Construction of Macromolecular Pinwheels Using Predesigned Metalloligands

Abstract

Developing a methodology to build target structures is one of the major themes of synthetic chemistry. However, it has proven to be immensely challenging to achieve multilevel elaborate molecular architectures in a predictable way. Herein, we describe the self-assembly of a series of pinwheel-shaped starlike supramolecules through three rationally preorganized metalloligands L1−L3. The key octa-uncomplexed terpyridine (tpy) metalloligand L3, synthesized with an 8-fold Suzuki coupling reaction to metal-containing complexes, has four different types of terpyridines connected with three ⟨tpy-Ru 2+ -tpy⟩ units, making this the most subunits known so far for a preorganized module. Based on the principle of geometric complementation and the high "density of coordination sites", these metalloligands were assembled with Zn 2+ ions to form a pinwheel-shaped star trigon P1, pentagram P2, and hexagram P3 with precisely controlled shapes in nearly quantitative yields. With molecular weights ranging from 16756 to 56053 Da and diameters of 6.7−13.6 nm, the structural composition, shape, and rigidity of these pinwheel-shaped architectures have been fully characterized by 1D and 2D (NMR), electrospray ionization mass spectrometry, traveling-wave ion mobility mass spectrometry, and transmission electron microscopy.

Structural Analysis and Controllable Fabrication of Two Pentazolate-Based 3D Topological Networks

“…Noticeably, MPF-1 demonstrates the simplicity and feasibility of the cyclo -N 5 – anion in assembling pentasil-zeolite topologies. Actually, the molecular design of topology networks heavily depends on coordination geometry and steric configuration of nodes and linkers. − However, the self-assembly process of linkers as well as metal nodes may not strictly follow angles and directions, which is bound to reduce the possibility of preparing the target structures. − This further implies that a cyclo -N 5 – anion with definite angles and shapes is an ideal ligand to use in preparing pentasil frameworks. The pentazolium salts of the same composition may form a variety of 3D crystal structures due to the multiple coordination capacity of the cyclo -N 5 – anion.…”

Reaction Monitoring and Structural Characterisation of Coordination Driven Self-Assembled Systems by Ion Mobility-Mass Spectrometry

“…Recently IMS-MS has not only characterized occluded CDSA products, such as constitutional isomers and configurational isomers ( Ujma et al, 2012 ; Schultz et al, 2013 ; Liang et al, 2015 ), but also the “erroneous” intermediates formed in multicomponent systems ( Wang et al, 2020c ), or impressively, the lack thereof in a multicomponent system, due to successful pre-organization ( Wang et al, 2020a ), and even the formation of pre-organized “sequenced” CDSA systems ( Song et al, 2018 ). As such, the structural analysis of CDSA systems using IMS-MS ultimately leads us beyond characterisation of the product and side products, and towards an understanding of CDSA mechanisms.…”

Synthesis of a novel nitrogen mustard–conjugated bis-terpyridine ruthenium(II) complex as a potent anticancer agent that induces cell cycle arrest and apoptosis

“…These Ru polypyridyl complexes are commonly analogues such as [Ru(tpy)Cl 3 ] (tpy = 2,2′:6′,2″-terpyridine), [Ru(tpy) 2 ] 2+ , [Ru(azpy) 2 Cl 2 ] 2+ , (azpy = 2-phenylazopyridine), [Ru(bpy) 2 Cl 2 ] 2+ , (bpy = 2,2'-bipyridine), and [Ru( bpy) 3 ] 2+ . [3][4][5][6][7] These Ru complexes exhibit their antiproliferative activity mostly through inhibition of DNA replication, 8 protein or enzyme activity, 9,10 and result in cell arrest or apoptosis. 11 Terpyridine ruthenium complexes are well known as effective non-covalent DNA binders.…”