Synthesis of Sterically Encumbered 2,9-Diaryl Substituted Phenanthrolines. Key Building Blocks for the Preparation of Mixed (Bis-Heteroleptic) Phenanthroline Copper(i) Complexes

Schmittel, Michael; Lüning, Ulrich; Meder, Markus B.; Ganz, Andrea; Michel, Christoph; Herderich, Markus

doi:10.1515/hc.1997.3.6.493

Cited by 53 publications

(71 citation statements)

References 7 publications

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“…Materials : Solvents and reagents were purchased from Aldrich, Merck and ABCR, unless otherwise stated, purified and dried by standard methods prior to use. 3,4‐Diethylthiophene,29 2‐pinacolborylthiophene,30 2,9‐diiodophenanthroline,11b 2,9‐di(thien‐2‐yl)‐1,10‐phenanthroline,10 2,9‐bis(5‐iodothien‐2‐yl)‐1,10‐phenanthroline,10 2,9‐dimesitylphenanthroline,31 [1,3‐bis(diphenylphosphino)propane]palladium(II) chloride,32 tetrakis(acetonitrile) copper(I) tetrafluoroborate,33 and oligothiophene building blocks C and E 34 were synthesized according to known literature procedures. N ‐Bromosuccinimide and thiophene were purchased from Merck.…”

Section: Methodsmentioning

confidence: 99%

π‐Conjugated [2]Catenanes Based on Oligothiophenes and Phenanthrolines: Efficient Synthesis and Electronic Properties

Götz

Zhu

Mishra

et al. 2015

Chemistry A European J

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Novel π-conjugated topologies based on oligothiophenes and phenanthroline have been assembled by combining their outstanding electronic and structural benefits with the specific properties of the topological structure. Macrocycles and catenanes are prepared by using an optimized protocol of transition metal-templated macrocyclization followed by efficient Pd-catalyzed cross-coupling reaction steps. By using this method, [2]catenanes comprising two interlocked π-conjugated macrocycles with different ring sizes have been synthesized. The structures of the [2]catenanes and corresponding macrocycles are confirmed by detailed (1) H NMR spectroscopy and high resolution mass spectrometry. Single crystal X-ray structural analysis of the quaterthiophene-diyne macrocycle affords important insight into the packing features and intermolecular interaction of the new systems. The fully conjugated interlocked [2]catenanes are fully characterized by spectroscopic and electrochemical measurements.

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Section: Methodsmentioning

confidence: 99%

π‐Conjugated [2]Catenanes Based on Oligothiophenes and Phenanthrolines: Efficient Synthesis and Electronic Properties

Götz

Zhu

Mishra

et al. 2015

Chemistry A European J

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“…[15] Cu + ensures that all ligands and all coordination sites of the copper(I) ion are occupied. Therefore, we have used here copper(I) complexes of sterically hindered 1,10-phenanthrolines that have originally been designed to be employed as concave reagents.…”

Section: Metal Coordinationmentioning

confidence: 99%

Towards Allosteric Receptors – Synthesis of Resorcinarene‐Functionalized 2,2′‐Bipyridines and Their Metal Complexes

et al. 2009

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Based on a first example of an allosteric hemicarcerand (1) we prepared four new 2,2′‐bipyridines that carry resorcinarene moieties in a highly convergent manner. Upon coordination to suitable transition metal ions or their complexes these compounds undergo conformational changes in a way that they switch between “open” and “closed” forms (2, 3, and 4) or vice versa (5), thus, bringing together or separating the two functional moieties on the central bipyridine. Among the transition metal complexes that act as effectors for the conformational switching, [Re(CO)5Cl] and monomeric copper(I) complexes of sterically hindered 2,9‐arylated 1,10‐phenanthrolines proved to be very effective. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

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“…Owing to our earlier results with the HETPHEN concept (allowing for the selective preparation of heteroleptic bisphenanthroline copper/silver complexes), we chose 2 as a counter part to the macrocycle to prepare the nanoscale basket assembly. The HETPHEN approach [15] utilises steric and electronic effects originating from bulky aryl substituents at one of the two phenanthroline ligands (as seen in 2 and in 10 and 11) to steer the coordination equilibrium both kinetically and thermodynamically towards the heteroleptic bisphenanthroline complex. Ligands 2, 10 and 11 are designed to carry steric stoppers at the 2-and 9-positions of the phenanthroline.…”

Section: Synthesis Of a Handle For A Supramolecular Basket Assemblymentioning

confidence: 99%

“…[15] First, the ability of macrocycle 1 to form complexes with 10 and 11 was probed in presence of Cu + (Scheme 4). Rewardingly, only complexes C1 and C2, but no oligomers of macrocycle, could be detected by both ESI-MS and 1 H NMR spectroscopy, highlighting the utility of the HETPHEN concept in engineering heteroleptic supramolecular assemblies.…”

Section: Self-assembly In Solutionmentioning

confidence: 99%

“…Characteristic high-field shifts were observed for aryl protons of ligands 10 and 11 in the complexes C1 or C2, respectively, a clear indication for formation of heteroleptic complexes as demonstrated earlier. [15] In the following we probed the complexation behaviour of the handle 2. 2 + , whose isotopic distribution is in agreement with its proposed composition (Supporting Information: Figure S3).…”

Section: Self-assembly In Solutionmentioning

confidence: 99%

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Synthesis and Self‐Assembly of a Rigid Exotopic Bisphenanthroline Macrocycle: Surface Patterning and a Supramolecular Nanobasket

Kalsani

Ammon

Jäckel

et al. 2004

Chemistry A European J

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The synthesis and characterisation of a rigid nanoscale macrocycle with two exotopic phenanthroline binding sites is reported. Scanning tunnelling microscopy (STM) at the solid-liquid interface reveals the formation of highly ordered monolayers of macrocycles with dimensions that are in good agreement with the calculated structure. Using the HETPHEN concept several bisheteroleptic coordination complexes with other phenanthrolines and a nanoscale basket assembly were prepared in presence of copper(I) ions. NMR spectroscopy, mass spectrometric data and elemental analysis point to three distinct isomers of the basket assembly in solution. A silver basket was prepared and readily converted to its copper analogue. Electrospray ionisation (ESI)-MS and spectrophotometric investigations provided additional mechanistic insight into the assembly process. Hence, the exotopic bisphenanthroline macrocycle in combination with HETPHEN concept proves to be very effective in controlling the compositional aspects of multicomponent self-assembly.

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Synthesis of Sterically Encumbered 2,9-Diaryl Substituted Phenanthrolines. Key Building Blocks for the Preparation of Mixed (Bis-Heteroleptic) Phenanthroline Copper(i) Complexes

Cited by 53 publications

References 7 publications

π‐Conjugated [2]Catenanes Based on Oligothiophenes and Phenanthrolines: Efficient Synthesis and Electronic Properties

π‐Conjugated [2]Catenanes Based on Oligothiophenes and Phenanthrolines: Efficient Synthesis and Electronic Properties

Towards Allosteric Receptors – Synthesis of Resorcinarene‐Functionalized 2,2′‐Bipyridines and Their Metal Complexes

Synthesis and Self‐Assembly of a Rigid Exotopic Bisphenanthroline Macrocycle: Surface Patterning and a Supramolecular Nanobasket

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