0000000000025087
AUTHOR
Niklas Struch
Frontispiece: An Octanuclear Metallosupramolecular Cage Designed To Exhibit Spin-Crossover Behavior
Electron-Deficient Pyridylimines: Versatile Building Blocks for Functional Metallosupramolecular Chemistry
Metallosupramolecular systems heavily rely on the correct choice of ligands to obtain materials with desired properties. Engaging this problem, we present three ligand systems and six of their mono- and dinuclear complexes, based on the subcomponent self-assembly approach using electron-deficient pyridylcarbaldehyde building blocks. The properties are examined in solution by NMR and UV-vis spectroscopy and CV measurements as well as in solid state by single crystal X-ray diffraction analysis. Ultimately, the choice of ligands allows for fine-tuning of the electronic properties of the metal centers, complex-to-complex transformations, as well as establishing distinct anion-π-interaction moti…
Ein achtkerniger metallosupramolekularer Würfel mit Spin-Crossover-Eigenschaften
Self-Sorting Effects in the Self-Assembly of Metallosupramolecular Rhombi from Chiral BINOL-Derived Bis(pyridine) Ligands
Four BINOL-based bis(4-pyridyl) ligands were synthesised in enantiopure and racemic form. These ligands form metallosupramolecular [(dppp)2M2L2] rhombi with cis-protected [(dppp)Pd]2+ and [(dppp)Pt]2+ ions. In principle, racemic ligands can self-assemble into three stereoisomeric rhombi. The degree of self-sorting in the self-assembly process crucially depends on the substitution pattern and the resulting bend angle of the V-shaped ligands as well as the degree of steric crowding within the assembly when racemic ligands are used. Thus, these processes either lead to homochiral assemblies in a narcissistic self-recognition manner, to heterochiral assemblies in a social self-discriminating ma…
Enantiomerically pure trinuclear helicates via diastereoselective self-assembly and characterization of their redox chemistry.
A tris(bipyridine) ligand 1 with two BINOL (BINOL = 2, 2′-dihydroxy-1, 1′-binaphthyl) groups has been prepared in two enantiomerically pure forms. This ligand undergoes completely diastereoselective self-assembly into D2-symmeteric double-stranded trinuclear helicates upon coordination to copper(I) and silver(I) ions and to D3-symmetric triple-stranded trinuclear helicates upon coordination to copper(II), zinc(II), and iron(II) ions as demonstrated by mass spectrometry, NMR and CD spectroscopy in combination with quantum chemical calculations and X-ray diffraction analysis. According to the calculations, the single diastereomers that are formed during the self-assembly process are strongly …
Electron-deficient trifluoromethyl-substituted sub-components affect the properties of M4L4 tetrahedral cages
Two supramolecular tetrahedral cages based on a new electron-deficient trifluoromethyl-substituted pyridylimine ligand are synthesised by sub-component self-assembly. Their structures are characterised by NMR und UV-Vis spectroscopy, high-resolution mass spectrometry and single crystal X-ray diffraction. The iron(II) complex shows host–guest chemistry, complex-to-complex transformations and novel electronic properties.
Electron-deficient trifluoromethyl-substituted sub-components affect the properties of M4L4 tetrahedral cages
Two supramolecular tetrahedral cages based on a new electron-deficient trifluoromethyl-substituted pyridylimine ligand are synthesised by sub-component self-assembly. Their structures are characterised by NMR und UV-Vis spectroscopy, high-resolution mass spectrometry and single crystal X-ray diffraction. The iron(II) complex shows host–guest chemistry, complex-to-complex transformations and novel electronic properties. peerReviewed
Influencing the Self‐Sorting Behavior of [2.2]Paracyclophane‐Based Ligands by Introducing Isostructural Binding Motifs
Abstract Two isostructural ligands with either nitrile (Lnit) or isonitrile (Liso) moieties directly connected to a [2.2]paracyclophane backbone with pseudo‐meta substitution pattern have been synthesized. The ligand itself (Lnit) or its precursors (Liso) were resolved by HPLC on a chiral stationary phase and the absolute configuration of the isolated enantiomers was assigned by XRD analysis and/or by comparison of quantum‐chemical simulated and experimental electronic circular dichroism (ECD) spectra. Surprisingly, the resulting metallosupramolecular aggregates formed in solution upon coordination of [(dppp)Pd(OTf)2] differ in their composition: whereas Lnit forms dinuclear complexes, Liso…
An Octanuclear Metallosupramolecular Cage Designed To Exhibit Spin-Crossover Behavior.
