Synthesis of Phenyl Ethynylene Coupled Biradicals and Polyradicals Based on Galvinoxyl

Abstract

A conjugated polyradical with galvinoxyl groups, poly{1-[(3-5-di-tert-butyl-4-hydroxyphenyl)(3,5-di-tert-butyl-4-oxocyclohexa-2,5-dienylidene)methyl]phenyl-3,5-diethynyl}-co-3,5-[1-(dodecyl)benzoate], poly(G), and two conjugated oligoradicals, 1,4-bis{[(3-5-di-tert-butyl-4-hydroxyphenyl)(3,5-di-tert-butyl-4-oxocyclohexa-2,5-dienylidene) methyl]phenyl)4-ethynyl}-2,5-di(dodecyloxy)benzene (G-3 p -G), and 1,3-bis{[(3-5-di-tert-butyl-4-hydroxyphenyl)(3,5-di-tert-butyl-4-oxocyclohexa-2,5-dienylidene)methyl]phenyl)4-ethynyl}benzene (G- pmp -G) were synthesized by a Heck-Sonogashira route. The molecules were investigated in dilute solution by UV-Vis and ESR spectroscopy. In the solid state for G-3 p -G and poly(G), both the ESR spectra and the SQUID magnetometry suggest the set up of magnetic interactions between the radicals. On solid state powders SQUID characterization of poly(G) shows a continuous decrease of χT at low temperature, which is characteristic of antiferromagnetic interactions; while for G-3 p -G a competition between weak ferromagnetic and antiferromagnetic interactions is observed.

phenyl-ethylene - cross-coupling - Heck Reaction - radicals

References

<A NAME="RC12002SS-1A">1a</A> Magnetic Properties of Organic Materials   Lahti PM. Marcel Dekker; New York: 1999. 

<A NAME="RC12002SS-1B">1b</A> Molecular Magnetism-New Magnetic Materials   Itoh K. Kinoshita M. Kodansha; Tokyo; Gordon and Breach Science Publishers: Amsterdam: 2000. 

<A NAME="RC12002SS-2">2</A> Gierke W. Harrer W. Kirste B. Kurrek H. Reusch J. Z. Naturforsh. Chem. Org. Chem.  1976,  31B:  965 

<A NAME="RC12002SS-3">3</A> Turek P. Wautelet P. Le Moigne J. Stanger JL. André JJ. Bieber A. Rey P. De Cian A. Fisher J. Mol Cryst. Liq. Cryst.  1995,  272:  99 

<A NAME="RC12002SS-4">4</A> Matsuda K. Ulrich G. Iwamura H. J. Chem. Soc., Perkin Trans. 2  1998,  1582 

<A NAME="RC12002SS-5">5</A> Fico RM. Hay MF. Reese S. Hammond S. Lambert E. Fox MA. J. Org. Chem.  1999,  64:  9386 

<A NAME="RC12002SS-6">6</A> Sasaki S. Iwamura H. Chem. Lett.  1992,  1759 

<A NAME="RC12002SS-7">7</A> Takahashi M. Nishide H. Tsuchida E. Lahti PM. Chem. Mat.  1997,  9:  11 

<A NAME="RC12002SS-8">8</A> Van Meurs PJ. Jansen RAJ. J. Org. Chem.  2000,  65:  5712 

<A NAME="RC12002SS-9">9</A> Akita T. Koga N. Polyhedron  2001,  20:  1475 

<A NAME="RC12002SS-10">10</A> Nishide H. Yoshioka N. Inagaki K. Tsuchida E. Macromolecules  1988,  21:  3120 

<A NAME="RC12002SS-11">11</A> Nishide H. Kaneko T. Igarashi M. Tsuchida E. Yoshioka N. Lahti PM. Macromolecules  1994,  27:  3082 

<A NAME="RC12002SS-12">12</A> Nishide H. Yoshioka N. Kaneko T. Tsuchida E. Macromolecules  1990,  23:  4487 

