Milan Kivala

 

Postdoctoral Fellow

Location:

HCI G-304

Phone:

+41-44-632 4501

e-mail:

Milan Kivala

Education

1998-2003:

Study of chemistry at Institute of Chemical Technology, Prague.

2001-2002:

Internship at Chalmers University of Technology, Department of Applied Surface Chemistry, Göteborg, Sweden.

2003:

Diploma thesis with Prof. F. Liška. Institute of Chemical Technology, Department of Organic Chemistry, Prague.

2004-2007:

PhD with Prof. F. Diederich at ETH Zurich. Thesis "Two-Dimensional Acetylenic Scaffolding: Extended Donor-Substituted Perethynylated Dehydroannulenes, Charge-Transfer Chromophores, and Cascade Reactions".

since 2008:

Postdoctoral Fellow with Prof. F. Diederich at the ETH Zurich.

Acetylenic Molecular Architecture


Dendrimer-like donor-substituted TCBD capable of taking up 24 electrons in a narrow potential range under electrochemical conditions.

Acetylenic molecular structures continue to be an intriguing and inspiring field of research at the interface between synthetic organic chemistry, physical organic chemistry and material sciences. Thermal [2+2] cycloadditions of tetracyanoethylene (TCNE) with electron-rich alkynes yield 1,1,4,4-tetracyanobuta-1,3-dienes (TCBDs). Recently, we found that a wide variety of N,N-dialkylanilino (DAA)-substituted alkynes react smoothly with TCNE to furnish DAA-donor-substituted TCBDs in often quantitative yield. This new class of chromophores features intense intramolecular charge-transfer (CT) interactions with absorption maxima in the visible spectral range as well as promising third-order optical nonlinearities. A similar reaction occurs under the conditions of inverse electron demand. The strong donor tetrathiafulvalene (TTF) undergoes cycloaddition with electron-deficient acetylene moieties in cyanoethynylethenes.

This research so far has culminated in the preparation of dendrimer-like, multivalent CT chromophores acting as a type of molecular batteries that are capable of taking up an exceptional number of electrons. Finally, a one-pot protocol for cascade TCNE/TTF additions to polyynes, controlled by the electronic properties of individual acetylenic triple bonds, has opened up an easy access to a new class of [AB]-type oligomers and polymers. Recently, we described a novel, completely regioselective [2+2] cycloaddition of 7,7,8,8-tetracyanoquinodimethane (TCNQ) with DAA-substituted alkynes.

The application of [2+2] thermal cycloadditions with alkynes to the preparation of functional carbon-rich architectures is currently being pursued.

Publications

M. Kivala, C. Boudon, J.-P. Gisselbrecht, B. Enko, P. Seiler, I. B. Müller, N. Langer, P. D. Jarowski, G. Gescheidt, F. Diederich, Chem. Eur. J. 2009 in press. Organic Super-Acceptors with Efficient Intramolecular Charge-Transfer Interactions by [2+2] Cycloadditions of TCNE, TCNQ and F4-TCNQ to Donor-Substituted Cyanoalkynes.

M. Kivala, F. Diederich, Acc. Chem. Res. 2009, 42, 235-248. Acetylene-Derived Strong Organic Acceptors for Planar and Nonplanar Push-Pull Chromophores.

M. Kivala, T. Stanoeva, T. Michinobu, B. Frank, G. Gescheidt, F. Diederich, Chem. Eur. J. 2008, 14, 7638-7647. One-Electron-Reduced and -Oxidized Stages of Donor-Substituted 1,1,4,4-Tetracyanobuta-1,3-dienes of Different Molecular Architectures.

M. Kivala, F. Diederich, Pure and Appl. Chem. 2008, 80, 413-429. Conjugation and Optoelectronic Properties of Acetylenic Scaffolds and Charge-Transfer Chromophores.

P. Reutenauer, M. Kivala, P. D. Jarowski, C. Boudon, J.-P. Gisselbrecht, M. Gross, F. Diederich, Chem. Commun. 2007, 4898-4900. New Strong Organic Acceptors by Cycloaddition of TCNE and TCNQ to Donor-substituted Cyanoalkynes.

M. Kivala, C. Boudon, J.-P. Gisselbrecht, P. Seiler, M. Gross, F. Diederich, Chem. Commun. 2007, 4731-4733. A Novel Reaction of 7,7,8,8-Tetracyanoquinodimethane (TCNQ): Charge-Transfer Chromophores by [2+2] Cycloaddition with Alkynes.

M. Kivala, C. Boudon, J.-P. Gisselbrecht, P. Seiler, M. Gross, F. Diederich, Angew. Chem. 2007, 119, 6473-6477; Angew. Chem. Int. Ed. 2007, 46, 6357-6350. Charge-Transfer Chromophores by Cycloaddition-Retro-electrocyclization: Multivalent Systems and Cascade Reactions.

M. Kivala, F. Mitzel, C. Boudon, J.-P. Gisselbrecht, P. Seiler, F. Diederich, Chem. Asian J. 2006, 1, 479-489. Two-Dimensional Acetylenic Scaffolding: Extended Donor-Substituted Perethynylated Dehydroannulenes.

M. Kivala, R. Cibulka, F. Hampl, Collect. Czech. Chem. Commun. 2006, 71, 1642-1658. Cleavage of 4-Nitrophenyl Diphenyl Phosphate by Isomeric Quaternary Pyridinium Ketoximes - How Can Structure and Lipophilicity of Functional Surfactants Influence Their Reactivity in Micelles and Microemulsions.

J. Pícha, K. Kuča, M. Kivala, M. Kohout, J. Cabal, F. Liška, J. Enzyme Inhib. Med. Chem. 2005, 20, 233-237. A New Group of Monoquaternary Reactivators of Acetylcholinesterase Inhibited by Nerve Agents.

K. Kuča, M. Kivala, V. Dohnal. J. Appl. Biomedicine 2004, 2, 195-198. A General Method for the Quaternization of N,N-Dimethyl Benzylamines with Long Chain n-Alkylbromides.

Last update: Feb 2009