A hydrocarbon hexaradical with three localized 1,3-cyclopentanediyl triplet diradicals linked by 1,3,5-trimethylenebenzene as ferromagnetic coupler: Synthesis of the azoalkane precursor, photochemical generation of the polyradical, and EPR characterization of its septet-spin ground state

被引:23
作者
Adam, W
Baumgarten, M
Maas, W
机构
[1] Univ Wurzburg, Inst Organ Chem, D-97074 Wurzburg, Germany
[2] Max Planck Inst Polymerforsch, D-55128 Mainz, Germany
关键词
D O I
10.1021/ja0003369
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The unknown trisazoalkane 3 was prepared and photodenitrogenated into the novel septet hexaradical H-3, which is composed of three localized 1,3-cyclopentanediyl triplet diradicals as spin carriers, connected to the cross-conjugated ferromagnetic coupler 1,3,5-trimethylenebenzene. On nitrogen extrusion during the UV photolysis of the trisazoalkane 3 in the toluene matrix at 77 K, the characteristic triplet, quintet, and septet EPR signals for the corresponding diradical D-3, tetraradical T-3, and hexaradical H-3 were observed, all persistent for months at 77 K. Computer simulation of the EPR signals for the hexaradical gave the zero-field parameters D = 0.00907 cm(-1) and E = 0.000187 cm(-1), which is in good agreement with related polyradicals.
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页码:6735 / 6738
页数:4
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共 26 条
[21]   ORGANIC AND ORGANOMETALLIC MOLECULAR MAGNETIC-MATERIALS - DESIGNER MAGNETS [J].
MILLER, JS ;
EPSTEIN, AJ .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1994, 33 (04) :385-415
[22]   ORGANIC DIRADICALS AND POLYRADICALS - FROM SPIN COUPLING TO MAGNETISM [J].
RAJCA, A .
CHEMICAL REVIEWS, 1994, 94 (04) :871-893
[23]   DER QUARTETT-ZUSTAND DES R-ZENTRUMS IN KALIUMCHLORID-KRISTALLEN [J].
SEIDEL, H ;
SCHWOERE.M ;
SCHMID, D .
ZEITSCHRIFT FUR PHYSIK, 1965, 182 (04) :398-&
[24]   DETECTION OF AN AROMATIC HYDROCARBON IN ITS SEPTET ELECTRONIC GROUND-STATE BY ELECTRON-SPIN RESONANCE [J].
TAKUI, T ;
ITOH, K .
CHEMICAL PHYSICS LETTERS, 1973, 19 (01) :120-124
[25]   Persistent high-spin polycarbene.: Generation of polybrominated 1,3,5-tris-[2-[4-(phenylcarbeno)phenyl]ethynyl]benzene (S = 3) and spin identification by two-dimensional electron spin transient nutation spectroscopy [J].
Tomioka, H ;
Hattori, M ;
Hirai, K ;
Sato, K ;
Shiomi, D ;
Takui, T ;
Itoh, K .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (05) :1106-1107
[26]   STABLE POLYRADICALS WITH HIGH-SPIN GROUND-STATES .2. SYNTHESIS AND CHARACTERIZATION OF A COMPLETE SERIES OF POLYRADICALS DERIVED FROM 2,4,6-TRICHLORO-ALPHA,ALPHA,ALPHA',ALPHA',ALPHA'',ALPHA''-HEXAKIS(PENTACHLOROPHENYL)MESITYLENE WITH S = 1/2, 1, AND 3/2 GROUND-STATES [J].
VECIANA, J ;
ROVIRA, C ;
VENTOSA, N ;
CRESPO, MI ;
PALACIO, F .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1993, 115 (01) :57-64