Synthesis and properties of cyclic sandwich compounds

Nature volume 620, pages 92–96 (2023)Cite this article

39 Altmetric

Metrics details

Cyclic nanometre-scale sandwich complexes assembled from individual building blocks were synthesized. Sandwich complexes, in which a metal ion is π-coordinated by two planar aromatic organic rings belong to the foundations of organometallic chemistry. They have been successfully used in a wide variety of applications ranging from catalysis, synthesis and electrochemistry to nanotechnology, materials science and medicine1,2. Extending the sandwich structural motif leads to linear multidecker compounds, in which aromatic organic rings and metal atoms are arranged in an alternating fashion. However, the extension to a cyclic multidecker scaffold is unprecedented. Here we show the design, synthesis and characterization of an isomorphous series of circular sandwich compounds, for which the term ‘cyclocenes’ is suggested. These cyclocenes consist of 18 repeating units, forming almost ideally circular, closed rings in the solid state, that can be described by the general formula [cyclo-MII(μ-η8:η8-CotTIPS)]18 (M = Sr, Sm, Eu; CotTIPS = 1,4-(iPr3Si)2C8H62−). Quantum chemical calculations lead to the conclusion that a unique interplay between the ionic metal-to-ligand bonds, the bulkiness of the ligand system and the energy gain on ring closure, which is crucially influenced by dispersion interactions, facilitate the formation of these cyclic systems. Up to now, only linear one-dimensional multidecker sandwich compounds have been investigated for possible applications such as nanowires3,4,5,6,7,8,9,10. This textbook example of cyclic sandwich compounds is expected to open the door for further innovations towards new functional organometallic materials.

This is a preview of subscription content, access via your institution

Access Nature and 54 other Nature Portfolio journals

Get Nature+, our best-value online-access subscription

$29.99 / 30 days

cancel any time

Subscribe to this journal

Receive 51 print issues and online access

$199.00 per year

only $3.90 per issue

Rent or buy this article

Prices vary by article type

from$1.95

to$39.95

Prices may be subject to local taxes which are calculated during checkout

All data are available in the main text or in the supplementary material. Correspondence and request for materials should be addressed to P.W.R.

The TURBOMOLE quantum chemistry program suite is available from https://www.turbomole.org. Calculations were done on a cluster consisting of 8 PCs with 24 Intel(R) Xeon(R) Gold 6212U CPUs each.

Togni, A. Metallocenes: Synthesis, Reactivity, Applications (Wiley-VCH, 1998).

Štěpnička, P. Ferrocenes: Ligands, Materials and Biomolecules (John Wiley & Sons, Ltd, 2008).

Miyajima, K., Knickelbein, M. B. & Nakajima, A. Stern−Gerlach study of multidecker lanthanide–cyclooctatetraene sandwich clusters. J. Phys. Chem. A. 112, 366–375 (2008).

Article CAS PubMed Google Scholar

Hosoya, N. et al. Lanthanide organometallic sandwich nanowires: formation mechanism. J. Phys. Chem. A. 109, 9–12 (2005).

Article CAS PubMed Google Scholar

Kurikawa, T. et al. Multiple-decker sandwich complexes of lanthanide-1,3,5,7-cyclooctatetraene [Lnn(C8H8)m] (Ln = Ce, Nd, Eu, Ho, and Yb); localized ionic bonding structure. J. Am. Chem. Soc. 120, 11766–11772 (1998).

Article CAS Google Scholar

Tsuji, T. et al. Liquid-phase synthesis of multidecker organoeuropium sandwich complexes and their physical properties. J. Phys. Chem. C. 118, 5896–5907 (2014).

Article CAS Google Scholar

Huttmann, F., Schleheck, N., Atodiresei, N. & Michely, T. On-surface synthesis of sandwich molecular nanowires on graphene. J. Am. Chem. Soc. 139, 9895–9900 (2017).

Article CAS PubMed Google Scholar

Hosoya, N. et al. Formation and electronic structures of organoeuropium sandwich nanowires. J. Phys. Chem. A 118, 8298–8308 (2014).

Article CAS PubMed Google Scholar

Miyajima, K., Nakajima, A., Yabushita, S., Knickelbein, M. B. & Kaya, K. Ferromagnetism in one-dimensional vanadium–benzene sandwich clusters. J. Am. Chem. Soc. 126, 13202–13203 (2004).

Article CAS PubMed Google Scholar

Xiang, H., Yang, J., Hou, J. G. & Zhu, Q. One-dimensional transition metal–benzene sandwich polymers: possible ideal conductors for spin transport. J. Am. Chem. Soc. 128, 2310–2314 (2006).

