Show/Hide Menu
Hide/Show Apps
Logout
Türkçe
Türkçe
Search
Search
Login
Login
OpenMETU
OpenMETU
About
About
Open Science Policy
Open Science Policy
Open Access Guideline
Open Access Guideline
Postgraduate Thesis Guideline
Postgraduate Thesis Guideline
Communities & Collections
Communities & Collections
Help
Help
Frequently Asked Questions
Frequently Asked Questions
Guides
Guides
Thesis submission
Thesis submission
MS without thesis term project submission
MS without thesis term project submission
Publication submission with DOI
Publication submission with DOI
Publication submission
Publication submission
Supporting Information
Supporting Information
General Information
General Information
Copyright, Embargo and License
Copyright, Embargo and License
Contact us
Contact us
Synthesis and Optoelectronic Properties of Janus-Dendrimer-Type Multivalent Donor Acceptor Systems
Date
2015-01-16
Author
Dengiz, Çağatay
GISSELBRECHT, Jean-Paul
BOUDON, Corinne
TRAPP, Nils
SCHWEIZER, W. Bernd
DIEDERICH, Francois
Metadata
Show full item record
This work is licensed under a
Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License
.
Item Usage Stats
187
views
0
downloads
Cite This
A convergent, multistep protocol was employed for the synthesis of a Janus-type multivalent donoracceptor system. The synthetic approach is based on a Sonogashira cross-coupling of two differently ferrocene-(Fc) substituted dendrons and a final sixfold [2 + 2] cycloaddition-retroelectrocyclization (CA-RE) reaction with tetracyanoethene, which occurs regioselectively at only one of the rigidly linked dendrons. The structural and optoelectronic properties of the compounds were investigated by X-ray analysis, UV/vis spectroscopy, and electrochemistry. The target Janus-system displays redox-amphoteric behavior. The nonalkynylated Fc end groups in one dendron are readily and reversibly oxidized. The second dendron, in which the terminal Fc-activated alkynes underwent the CA-RE reaction to give tetracyanobuta-1,3-dienes in the final step of the synthesis, undergoes four reversible 3-e reductions in the very narrow potential range of 1 V. A spontaneous intramolecular charge transfer from the donor into the acceptor hemisphere was not observed. Furthermore, the oxidation potential of the Fc donors in one hemisphere is hardly perturbed by the pushpull acceptors in the other, which suggests that electronic communication along the p-system, with several meta-connectivities, is not efficient. Therefore, the charge-transfer bands seen in the Janus-type system originate from the interaction of the Fc donors with the directly connected tetracyanobuta-1,3-diene acceptors in the same hemisphere.
Subject Keywords
Amphiphilic diblock dendrimers
,
Charge-transfer interactions
,
Crystal-structures
,
Shape-persistent
,
Molecular architectures
,
Convenient synthesis
,
2+2 cycloaddition
,
Dendrons
,
Macromolecules
,
Chromophores
URI
https://hdl.handle.net/11511/42926
Journal
JOURNAL OF ORGANIC CHEMISTRY
DOI
https://doi.org/10.1021/jo502367h
Collections
Department of Chemistry, Article
Suggestions
OpenMETU
Core
Synthesis of Bishomoinositols and an Entry for Construction of a Substituted 3-Oxabicyclo[3.3.1]nonane Skeleton
BARAN, ARİF; Bekarlar, Merve; Aydin, Gokay; NEBİOĞLU, MEHMET; ŞAHİN, Ertan; Balcı, Metin (2012-02-03)
1,3,3a,7a-Tetrahydro-2-benzofuran was used as key compound for the synthesis of various bishomoinositol derivatives. The diene was subjected to an epoxidation reaction for further functionalization of the diene unit. The bisepoxide obtained was submitted to a ring-opening reaction with acid in the presence of water. Various bishomoinositols were synthesized. However, when the reaction was carried out in the presence of acetic anhydride, a substituted 3-oxabicyclo[3.3.1]nonane skeleton was formed. The mechan...
