One Dimensional Coordination Polymers Based on Bridging N,N Donor Ligands Der Naturwissenschaftlichen Fakultät der Friedrich-Alexander-Universität Erlangen-Nürnberg zur Erlangung des Doktorgrades Dr. rer. nat. vorgelegt von Nico Fritsch aus Forchheim Als Dissertation genehmigt von der Naturwissen- schaftlichen Fakultät der Friedrich-Alexander-Universität Erlangen-Nürnberg Tag der mündlichen Prüfung: 13. Juni 2014 Vorsitzender des Promotionsorgans: Prof. Dr. Johannes Barth Gutachter: Prof. Dr. Nicolai Burzlaff Prof. Dr. Julien Bachmann Die vorliegende Arbeit entstand in der Zeit von Juni 2011 bis März 2014 im Department für Chemie und Pharmazie (Lehrstuhl für Anorganische und Metallorganische Chemie) der Friedrich-Alexander-Universität Erlangen-Nürnberg unter der Anleitung von Prof. Dr. Nicolai Burzlaff. Teile dieser Dissertation wurden bereits veröffentlicht: “trans-1,2-Bis(N-methylimidazol-2-yl)ethylene: Towards Building Blocks of 2D Fabrics and MML-Type 2D Molecular Strands”, N.V. Fischer, M. S. Alam, I. Jum´h, M. Stocker, N. Fritsch, V. Dremov, F.W. Heinemann, N. Burzlaff, P. Müller, Chem. – Eur. J., 2011, 17, 9293-9297. “Battlement-shaped 1D coordination polymer based on bis(N-methylimidazole-2yl)butadiyne ligand”, T. Waidmann, N. Fritsch, J. Tucher, M. Rudolf, F. Glaser, D.M. Guldi, N. Burzlaff, CrystEngComm, 2013, 10157-10160. – Reproduced by permission of The Royal Society of Chemistry. You can´t always get what you want. But if you try sometimes you might find, You get what you need. (Sir Mick Jagger) Table of contents 1! GENERAL INTRODUCTION ............................................................................................ 1! 1.1! From metal organic frameworks to 1D coordination polymers ........................................... 2! 1.2! Different concepts of molecular wires .................................................................................... 5! 1.2.1! Organic based molecular wires ........................................................................................... 5! 1.2.2! Inorganic based molecular wires ......................................................................................... 9! 1.3! Synthesis of trans-bis(N-methylimidazol-2-yl)ethylene (trans-bie) ..................................... 20! 1.4! Synthesis of the first 1D coordination polymer with trans-bie ........................................... 21! 1.5! Scanning tunneling microscopy ............................................................................................. 25! 1.5.1! Theory ............................................................................................................................... 25! 1.5.2! Function and surface property ........................................................................................... 27! 2! AIMS AND OBJECTIVES ................................................................................................ 31! 3! RESULTS AND DISCUSSION ......................................................................................... 33! 3.1! From single to quadruple bond metal(II) acetate complexes with trans-bie ..................... 34! 3.1.1! Preparation and Characterisation of [Rh2(OAc)4(trans-bie)]n (4) ...................................... 34! 3.1.2! Preparation and Characterization of [Ru2(OAc)4(trans-bie)]n (5) ..................................... 38! 3.1.3! Preparation and Characterization of [Mo2(OAc)4(trans-bie)]n (6) ..................................... 41! 3.1.4! Preparation and Characterization of [Cr2(OAc)4(trans-bie)]n (7) and [Cr2(OAc)4(trans-bie)2] (8). ............................................................................................... 43! 3.1.5! Preparation and Characterisation of [Zn3(OAc)6(trans-bie)]n (9) ..................................... 47! 3.1.6! Electronic structure and bond orders of binuclear units within polymers ......................... 50! 3.1.7! Comparison of the metal(II) acetate compounds .............................................................. 56! 3.2! Battlement shaped 1D coordination polymer based on bmib ............................................. 58! 3.2.1! Synthesis and Characterization of bmib (3) ...................................................................... 58! 3.2.2! Preparation and Characterization of [Zn5(OAc)10(bmib)2]n (10) ....................................... 64! 3.3! Sawhorse-type diruthenium tetracarbonyl polymers with N,N ligands ............................ 68! 3.3.1! Preparation and Characterisation of [Ru2(OAc)2(CO)4(L)]n .............................................. 68! 3.3.2! Comparison of sawhorse-type compounds ....................................................................... 73! 3.3.3! STM images on HOPG ..................................................................................................... 75! 4! SUMMARY ....................................................................................................................... 79! 5! ZUSAMMENFASSUNG ................................................................................................... 84! 6! EXPERIMENTAL SECTION ............................................................................................ 90! 6.1! Physical part ............................................................................................................................ 91! 6.1.1! Experimental ..................................................................................................................... 91! 6.2! Chemical part .......................................................................................................................... 92! 6.2.1! General remarks ................................................................................................................ 92! I Table of contents 6.2.1.1! Working techniques ................................................................................................................. 92! 6.2.1.2! Instrumentation ........................................................................................................................ 92! 6.2.1.3! Chemicals ................................................................................................................................. 93! 6.2.2! Synthesis of ligands .......................................................................................................... 94! 6.2.2.1! Synthesis of rac-1,2-Hbmie (1)[145] .......................................................................................... 94! 6.2.2.2! Synthesis of trans-bie (2)[145] ................................................................................................... 94! 6.2.2.3! Synthesis of bmib (3)[219] .......................................................................................................... 95! 6.2.3! Synthesis of paddlewheel polymers ................................................................................. 96! 6.2.3.1! Synthesis of [Rh2(OAc)4(trans-bie)]n (4) ................................................................................. 96! 6.2.3.2! Synthesis of [Ru2(OAc)4(trans-bie)]n (5) ................................................................................. 97! 6.2.3.3! Synthesis of [Mo2(OAc)4(trans-bie)]n (6) ................................................................................ 97! 6.2.3.4! Synthesis of [Cr2(OAc)4(trans-bie)]n (7) .................................................................................. 98! 6.2.3.5! Synthesis of [Cr2(OAc)4(trans-bie)2] (8) .................................................................................. 99! 6.2.4! Synthesis of zinc-polymers ............................................................................................... 99! 6.2.4.1! Synthesis of [Zn3(OAc)6(trans-bie)]n (9) ................................................................................. 99! [219] 6.2.4.2! Synthesis of [Zn5(OAc)10(bmib)2]n (10) ............................................................................ 100! 6.2.5! Synthesis of sawhorse-type polymers ............................................................................. 101! 6.2.5.1! Synthesis of [Ru2(OAc)2(CO)4(trans-bie)]n (11) ................................................................... 101! 6.2.5.2! Synthesis of [Ru2(OAc)2(CO)4(pyz)]n (12) ............................................................................ 102! 6.2.5.3! Synthesis of [Ru2(OAc)2(CO)4(4,4’-bipy)]n (13) ................................................................... 102! 6.2.5.4! Synthesis of [Ru2(OAc)2(CO)4(bpe)]n (14) ............................................................................ 103! 6.2.5.5! Synthesis of [Ru2(OAc)2(CO)4(DABCO)]n (15) .................................................................... 104! 6.3! Computational details .......................................................................................................... 104! 7! APPENDIX ...................................................................................................................... 106! 7.1! Details of the structure determinations .............................................................................. 107! 7.2! Powder X-ray diffraction patterns ..................................................................................... 112! 7.3! UV-Vis spectra ..................................................................................................................... 115! 7.4! Computational details .........................................................................................................