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(trimethylsilyl-ethynyl)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(Et 3P)2PtCl] with an equivalent of the terminal dialkynes 1,4-bis(ethynyl)benzene 1b and 2b-3b, in Pr2NH-CH2Cl 2, in the presence of Cul, at room temperature, afforded the platium(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(III) 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(n) 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 language | English |
|---|---|
| Pages (from-to) | 2377-2385 |
| Number of pages | 9 |
| Journal | Dalton Transactions |
| Issue number | 15 |
| Publication status | Published - Aug 7 2004 |
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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: Dalton Transactions, No. 15, 07.08.2004, p. 2377-2385.Research output: Contribution to journal › Article
}
TY - JOUR
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 - 2004/8/7
Y1 - 2004/8/7
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(trimethylsilyl-ethynyl)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(Et 3P)2PtCl] with an equivalent of the terminal dialkynes 1,4-bis(ethynyl)benzene 1b and 2b-3b, in Pr2NH-CH2Cl 2, in the presence of Cul, at room temperature, afforded the platium(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(III) 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(n) 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(trimethylsilyl-ethynyl)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(Et 3P)2PtCl] with an equivalent of the terminal dialkynes 1,4-bis(ethynyl)benzene 1b and 2b-3b, in Pr2NH-CH2Cl 2, in the presence of Cul, at room temperature, afforded the platium(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(III) 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(n) 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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M3 - Article
AN - SCOPUS:4344623508
SP - 2377
EP - 2385
JO - Dalton Transactions
JF - Dalton Transactions
SN - 1477-9226
IS - 15
ER -