Synthesis of conducting block and graft copolymers with polyether segments
Yagci, Y; Toppare, Levent Kamil (Wiley, 2000-07-01)
Synthesis of block and graft copolymers containing polyether and conducting polypyrrole sequences were described. Pyrrole moieties were incorporated at the chain ends of polytetrahydrofuran and polysiloxane and at the side chains of polyethyl vinylether by ionic polymerization and appropriate chemical reactions. Subsequent electropolymerization with pyrrole through these moities yielded free standing films of the corresponding block and graft copolymers. The formation copolymers was evidenced by FTIR spectr...
Synthesis, characterizations and investigation of thermoluminescence properties of strontium pyrophosphate doped with metals
Ilkay, L. S.; ÖZBAYOĞLU, GÜLHAN; Yılmaz, Ayşen (2014-11-01)
Strontium pyrophosphate, Sr2P2O7, was synthesized by solid-state synthesis method; the product was co-doped with copper-silver (Cu-Ag), copper-indium (Cu-In) and manganese-praseodymium (Mn-Pr) oxides (CuO, MnO, In2O3, Pr6O11 and AgNO3) by solid-state reaction method. The variation of dopant concentrations was investigated from 0.5 to 15% by weight. In addition to these processes, chemical characterizations of samples and the investigation of thermoluminescence (TLD) properties of strontium pyrophosphate wit...
Synthesis of ferrocene substituted pyrrolidine derivatives via Et2Zn catalyzed 1 3 dipolar cycloaddition reactions of azomethine ylides
Doğan, Özdemir (2001-05-01)
Synthesis of ferrocene substituted pyrrolidine derivatives via diethylzinc catalyzed 1,3-dipolar cycloadditions of azomethine ylides is described. Azomethine ylides were generated from glycine methyl ester and ferrocenecarboxaldehyde by the 'imine tautomerization' method and trapped with dipolarophiles to give the corresponding cycloadducts in reasonable yields and high regio- and stereoselectivity.
Design and Synthesis of Aviram-Ratner-Type Dyads and Rectification Studies in Langmuir-Blodgett (LB) Films
JAYAMURUGAN, Govindasamy; GOWRI, Vijayendran; HERNANDEZ, David; MARTIN, Santiago; Gonzalez-Orive, Alejandro; Dengiz, Çağatay; DUMELE, Oliver; PEREZ-MURANO, Francesc; GISSELBRECHT, Jean-Paul; BOUDON, Corinne; SCHWEIZER, W. Bernd; BREITEN, Benjamin; FINKE, Aaron D.; JESCHKE, Gunnar; BERNET, Bruno; RUHLMANN, Laurent; CEA, Pilar; DIEDERICH, Francois (2016-07-18)
The design and synthesis of Aviram-Ratner-type molecular rectifiers, featuring an anilino-substituted extended tetracyanoquinodimethane (exTCNQ) acceptor, covalently linked by the sigma-spacer bicyclo[2.2.2]octane (BCO) to a tetrathiafulvalene (TTF) donor moiety, are described. The rigid BCO spacer keeps the TTF donor and exTCNQ acceptor moieties apart, as demonstrated by X-ray analysis. The photophysical properties of the TTF-BCO-exTCNQ dyads were investigated by UV/Vis and EPR spectroscopy, electrochemica...
Citation Formats
IEEE
ACM
APA
CHICAGO
MLA
BibTeX
Ç. Dengiz, J.-P. GISSELBRECHT, C. BOUDON, N. TRAPP, W. B. SCHWEIZER, and F. DIEDERICH, “Synthesis and Optoelectronic Properties of Janus-Dendrimer-Type Multivalent Donor Acceptor Systems,”
JOURNAL OF ORGANIC CHEMISTRY
, pp. 882–896, 2015, Accessed: 00, 2020. [Online]. Available: https://hdl.handle.net/11511/42926.