Thianthrene and related heterocycles [Elektronische Ressource] : metal complexes, radical cation salts and semiconductors / vorgelegt von Rachmat Triandi Tjahjanto

Thianthrene and related heterocycles [Elektronische Ressource] : metal complexes, radical cation salts and semiconductors / vorgelegt von Rachmat Triandi Tjahjanto

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Thianthrene and Related Heterocycles:Metal Complexes, Radical Cation Saltsand SemiconductorsD I S S E R T A T I O Nzur Erlangungdes Doktogrades (Dr. rer. nat.)der Mathematisch-Naturwissenschaftlichen Fakultatder Rheinischen Friedrich-Wilhelms-Universitat Bonnvorgelegt vonRachmat Triandi Tjahjanto, M. Sc.ausMakassar/IndonesienBonn 2009Angefertigt mit Genehmigung der Mathematischen-Naturwissenschaftlichen Fakult atder Rheinischen Friedrich-Wilhelms-Universit at Bonn1. Gutachter: Prof. Dr. Johannes Beck2. Gutachter: Prof. Dr. Alexander C. FilippouTag der Promotion: 17.7.2009Erscheinungsjahr: 2009Diese Dissertation ist auf dem Hochschulschriftenserver der ULB Bonn unterhttp://hss.ulb.uni-bonn.de/diss online elektronisch publiziert.AbstractLiquid SO was used as a solvent for complexation as well as redox reactions based2{on thianthrene and related heterocyclic molecules. With silver salt, AgX (X = BF ,4{SbF ), the complexes [Ag (TA) ][BF ] 3 SO (1) and [Ag (TA) ][SbF ] 5 SO (2),6 2 2 4 2 2 2 3 6 2 2and with gold(III) chloride, the complex [AuCl (TA) ][AuCl ] (3) were obtained.2 2 4+The oxidation products contain radical cations of thianthrene, TA , as found in the structure of (TA )(HSO ) H SO (5) and (TA )[FeCl ] (6), radical cation of se-4 2 4 4 lenanthrene in the structure of (SA )[AlCl ] (8) and (SA ) [SO (BF ) ] (10), and4 2 4 3 2a structure with a bridging oxygen of -oxy-selenanthrene(2+), SAO(HSO ) (9).

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Thianthrene and Related Heterocycles:
Metal Complexes, Radical Cation Salts
and Semiconductors
D I S S E R T A T I O N
zur Erlangung
des Doktogrades (Dr. rer. nat.)
der Mathematisch-Naturwissenschaftlichen Fakultat
der Rheinischen Friedrich-Wilhelms-Universitat Bonn
vorgelegt von
Rachmat Triandi Tjahjanto, M. Sc.
aus
Makassar/Indonesien
Bonn 2009Angefertigt mit Genehmigung der Mathematischen-Naturwissenschaftlichen Fakult at
der Rheinischen Friedrich-Wilhelms-Universit at Bonn
1. Gutachter: Prof. Dr. Johannes Beck
2. Gutachter: Prof. Dr. Alexander C. Filippou
Tag der Promotion: 17.7.2009
Erscheinungsjahr: 2009
Diese Dissertation ist auf dem Hochschulschriftenserver der ULB Bonn unter
http://hss.ulb.uni-bonn.de/diss online elektronisch publiziert.Abstract
Liquid SO was used as a solvent for complexation as well as redox reactions based2
{on thianthrene and related heterocyclic molecules. With silver salt, AgX (X = BF ,4
{SbF ), the complexes [Ag (TA) ][BF ] 3 SO (1) and [Ag (TA) ][SbF ] 5 SO (2),6 2 2 4 2 2 2 3 6 2 2
and with gold(III) chloride, the complex [AuCl (TA) ][AuCl ] (3) were obtained.2 2 4
+The oxidation products contain radical cations of thianthrene, TA , as found in
the structure of (TA )(HSO ) H SO (5) and (TA )[FeCl ] (6), radical cation of se-4 2 4 4
lenanthrene in the structure of (SA )[AlCl ] (8) and (SA ) [SO (BF ) ] (10), and4 2 4 3 2
a structure with a bridging oxygen of -oxy-selenanthrene(2+), SAO(HSO ) (9).4 2
The reaction between thianthrene and aluminum chloride was also performed with-
out solvent, resulting in an adduct [AlCl (TA)] (4) and a unique thianthrene "triple3
decker", (TA )[Al Cl ] (7). An unexpected phenazine salt, (H PAz)(HSO ) (11)3 2 7 2 2 4 2
was obtained from phenazine in an oxidative environment. All compounds were ex-
amined by single crystal X -ray di ractometry. The gold and aluminum complexes
were additionally characterized by UV-Vis, IR and Raman spectra, calorimetry and
conductivity measurements. Cyclic voltammetry measurements of thianthrene in SO2
at room temperature were performed using a self-made pressure-tight electrochemi-
cal cell and electrodes with the result that liquid SO does not reduce the oxidation2
potential of thianthrene. The in uence of SO , which is often present in liquid SO3 2
as impurity, was also studied, con rming its role in the oxidation of thianthrene. The
use of liquid SO combined with weak coordinating anions allows complexation of sil-2
ver ion with higher coordination number, bonded to thianthene via S atoms. SO as3
an impurity in liquid SO is the most probable source for oxidation reaction leading2
to the compounds containing radical cations. Thianthrene undergoes self-oxidation
processes in the presence of AlCl , both with or without solvent. Close TA TA3
arrangements in the crystal structures should be an indication of the electrical semi-
conductivity.vii
Preface
This dissertation is written to ful ll the the requirement for doctoral grade in Math
and Natural Science from the Institute of Inorganic Chemistry of University of Bonn.
It is based on a series of experimental works during the period from the very beginning
of 2004 to the mid of 2008 in the Institute for Inorganic Chemistry, the University of
Bonn. Most part of this dissertation is already reported, in short, in six workgroup
seminars in the Institute and two poster presentations in GDCh-Jahrestagung in
Aachen and in Ulm and one oral speech in Hirschegg, Austria. Besides, parts of it
have been also published in three publications.
For all material supports and intensive supervisions during the period of doc-
toral program I thank Professor Dr. Johannes Beck as my supervisor and I thank
Dr. J org Daniels for the crystal selections and measurements. Norbert Wagner, Volker
Bendish, Marcus Zink, Doris Ernsth auser, Dr. Ralf Weisbarth and Barbara Knopp
are thanked for performing measurements in this work.ix
Parts of this dissertation are published in the following papers:
R. T. Tjahjanto and J. Beck, Synthesis and crystal structures of silver thianthrene
complexes with weakly coordinating anions, Zeitschrift fur Naturforschung, B, vol.
62, pp. 1291{1297, 2007.
J. Beck, T. Bredow, and R. T. Tjahjanto, Thianthrene radical cation hexa uorophos-
phate, Zeitschrift fur Naturforschung, B, vol. 64b, pp. 145{152, 2009.
R. T. Tjahjanto and J. Beck, Synthesis and Characterization of Semiconductive
Dichloridobis(thianthrene)gold(1+) tetrachloridoaurate(1{), European Journal of In-
organic Chemistry, 2524{2528, 2009.