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Trovacene Chemistry. 16, 1,1a‐Di([5]trovacenyl)‐1,1,1a,1a‐tetraphenyl‐disiloxane: Electro‐ and Magneto‐Communication Across a Si‐O‐Si Spacer
Author(s) -
Elschenbroich Christoph,
Lu Feng,
Burghaus Olaf,
Harms Klaus,
Nowotny Mathias
Publication year - 2007
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.200700275
Subject(s) - disiloxane , chemistry , cyclic voltammetry , polarizability , electron paramagnetic resonance , analytical chemistry (journal) , crystallography , nuclear magnetic resonance , organic chemistry , electrochemistry , molecule , electrode , physics , catalysis
Abstract By means of lithiation and subsequent derivatization [5]trovacenyl‐diphenylsilanol ( 2· ), di([5]trovacenyl)tetraphenyl‐disiloxane ( 3·· ), di([5]trovacenyl)tetramethyl‐disiloxane ( 4·· ) and di([5]trovacenyldimethylsilyl)methane ( 6·· ) have been prepared and characterized by X‐ray diffraction ( 2· , 3·· , 6·· ). Although the bond angles of the disiloxane bridges differ considerably, magnetic exchange interaction in these organometallic diradicals is practically unaffected as shown by fluid solution EPR spectroscopy. By way of contrast, electrocommunication clearly responds to change in the structure of the SiOSi spacer in that the redox splittings derived from cyclic voltammetry display the gradation δE 1/2 (0/–/2–) 4·· < 6·· < 3·· . It is proposed that in this order electronic polarizability in the intervening spacer increases thereby facilitating the transmission of electrostatic effects.