Synthesis of Nanometer-Sized Cylinder-Like Structures from a 1,3,5-Triphenylbenzene-Bridged Tris-NHC Ligand and Ag^I, Au^I, and Cu^I

Abstract

Registro de acceso restringido Este recurso no está disponible en acceso abierto por política de la editorial. No obstante, se puede acceder al texto completo desde la Universitat Jaume I o si el usuario cuenta con suscripción. Registre d'accés restringit Aquest recurs no està disponible en accés obert per política de l'editorial. No obstant això, es pot accedir al text complet des de la Universitat Jaume I o si l'usuari compta amb subscripció. Restricted access item This item isn't open access because of publisher's policy. The full--text version is only available from Jaume I University or if the user has a running suscription to the publisher's contents.

Homo‐ and Heteroligand Poly‐NHC Metal Assemblies: Synthesis by Narcissistic and Social Self‐Sorting

“…We have previously observed that assemblies of type [Au 3 ( L ) 2 ](BF 4 ) 3 ( L =tris‐NHC ligand with a 1,3,5‐triphenylbenzene‐backbone), where tris‐NHC ligand L is closely related to A1 and D1 , feature two nearly coplanar orientated central benzene rings within two concave distorted tris‐NHC ligands. The concave distortion allows the central benzene rings to approach each other (centroid⋅⋅⋅centroid distance 3.644 Å, cf C NHC ⋅⋅⋅C NHC separation at the C NHC −Au−C NHC groups ≈4.0 Å) with formation of π⋅⋅⋅π stacking interactions . Similar, but much stronger π⋅⋅⋅π stacking interactions can be assumed between the triazine acceptor in A1 and the benzene donor in D1 of [Ag 3 ( A1 )( D1 )](BF 4 ) 3 .…”

“…The olefin substituents were selected for subsequent postsynthetic modifications ([2+2] cycloadditions or olefin metathesis) in case heteroligand complexes of type [Ag 3 ( L )( L′ )]X 3 ( L , L′ = A , B , C , D ) could be obtained with the olefins properly oriented . The trisimidazolium salts H 3 ‐ L (BF 4 ) 3 ( L=A – D ) were synthesized using slightly modified protocols of published procedures ,,. All trisimidazolium salts H 3 ‐ L (BF 4 ) 3 ( L=A – D ) were fully characterized by 1 H and 13 C{ 1 H} NMR spectroscopy, and mass spectrometry (see the Supporting Information).…”

“…All of these complexes were fully characterized (see the Supporting Information). While the trinuclear homoligand assemblies of type H 3 ‐( L )(BF 4 ) 3 ( L = A – D ) are promising starting materials for postsynthetic modifications involving the olefins, related trinuclear assemblies obtained from various other trisimidazolium salts have been described ,,…”

Selektive, narzisstische Selbstsortierung bei der Synthese von metallorganischen Strukturen mit Poly‐NHC‐Liganden

“… für [ 4 ‐Et](PF 6 ) 3 , Lit. für [ 6 ‐Et](PF 6 ) 3 und in den Hintergrundinformationen für [ 5 ‐Et](PF 6 ) 3 .) Da die drei Tris‐NHC‐Liganden identische Donorgruppen und eine sehr ähnliche trigonale Topologie aufweisen, besteht eine hohe Wahrscheinlichkeit für die Bildung von Heteroligand‐ oder oligomeren Reaktionsprodukten.…”

Single‐Step Synthesis of Organometallic Molecular Squares from NR,NR′,NR′′,NR′′′‐Substituted Benzobiscarbenes

“…[6] Most of the metallosupramolecular host molecules are polynuclear Werner-type coordinationc ompounds in which the metal centers are coordinated by nitrogen and/or oxygen donor atoms of polydentate ligands. Recently,N -heterocyclic carbenes (NHCs) [7] have emergeda sanew class of ligands for the preparationo fm etallosupramolecular structures such as dinuclearm olecular rectangles, [8] molecular cylinders, [9] and organometallic polymers. [10] Amongt he coordination-driven supramolecular architectures, molecular squares are the moste xtensively studied derivatives startingw ith the pioneering work by Fujitae tal.…”