By employing the subcomponent self-assembly approach utilizing 5,10,15,20-tetrakis(4-aminophenyl)porphyrin or its zinc(II) complex, 1H-4-imidazolecarbaldehyde, and either zinc(II) or iron(II) salts, we were able to prepare O-symmetric cages having a confined volume of ca. 1300 Å3 . The use of iron(II) salts yielded coordination cages in the high-spin state at room temperature, manifesting spin-crossover in solution at low temperatures, whereas corresponding zinc(II) salts led to the corresponding diamagnetic analogues. The new cages were characterized by synchrotron X-ray crystallography, high-resolution mass spectrometry, and NMR, Mössbauer, IR, and UV/Vis spectroscopy. The cage structures…
Influencing the self‐sorting behavior of [2.2]paracyclophane based ligands by introducing isostructural binding motifs
Two isostructural ligands with either nitrile ( L nit ) or isonitrile ( L iso ) moieties directly connected to a [2.2]paracyclophane backbone with pseudo‐meta substitution pattern have been synthesized. The ligand itself ( L nit ) or its precursors ( L iso ) were resolved via HPLC on a chiral stationary phase and the absolute configuration of the isolated enantiomers was assigned by XRD analysis and/or by comparison of quantum‐chemical simulated and experimental ECD‐spectra. Surprisingly, the resulting metallosupramolecular aggregates formed in solution upon coordination of [(dppp)Pd(OTf) 2 ] differ in their composition: whereas L nit forms dinuclear complexes L iso exclusively forms trinuc…
Stepwise Construction of Heterobimetallic Cages by an Extended Molecular Library Approach.
Two novel heterobimetallic complexes, a trigonal-bipyramidal and a cubic one, have been synthesized and characterized using the same C3-symmetric metalloligand, prepared by a simple subcomponent self-assembly strategy. Adopting the molecular library approach, we chose a mononuclear, preorganized iron(II) complex as the metalloligand capable of self-assembly into a trigonal-bipyramidal or a cubic aggregate upon coordination to cis-protected C2-symmetric palladium(II) or unprotected tetravalent palladium(II) ions, respectively. The trigonal-bipyramidal complex was characterized by NMR and UV–vis spectroscopy, electrospray ionization mass spectrometry (ESI-MS), and single-crystal X-ray diffrac…
CCDC 1573413: Experimental Crystal Structure Determination
Related Article: Niklas Struch, Filip Topic, Gregor Schnakenburg, Kari Rissanen, Arne Lützen|2018|Inorg.Chem.|57|241|doi:10.1021/acs.inorgchem.7b02412
CCDC 1451726: Experimental Crystal Structure Determination
Related Article: Niklas Struch, Christoph Bannwarth, Tanya K. Ronson, Yvonne Lorenz, Bernd Mienert, Norbert Wagner, Marianne Engeser, Eckhard Bill, Rakesh Puttreddy, Kari Rissanen, Johannes Beck, Stefan Grimme, Jonathan R. Nitschke, Arne Lützen|2017|Angew.Chem.,Int.Ed.|56|4930|doi:10.1002/anie.201700832
CCDC 945021: Experimental Crystal Structure Determination
Related Article: Christoph Gütz, Rainer Hovorka, Caroline Stobe, Niklas Struch, Filip Topić, Gregor Schnakenburg, Kari Rissanen, Arne Lützen|2014|Eur.J.Org.Chem.|2014|206|doi:10.1002/ejoc.201301314
CCDC 1573412: Experimental Crystal Structure Determination
Related Article: Niklas Struch, Filip Topic, Gregor Schnakenburg, Kari Rissanen, Arne Lützen|2018|Inorg.Chem.|57|241|doi:10.1021/acs.inorgchem.7b02412
CCDC 1573312: Experimental Crystal Structure Determination
Related Article: Niklas Struch, Filip Topic, Gregor Schnakenburg, Kari Rissanen, Arne Lützen|2018|Inorg.Chem.|57|241|doi:10.1021/acs.inorgchem.7b02412
CCDC 1824417: Experimental Crystal Structure Determination
Related Article: Lucia Volbach, Niklas Struch, Fabian Bohle, Filip Topić, Gregor Schnakenburg, Andreas Schneider, Kari Rissanen, Stefan Grimme, Arne Lützen|2020|Chem.-Eur.J.|26|3335|doi:10.1002/chem.201905070
