph(Et3P)2Pt–C≡C–R–C≡C–Pt(PEt3)2Ph] (R = benzene-1,4-diyl 1c; naphthalene-1,4-diyl 2c and anthracene-9,10-diyl 3c) while reactions between equimolar quantities of trans-[(nBu3P)2PtCl2] and 2b–3b under similar conditions readily afforded the platinum(ii) poly-ynes trans-[–(nBu3P)2Pt–C≡C–R–C≡C–]n(R = naphthalene-1,4-diyl 2d and anthracene-9,10-diyl 3d). The Pt(ii) diynes and poly-ynes have been characterized by analytical and spectroscopic methods, and the single crystal X-ray structures of 1c and 2c have been determined. These structures confirm the trans-square planar geometry at the platinum centres and the linear nature of the molecules. The di-ynes and poly-ynes are soluble in organic solvents and readily cast into thin films. Optical spectroscopic measurements reveal that the electron-rich naphthalene and anthracene spacers create strong donor–acceptor interactions between the Pt(ii) centres and conjugated ligands along the rigid backbone of the organometallic polymers. Thermogravimetry shows that the di-ynes possess a somewhat higher thermal stability than the corresponding poly-ynes. Both the Pt(ii) di-ynes and the poly-ynes exhibit increasing thermal stability along the series of spacers from phenylene through naphthalene to anthracene.",
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T1 - Synthesis, characterisation and optical spectroscopy of platinum(ii) di-ynes and poly-ynes incorporating condensed aromatic spacers in the backbone

AU - Khan, Muhammad S.

AU - Al-Mandhary, Muna R.A.

AU - Al-Suti, Mohammed K.

AU - Al-Battashi, Fathiya R.

AU - Al-Saadi, Sultan

AU - Ahrens, Birte

AU - Bjernemose, Jens K.

AU - Mahon, Mary F.

AU - Raithby, Paul R.

AU - Younus, Muhammad

AU - Chawdhury, Nazia

AU - Köhler, Anna

AU - Marseglia, Elizabeth A.

AU - Tedesco, Emilio

AU - Feeder, Neil

AU - Teat, Simon J.

PY - 2004/7/26

Y1 - 2004/7/26

N2 - A series of protected and terminal dialkynes with extended π-conjugation through a condensed aromatic linker unit in the backbone, 1,4-bis(trimethylsilylethynyl)naphthalene, 2a, 1,4-bis(ethynyl)naphthalene, 2b, 9,10-bis(trimethylsilylethynyl)anthracene 3a, 9,10-bis(ethynyl)anthracene 3b, have been synthesized and characterized spectroscopically. The solid-state structures of 2a and 3a have been confirmed by single crystal X-ray diffraction studies. Reaction of two equivalents of the complex trans-[Ph(Et3P)2PtCl] with an equivalent of the terminal dialkynes 1,4-bis(ethynyl)benzene 1b and 2b–3b, in iPr2NH–CH2Cl2, in the presence of CuI, at room temperature, afforded the platinum(ii) di-ynes trans-[Ph(Et3P)2Pt–C≡C–R–C≡C–Pt(PEt3)2Ph] (R = benzene-1,4-diyl 1c; naphthalene-1,4-diyl 2c and anthracene-9,10-diyl 3c) while reactions between equimolar quantities of trans-[(nBu3P)2PtCl2] and 2b–3b under similar conditions readily afforded the platinum(ii) poly-ynes trans-[–(nBu3P)2Pt–C≡C–R–C≡C–]n(R = naphthalene-1,4-diyl 2d and anthracene-9,10-diyl 3d). The Pt(ii) diynes and poly-ynes have been characterized by analytical and spectroscopic methods, and the single crystal X-ray structures of 1c and 2c have been determined. These structures confirm the trans-square planar geometry at the platinum centres and the linear nature of the molecules. The di-ynes and poly-ynes are soluble in organic solvents and readily cast into thin films. Optical spectroscopic measurements reveal that the electron-rich naphthalene and anthracene spacers create strong donor–acceptor interactions between the Pt(ii) centres and conjugated ligands along the rigid backbone of the organometallic polymers. Thermogravimetry shows that the di-ynes possess a somewhat higher thermal stability than the corresponding poly-ynes. Both the Pt(ii) di-ynes and the poly-ynes exhibit increasing thermal stability along the series of spacers from phenylene through naphthalene to anthracene.

AB - A series of protected and terminal dialkynes with extended π-conjugation through a condensed aromatic linker unit in the backbone, 1,4-bis(trimethylsilylethynyl)naphthalene, 2a, 1,4-bis(ethynyl)naphthalene, 2b, 9,10-bis(trimethylsilylethynyl)anthracene 3a, 9,10-bis(ethynyl)anthracene 3b, have been synthesized and characterized spectroscopically. The solid-state structures of 2a and 3a have been confirmed by single crystal X-ray diffraction studies. Reaction of two equivalents of the complex trans-[Ph(Et3P)2PtCl] with an equivalent of the terminal dialkynes 1,4-bis(ethynyl)benzene 1b and 2b–3b, in iPr2NH–CH2Cl2, in the presence of CuI, at room temperature, afforded the platinum(ii) di-ynes trans-[Ph(Et3P)2Pt–C≡C–R–C≡C–Pt(PEt3)2Ph] (R = benzene-1,4-diyl 1c; naphthalene-1,4-diyl 2c and anthracene-9,10-diyl 3c) while reactions between equimolar quantities of trans-[(nBu3P)2PtCl2] and 2b–3b under similar conditions readily afforded the platinum(ii) poly-ynes trans-[–(nBu3P)2Pt–C≡C–R–C≡C–]n(R = naphthalene-1,4-diyl 2d and anthracene-9,10-diyl 3d). The Pt(ii) diynes and poly-ynes have been characterized by analytical and spectroscopic methods, and the single crystal X-ray structures of 1c and 2c have been determined. These structures confirm the trans-square planar geometry at the platinum centres and the linear nature of the molecules. The di-ynes and poly-ynes are soluble in organic solvents and readily cast into thin films. Optical spectroscopic measurements reveal that the electron-rich naphthalene and anthracene spacers create strong donor–acceptor interactions between the Pt(ii) centres and conjugated ligands along the rigid backbone of the organometallic polymers. Thermogravimetry shows that the di-ynes possess a somewhat higher thermal stability than the corresponding poly-ynes. Both the Pt(ii) di-ynes and the poly-ynes exhibit increasing thermal stability along the series of spacers from phenylene through naphthalene to anthracene.

KW - Coordination chemistry

KW - Fluorescence

KW - Luminescence

KW - Polymers

KW - X-ray diffraction

KW - X-ray powder diffraction

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