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.
引用
收藏
页码:6735 / 6738
页数:4
相关论文
共 26 条
[11]   PHOTOKINETIC BASES FOR MODERN CHEMICAL ACTINOMETERS [J].
GAUGLITZ, G ;
HUBIG, S .
ZEITSCHRIFT FUR PHYSIKALISCHE CHEMIE-WIESBADEN, 1984, 139 :237-246
[12]   SYNTHESIS AND EPR-SPECTROSCOPY OF PHENYL-SUBSTITUTED AND PARTIALLY DEUTERATED SCHLENKS HYDROCARBONS [J].
HINRICHS, K ;
KURRECK, H ;
NIEMEIER, W .
TETRAHEDRON, 1974, 30 (02) :315-320
[13]   STUDIES OF ORGANIC DIRADICALS, OLIGORADICALS, AND POLYRADICALS BY MEANS OF THEIR BULK MAGNETIC-PROPERTIES [J].
IWAMURA, H ;
KOGA, N .
ACCOUNTS OF CHEMICAL RESEARCH, 1993, 26 (06) :346-351
[14]   COMBINATION OF SUPEREXCHANGE AND SPIN-POLARIZATION MECHANISMS LEADS TO A NOVEL HYDROCARBON TETRARADICAL WITH A HIGH-SPIN GROUND-STATE [J].
JACOBS, SJ ;
DOUGHERTY, DA .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 1994, 33 (10) :1104-1106
[15]   Ab initio calculations on 1,3,5,-trimethylenebenzene and its negative ion provide predictions about the photoelectron spectrum of the ion [J].
Kemnitz, CR ;
Squires, RR ;
Borden, WT .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (28) :6564-6574
[16]   1,3-cyclopentanediyl diradicals: Substituent and temperature dependence of triplet-singlet intersystem crossing [J].
Kita, F ;
Adam, W ;
Jordan, P ;
Nau, WM ;
Wirz, J .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1999, 121 (40) :9265-9275
[17]   SCHLENKS BIRADICAL - MOLECULE IN TRIPLET GROUND STATE [J].
KOTHE, G ;
DENKEL, KH ;
SUMMERMA.W .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 1970, 9 (11) :906-&
[18]  
KOTHE G, 1975, CHEM BER, V108, P2124
[19]  
KUHLMEY SR, 1979, LIEBIGS ANN CHEM, P617
[20]   EXPLORATORY AND MECHANISTIC STUDIES OF THE TRIMERIZATION REACTION OF BENZOYLACETYLENES IN THE PRESENCE OF A SECONDARY AMINE [J].
MATSUDA, K ;
NAKAMURA, N ;
IWAMURA, H .
CHEMISTRY LETTERS, 1994, (09) :1765-1768