CCDC 1824416: Experimental Crystal Structure Determination
Related Article: Lucia Volbach, Niklas Struch, Fabian Bohle, Filip Topić, Gregor Schnakenburg, Andreas Schneider, Kari Rissanen, Stefan Grimme, Arne Lützen|2020|Chem.-Eur.J.|26|3335|doi:10.1002/chem.201905070
CCDC 1955599: Experimental Crystal Structure Determination
Related Article: Lucia Volbach, Niklas Struch, Fabian Bohle, Filip Topić, Gregor Schnakenburg, Andreas Schneider, Kari Rissanen, Stefan Grimme, Arne Lützen|2020|Chem.-Eur.J.|26|3335|doi:10.1002/chem.201905070
CCDC 945019: Experimental Crystal Structure Determination
Related Article: Christoph Gütz, Rainer Hovorka, Caroline Stobe, Niklas Struch, Filip Topić, Gregor Schnakenburg, Kari Rissanen, Arne Lützen|2014|Eur.J.Org.Chem.|2014|206|doi:10.1002/ejoc.201301314
CCDC 1573313: Experimental Crystal Structure Determination
Related Article: Niklas Struch, Filip Topic, Gregor Schnakenburg, Kari Rissanen, Arne Lützen|2018|Inorg.Chem.|57|241|doi:10.1021/acs.inorgchem.7b02412
CCDC 1550913: Experimental Crystal Structure Determination
Related Article: Matthias Hardy, Niklas Struch, Filip Topic, Gregor Schnakenburg, Kari Rissanen, Arne Lützen|2018|Inorg.Chem.|57|3507|doi:10.1021/acs.inorgchem.7b02516
CCDC 1573410: Experimental Crystal Structure Determination
Related Article: Niklas Struch, Filip Topic, Gregor Schnakenburg, Kari Rissanen, Arne Lützen|2018|Inorg.Chem.|57|241|doi:10.1021/acs.inorgchem.7b02412
CCDC 1003004: Experimental Crystal Structure Determination
Related Article: Christoph Gütz , Rainer Hovorka , Niklas Struch , Jens Bunzen , Georg Meyer-Eppler , Zheng-Wang Qu , Stefan Grimme , Filip Topić, Kari Rissanen, Mario Cetina, Marianne Engeser, Arne Lützen|2014|J.Am.Chem.Soc.|136|11830|doi:10.1021/ja506327c
CCDC 1573414: Experimental Crystal Structure Determination
Related Article: Niklas Struch, Filip Topic, Gregor Schnakenburg, Kari Rissanen, Arne Lützen|2018|Inorg.Chem.|57|241|doi:10.1021/acs.inorgchem.7b02412
CCDC 941094: Experimental Crystal Structure Determination
Related Article: Christoph Gütz, Rainer Hovorka, Caroline Stobe, Niklas Struch, Filip Topić, Gregor Schnakenburg, Kari Rissanen, Arne Lützen|2014|Eur.J.Org.Chem.|2014|206|doi:10.1002/ejoc.201301314
CCDC 945020: Experimental Crystal Structure Determination
Related Article: Christoph Gütz, Rainer Hovorka, Caroline Stobe, Niklas Struch, Filip Topić, Gregor Schnakenburg, Kari Rissanen, Arne Lützen|2014|Eur.J.Org.Chem.|2014|206|doi:10.1002/ejoc.201301314
CCDC 941095: Experimental Crystal Structure Determination
Related Article: Christoph Gütz, Rainer Hovorka, Caroline Stobe, Niklas Struch, Filip Topić, Gregor Schnakenburg, Kari Rissanen, Arne Lützen|2014|Eur.J.Org.Chem.|2014|206|doi:10.1002/ejoc.201301314
CCDC 1955601: Experimental Crystal Structure Determination
Related Article: Lucia Volbach, Niklas Struch, Fabian Bohle, Filip Topić, Gregor Schnakenburg, Andreas Schneider, Kari Rissanen, Stefan Grimme, Arne Lützen|2020|Chem.-Eur.J.|26|3335|doi:10.1002/chem.201905070
CCDC 1575238: Experimental Crystal Structure Determination
Related Article: Matthias Hardy, Niklas Struch, Filip Topic, Gregor Schnakenburg, Kari Rissanen, Arne Lützen|2018|Inorg.Chem.|57|3507|doi:10.1021/acs.inorgchem.7b02516
CCDC 1573411: Experimental Crystal Structure Determination
Related Article: Niklas Struch, Filip Topic, Gregor Schnakenburg, Kari Rissanen, Arne Lützen|2018|Inorg.Chem.|57|241|doi:10.1021/acs.inorgchem.7b02412
CCDC 1955600: Experimental Crystal Structure Determination
Related Article: Lucia Volbach, Niklas Struch, Fabian Bohle, Filip Topić, Gregor Schnakenburg, Andreas Schneider, Kari Rissanen, Stefan Grimme, Arne Lützen|2020|Chem.-Eur.J.|26|3335|doi:10.1002/chem.201905070