Article CAS PubMed Google Scholar

Kealy, T. J. & Pauson, P. L. A new type of organo-iron compound. Nature 168, 1039–1040 (1951).

Article ADS CAS Google Scholar

Fischer, E. O. & Pfab, W. Cyclopentadien-Metallkomplexe, ein neuer Typ metallorganischer Verbindungen. Z. Naturforsch., B: Chem. Sci. 7, 377–379 (1952).

Article Google Scholar

Wilkinson, G., Rosenblum, M., Whiting, M. C. & Woodward, R. B. The structure of iron bis-cyclopentadienyl. J. Am. Chem. Soc. 74, 2125–2126 (1952).

Article CAS Google Scholar

Werner, H. & Salzer, A. Die Synthese Eines Ersten Doppel-Sandwich-Komplexes: Das Dinickeltricyclopentadienyl-Kation. Synth. React. Inorg. Met.-Org. Chem. 2, 239–248 (1972).

Elschenbroich, C. Organometallics (Wiley-VCH, 2008).

Zhuo, H.-C., Long, J. R. & Yaghi, O. M. Introduction to metal–organic frameworks. Chem. Rev. 112, 673–674 (2012).

Article Google Scholar

Kreno, L. E. et al. Metal–organic framework materials as chemical sensors. Chem. Rev. 112, 1105–1125 (2012).

Article CAS PubMed Google Scholar

Edelmann, F. T. Multiple-decker sandwich complexes of f-elements. New J. Chem. 35, 517–528 (2011).

Article CAS Google Scholar

Grossmann, B. et al. Seven doubly bridged ferrocene units in a cycle. Angew. Chem. Int. Ed. 36, 387–389 (1997).

Article CAS Google Scholar

Herbert, D. E. et al. Redox-active metallomacrocycles and cyclic metallopolymers: photocontrolled ring-opening oligomerization and polymerization of silicon-bridged [1]ferrocenophanes using substitutionally-labile Lewis bases as initiators. J. Am. Chem. Soc. 131, 14958–14968 (2009).

Article CAS PubMed Google Scholar

Chan, W. Y., Lough, A. J. & Manners, I. Organometallic macrocycles and cyclic polymers by the bipyridine-initiated photolytic ring opening of a silicon-bridged [1]ferrocenophane. Angew. Chem. Int. Ed. 46, 9069–9072 (2007).

Article CAS Google Scholar

Watts, W. E. The [1,1]ferrocenophane system 1. J. Am. Chem. Soc. 88, 855–856 (1966).

Article CAS Google Scholar

Katz, T. J., Acton, N. & Martin, G. [1n]Ferrocenophanes. J. Am. Chem. Soc. 91, 2804–2805 (1969).

Article CAS Google Scholar

Mueller-Westerhoff, U. T. & Swiegers, G. F. A synthesis of the cyclic ferrocene tetramer [1]4ferrocenophane. Chem. Lett. 23, 67–68 (1994).

Article Google Scholar

Inkpen, M. S. et al. Oligomeric ferrocene rings. Nat. Chem. 8, 825–830 (2016).

Article CAS PubMed Google Scholar

Wayda, A. L., Mukerji, I., Dye, J. L. & Rogers, R. D. Divalent lanthanoid synthesis in liquid ammonia. 2. The synthesis and X-ray crystal structure of (C8H8)Yb(C5H5N)3.1/2C5H5N. Organometallics 6, 1328–1332 (1987).

Article CAS Google Scholar

Hayes, R. G. & Thomas, J. L. Synthesis of cyclooctatetraenyleuropium and cyclooctatetraenylytterbium. J. Am. Chem. Soc. 91, 6876–6876 (1969).

Article CAS Google Scholar

Münzfeld, L., Hauser, A., Hädinger, P., Weigend, F. & Roesky, P. W. The archetypal homoleptic lanthanide quadruple-decker—synthesis, mechanistic studies, and quantum chemical investigations. Angew. Chem. Int. Ed. 60, 24493–24499 (2021).

Article Google Scholar

Overby, J. S., Hanusa, T. P. & Young, V. G. Redetermination of the zigzag modification of plumbocene at 173 K. Inorg. Chem. 37, 163–165 (1998).

Article CAS PubMed Google Scholar

Morrison, C. A., Wright, D. S. & Layfield, R. A. Interpreting molecular crystal disorder in plumbocene, Pb(C5H5)2: insight from theory. J. Am. Chem. Soc. 124, 6775–6780 (2002).

