TY  - THES
A1  - Bold, Kevin
T1  - Macrocyclic Oligothiophene Bridged Perylene Bisimide Donor−Acceptor Dyads
T1  - Makrozyklische Oligothiophen-überbrückte Perylenbisimid Donor-Akzeptor Dioden
N2  - A series of donor-acceptor macrocyclic architectures comprising oligothiophene strands that connect the imide positions of a perylene bisimide have been synthesized via a platinum-mediated cross-coupling strategy. The target structures were characterized by steady-state UV/Vis absorption, fluorescence and transient absorption spectroscopy, as well as cyclic and differential pulse voltammetry. Crystal structure analysis of the macrocycles revealed insights into the bridge arrangements. The properties of the macrocyclic bridges were compared to linear oligothiophene reference compounds which itself exhibited an unusual electrochemical effect.
N2  - In der vorliegenden Dissertation wurde eine Reihe von Donor-Akzeptor Makrozyklen bestehend aus Oligothiophensträngen, welche die Imid-Positionen eines Perylenbisimids kovalent verbinden, in einer Platin-vermittelten Kreuzkupplungsreaktion synthetisiert. Die Zielstrukturen wurden anschließend mittels UV/Vis-, Fluoreszenz-und transienter Absorptionsspektroskopie, sowie zyklischer- bzw. Differential-Puls-Voltammetry charakterisiert. Ferner gewährten Kristallstrukturen von drei der insgesamt fünf Makrozyklen strukturelle Einblicke in die Oligothiophen-Brückengeometrie. Die photophysikalischen und elektrochemischen Eigenschaften der makrozyklischen Brücken wurden mit solchen linearer Oligothiophen-Referenzsystemen verglichen, welche selber ein ungewöhnliches Phänomen in der Elektrochemie aufwiesen.
KW  - Perylenbisdicarboximide
KW  - Makrocyclische Verbindungen
KW  - Thiophen
KW  - Farbstoff
KW  - donor-acceptor dyads
KW  - macrocycles
KW  - electron transfer
KW  - perylene bisimide
KW  - oligothiophenes
Y1  - 2022
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-271926
ER  - 
TY  - JOUR
A1  - Bold, Kevin
A1  - Stolte, Matthias
A1  - Shoyama, Kazutaka
A1  - Holzapfel, Marco
A1  - Schmiedel, Alexander
A1  - Lambert, Christoph
A1  - Würthner, Frank
T1  - Macrocyclic donor-acceptor dyads composed of a perylene bisimide dye surrounded by oligothiophene bridges
JF  - Angewandte Chemie Internationale Edition
N2  - Two macrocyclic architectures comprising oligothiophene strands that connect the imide positions of a perylene bisimide (PBI) dye have been synthesized via a platinum-mediated cross-coupling strategy. The crystal structure of the double bridged PBI reveals all syn-arranged thiophene units that completely enclose the planar PBI chromophore via a 12-membered macrocycle. The target structures were characterized by steady-state UV/Vis absorption, fluorescence and transient absorption spectroscopy, as well as cyclic and differential pulse voltammetry. Both donor–acceptor dyads show ultrafast Förster Resonance Energy Transfer and photoinduced electron transfer, thereby leading to extremely low fluorescence quantum yields even in the lowest polarity cyclohexane solvent.
KW  - organic chemistry
KW  - photoinduced electron transfer
KW  - donor–acceptor dyads
KW  - macrocycles
KW  - oligothiophenes
KW  - perylenebisimide
Y1  - 2022
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-256569
VL  - 61
IS  - 1
ER  - 
TY  - JOUR
A1  - Bold, Kevin
A1  - Stolte, Matthias
A1  - Shoyama, Kazutaka
A1  - Krause, Ana‐Maria
A1  - Schmiedel, Alexander
A1  - Holzapfel, Marco
A1  - Lambert, Christoph
A1  - Würthner, Frank
T1  - Macrocyclic Donor‐Acceptor Dyads Composed of Oligothiophene Half‐Cycles and Perylene Bisimides
JF  - Chemistry – A European Journal
N2  - A series of donor‐acceptor (D−A) macrocyclic dyads consisting of an electron‐poor perylene bisimide (PBI) π‐scaffold bridged with electron‐rich α‐oligothiophenes bearing four, five, six and seven thiophene units between the two phenyl‐imide substituents has been synthesized and characterized by steady‐state UV/Vis absorption and fluorescence spectroscopy, cyclic and differential pulse voltammetry as well as transient absorption spectroscopy. Tying the oligothiophene strands in a conformationally fixed macrocyclic arrangement leads to a more rigid π‐scaffold with vibronic fine structure in the respective absorption spectra. Electrochemical analysis disclosed charged state properties in solution which are strongly dependent on the degree of rigidification within the individual macrocycle. Investigation of the excited state dynamics revealed an oligothiophene bridge size‐dependent fast charge transfer process for the macrocyclic dyads upon PBI subunit excitation.
KW  - donor-acceptor dyad
KW  - macrocycle
KW  - oligothiophene
KW  - perylene bisimide
KW  - photoinduced electron transfer
Y1  - 2022
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-276435
VL  - 28
IS  - 30
ER  -