<A NAME="RC12002SS-13">13</A> Yoshioka N., Nishide H., Kaneko T., Yoshiki H., Tsuchida E.; Macromolecules; 1992, 25: 3838

<A NAME="RC12002SS-14">14</A> Rajca A. Wongsriratanakul J. Rajca S. Cerny R. Angew. Chem. Int. Ed.  1998,  37:  1229 

<A NAME="RC12002SS-15">15</A> Rajca A. Rajca S. Wongsriratanakul J. J. Am. Chem. Soc.  1999,  121:  6308 

<A NAME="RC12002SS-16">16</A> Rajca A. Wongsriratanakul J. Rajca S. Science  2001,  294:  1503 

<A NAME="RC12002SS-17">17</A> Murata S. Iwamura H. J. Am. Chem. Soc.  1991,  113:  5547 

<A NAME="RC12002SS-18">18</A> Wautelet P. Bieber A. Turek P. Le Moigne J. André JJ. Mol Cryst. Liq. Cryst.  1997,  305:  55 

<A NAME="RC12002SS-19">19</A> Miura Y. Issiki T. Ushitani Y. Teki Y. Itoh K. J. Mater. Chem.  1996,  6:  1745 

<A NAME="RC12002SS-20">20</A> Swoboda P. Saf R. Hummel K. Hofer F. Czaputa R. Macromolecules  1995,  28:  4255 

<A NAME="RC12002SS-21">21</A> Catala L. Turek P. Le Moigne J. De Cian A. Kyritsakas N. Tetrahedron Lett.  2000,  41:  1015 

<A NAME="RC12002SS-22">22</A>

Wautelet, P.; Turek, P.; Le Moigne, J.; André J. J.; Bieber, A. J. Org. Chem. 2002, submitted.

<A NAME="RC12002SS-23">23</A> Austin WB. Bilow N. Kelleghan WJ. Lau KSY. J. Org. Chem.  1981,  46:  2280 

<A NAME="RC12002SS-24">24</A> Harrer W. Kurrek H. Reusch J. Gierke W. Tetrahedron  1975,  31:  625 

<A NAME="RC12002SS-25A">25a</A> Trumbo DL. Marvel CS. J. Polym. Sci. Polym. Chem.  1987,  25:  839 

<A NAME="RC12002SS-25B">25b</A> Moroni M. Le Moigne J. Luzzati S. Macromolecules  1994,  27:  562 

<A NAME="RC12002SS-25C">25c</A> Mangel T. Eberhardt A. Bunz UHF. Müllen K. Macromol. Rapid Commun.  1995,  16:  571 

<A NAME="RC12002SS-25D">25d</A> For a review, see: Bunz UHF. Chem. Rev.  2000,  100:  1605 

<A NAME="RC12002SS-26">26</A>

The magnetic properties of G- pmp -G have not been studied, due to the rapid decomposition of the radicals even in the solid state.

<A NAME="RC12002SS-27">27</A> Becconsall JK. Clough S. Scott G. Trans Faraday Soc.  1960,  56:  459 

<A NAME="RC12002SS-28">28</A> Mukai K. Iizuka M. Ishizu K. Bull. Chem. Soc. Jpn.  1973,  46:  3578 

<A NAME="RC12002SS-29">29</A>

The phenylene-ethynylene unit with similar connectivity has been shown to be an efficient coupler at a distance of 20 Å between imino-nitroxide radical derivatives. [3] It is assumed here, that the through bond spin exchange should set up as well at the same distance range (ca. 17-20 Å).

<A NAME="RC12002SS-30">30</A> Volod’kin AA. Ershov VV. Izv. Akad. Nauk SSSR  1962,  11:  2022 

<A NAME="RC12002SS-31">31</A> Klebe JF. Finkbeiner H. White DM. J. Am. Chem. Soc.  1966,  88:  3391 

<A NAME="RC12002SS-32">32</A>

A summary of the route to G- pmp -G.