Article CAS PubMed Google Scholar

Suta, M., Kühling, M., Liebing, P., Edelmann, F. T. & Wickleder, C. Photoluminescence properties of the ‘bent sandwich-like’ compounds [Eu(TpiPr2)2] and [Yb(TpiPr2)2] – intermediates between nitride-based phosphors and metallocenes. J. Lumin. 187, 62–68 (2017).

Sztainbuch, I. W., Soos, Z. G. & Spiro, T. G. Herzberg–Teller coupling and configuration interaction in a metalloporphyrin model: 1,3,5,7‐tetramethylcyclo‐octatetraene dianion. J. Chem. Phys. 101, 4644–4648 (1994).

Article ADS CAS Google Scholar

Dorenbos, P. Anomalous luminescence of Eu2+ and Yb2+ in inorganic compounds. J. Phys. Condens. Matter 15, 2645–2665 (2003).

Article ADS CAS Google Scholar

TURBOMOLE v.7.6 (University of Karlsruhe and Forschungszentrum Karlsruhe, 1989–2007).

Balasubramani, S. G. et al. TURBOMOLE: modular program suite for ab initio quantum-chemical and condensed-matter simulations. J. Chem. Phys. 152, 184107 (2020).

Article ADS CAS PubMed PubMed Central Google Scholar

Foster, J. M. & Boys, S. F. Canonical configurational interaction procedure. Rev. Mod. Phys. 32, 300–302 (1960).

Article ADS MathSciNet CAS Google Scholar

Reed, A. E., Weinstock, R. B. & Weinhold, F. Natural population analysis. J. Chem. Phys. 83, 735–746 (1985).

Article ADS CAS Google Scholar

Schneider, E. K., Weis, P., Münzfeld, L., Roesky, P. W. & Kappes, M. M. Anionic stacks of alkali-interlinked yttrium and dysprosium bicyclooctatetraenes in isolation. J. Am. Soc. Mass. Spectrom. 33, 695–703 (2022).

Article CAS PubMed Google Scholar

Shannon, R. Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallogr., Sect. A. 32, 751–767 (1976).

Article ADS Google Scholar

Download references

C. Anson, M. Bodensteiner and F. Meurer are acknowledged for discussions about single-crystal X-ray diffraction data refinement. M. Dahlen is acknowledged for supporting PL measurements. Funding was provided by Fonds der Chemischen Industrie, Kekulé fellowship (grant no. 110160). We acknowledge support from the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) through the Collaborative Research Centre ‘4f for Future’ (CRC 1573 project no. 471424360, projects C1 and Q).

Institute of Inorganic Chemistry, Karlsruhe Institute of Technology (KIT), Karlsruhe, Germany

Luca Münzfeld, Sebastian Gillhuber, Adrian Hauser, Pauline Hädinger, Nicolai D. Knöfel, Christina Zovko, Michael T. Gamer & Peter W. Roesky

Institute of Nanotechnology, Karlsruhe Institute of Technology (KIT), Eggenstein-Leopoldshafen, Germany

Sergei Lebedkin & Manfred M. Kappes

Department of Chemistry, Philipps University of Marburg, Marburg, Germany

Florian Weigend

Institute of Physical Chemistry, Karlsruhe Institute of Technology (KIT), Karlsruhe, Germany

Manfred M. Kappes

You can also search for this author in PubMed Google Scholar

Experimental work was carried out by L.M. with support from A.H., P.H. and S.G. PL measurements were carried out by S.L. Single-crystal X-ray diffraction experiments and refinement were done by M.T.G. and L.M. DOSY-NMR was done by N.D.K. and C.Z. Density functional theory calculations were performed by S.G. and F.W. Project administration was done by P.W.R. Supervision was the responsibility of F.W., M.M.K. and P.W.R.

Correspondence to Peter W. Roesky.

The authors declare no competing interests.

Nature thanks Conrad Goodwin, Andre Schafer and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Peer reviewer reports are available.

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and Permissions

Münzfeld, L., Gillhuber, S., Hauser, A. et al. Synthesis and properties of cyclic sandwich compounds. Nature 620, 92–96 (2023). https://doi.org/10.1038/s41586-023-06192-4

Download citation

Received: 12 October 2022

Accepted: 10 May 2023

Published: 02 August 2023

Issue Date: 03 August 2023

DOI: https://doi.org/10.1038/s41586-023-06192-4

Anyone you share the following link with will be able to read this content:

Sorry, a shareable link is not currently available for this article.

Provided by the Springer Nature SharedIt content-sharing initiative

By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.