A Concept for Synthesis Planning in Solid-State Chemistry - Jansen - 2002 - Angewandte Chemie International Edition - Wiley Online Library

2/6/12 5:22 PM

Review

A Concept for Synthesis Planning in Solid-State Chemistry

1. Martin Jansen Prof. Dr. Article first published online: 18 OCT 2002 DOI: 10.1002/1521-3773(20021018)41:20<3746::AID-ANIE3746>3.0.CO;2-2 2002 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Issue

Angewandte Chemie International Edition

Volume 41, Issue 20, (/doi/10.1002/1521-3773(20021018)41:20<>1.0.CO;2-D/issuetoc) pages 37463766, October 18, 2002 Additional Information How to Cite Jansen, M. (2002), A Concept for Synthesis Planning in Solid-State Chemistry. Angewandte Chemie International Edition, 41: 37463766. doi: 10.1002/1521-3773(20021018)41:20<3746::AIDANIE3746>3.0.CO;2-2 Author Information Max-Planck-Institut fr Festkrperforschung Heisenbergstrasse 1, 70569 Stuttgart (Germany) Fax: (+49)!711-689-1502 Email: Martin Jansen Prof. Dr. (m.jansen@fkf.mpg.de)
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A Concept for Synthesis Planning in Solid-State Chemistry - Jansen - 2002 - Angewandte Chemie International Edition - Wiley Online Library

2/6/12 5:22 PM

Publication History 1. Issue published online: 18 OCT 2002 2. Article first published online: 18 OCT 2002 3. Manuscript Received: 18 APR 2002 Abstract Article (full) References (references) Cited By (citedby) View Full Article (HTML) (/doi/10.1002/1521-3773(20021018)41:20<3746::AID-ANIE3746>3.0.CO;22/full) Get PDF (594K) (/doi/10.1002/1521-3773(20021018)41:20<3746::AID-ANIE3746>3.0.CO;2-2/pdf)

Keywords:
solid-state chemistry; solid-state reactions; structure prediction; synthesis planning

Graphical Abstract
Hunter gatherers and not creators is how synthetic chemists could be described following a concept for the development of the (currently not yet feasible) goal-oriented synthesis of new solidstate compounds. The first step consists of the identification of realistic synthesis goals, which is achieved by the exploration of the energy landscape of the chemical system of interest using global optimization methods. Less developed are approaches for the second step, the rational design of feasible synthesis routes. Here, the crucial issues are the use of synthesis routes with extremely low activation and the control of nucleation processes. The picture shows the results of the theoretical exploration of the energy landscape of MgF 2 (structure candidates of low energy and the barrier structure depicted as a tree graph.)

Abstract
There is a widely-held belief that the preparation of new solid-state compounds based on rational design is not possible. Herein, we present a concept that points the way towards a rational design of syntheses in solid-state chemistry. The foundation of our approach is the representation of the whole material world, that is, the known and not-yet-known compounds, on an energy landscape, which gives information about the free energies of these compounds. From this it follows that all chemical compounds capable of existence are present on this landscape. Thus the chemical synthesis always corresponds to the discovery of compounds, not their creation. Consequently, the first step in planning a synthesis can and must be to identify a synthesizable compound. Up to now, materials capable of existence are discovered in the course of an experimental exploration of the energy landscape; however, an a priori identification of a synthesis goal
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A Concept for Synthesis Planning in Solid-State Chemistry - Jansen - 2002 - Angewandte Chemie International Edition - Wiley Online Library

2/6/12 5:22 PM

requires an exploration using theoretical methods. In contrast to those computational approaches currently employed for structure determination for fixed composition and already known unit cells, our aims clash with such restrictions and full global optimizations have to be performed on the landscape. Although for reasons of computational feasibility the accuracy of the energy calculations is not yet as high as one would wish, our approach proves to be surprisingly robust. One always finds the already known compounds of a given chemical system, and, in addition, further plausible structure candidates are discovered. The second step of a rational planning of syntheses is the design of feasible synthesis routes. Modeling such routes requires highly accurate computations for realistic thermodynamic conditions, however this is usually beyond our current capabilities. Thus, we have not seriously pursued such a deductive approach; instead we have attempted, to reproduce the computational annealing employed during our structure predictions in the experiment. Educts, generated by vapor deposition methods, that are disperse on an atomic level are found to react with surprisingly low activation energies to give highly crystallized products. However, even this technique does not yet provide the possibility to selectively synthesize a specific solid compound. For this final step, modeling and experimental control of nucleation processes will be the key ingredient. Only when viewed superficially, our goal of a rational design of solid-state syntheses and the highthroughput syntheses are in contradiction. But an exhaustive exploration of the unimaginably large combinatorial diversity of chemistry remains beyond our capabilities, even with an exceedingly high throughput. The future of solid-state synthesis will be found in a union of these two conceptual approaches. View Full Article (HTML) (/doi/10.1002/1521-3773(20021018)41:20<3746::AID-ANIE3746>3.0.CO;22/full) Get PDF (594K) (/doi/10.1002/1521-3773(20021018)41:20<3746::AID-ANIE3746>3.0.CO;2-2/pdf)

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