Supercharged, Precise, Megametallodendrimers via a Single-Step, Quantitative, Assembly Process

Xie, Ting‐Zheng; Wu, Xianxin; Endres, Kevin J.; Guo, Zaihong; Lu, Xiaocun; Li, Jingyi; Manandhar, Erendra; Ludlow, James M.; Moorefield, Charles N.; Saunders, Mary Jane; Wesdemiotis, Chrys; Newkome, George R.

doi:10.1021/jacs.7b10328

Cited by 39 publications

(19 citation statements)

References 40 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…The TWIM‐MS spectrum (Figure b) clearly showed a set of narrow drift time distribution plots for the 14+ to 21+ species, demonstrating that no superimposed fragments, isomers, or conformers are present in the resultant self‐assemblies. After deconvolution, the molecule weight of S 6 was measured to be 42 014.3 Da, which is among one of the largest metallo‐supramolecules in the field of coordination‐driven supramolecular self‐assembly ,…”

Section: Figurementioning

confidence: 99%

See 1 more Smart Citation

Vertical Assembly of Giant Double‐ and Triple‐Decker Spoked Wheel Supramolecular Structures

Liu

Chen

et al. 2018

Angew Chem Int Ed

Self Cite

View full text Add to dashboard Cite

The double- or triple-decker 3D metallo-hexagons were obtained by self-assembly of multitopic tris-terpyridines with Cd ions in near-quantitative yield. Comprising up to 72 ionic pairs, the multiple spoked wheels display characteristic reversible gelation properties under thermodynamic conditions. The supramolecular metallo-nanoarchitectures were characterized by H NMR, 2D NMR (COSY and NOESY), and diffusion-ordered spectroscopy (DOSY) and HR-ESI-MS, traveling-wave ion mobility mass spectrometry (TWIM-MS), TEM, and AFM. For the first time, the self-assembly of 45 units at once was demonstrated to yield exceptional giant triple-decker hexagons of up to circa 42 000 Da.

show abstract

Section: Figurementioning

confidence: 99%

“…After deconvolution, the molecule weight of S 6 was measured to be 42014.3 Da, which is among one of the largest metallo-supramolecules in the field of coordination-driven supramolecular self-assembly. [10a,20] …”

mentioning

confidence: 99%

Vertical Assembly of Giant Double‐ and Triple‐Decker Spoked Wheel Supramolecular Structures

Liu

Chen

et al. 2018

Angew Chem Int Ed

Self Cite

View full text Add to dashboard Cite

show abstract

“…Although the <tpy‐Fe II /Ru II ‐tpy>‐based metallo‐ligand approach has been ubiquitously utilized in construction of metallo‐supramolecules,–,, the resultant complexes emit practically nothing at room temperature because of the short lifetime of the metal‐to‐ligand charge transfer (MLCT) excited states . In contrast, <tpy‐Zn II /Cd II ‐tpy>‐based derivatives preserve the ligand‐based luminescence owing to the filled d 10 shell of the metal ions .…”

Section: Resultsmentioning

confidence: 99%

Multicomponent Self‐Assembly of Metallo‐Supramolecular Macrocycles and Cages through Dynamic Heteroleptic Terpyridine Complexation

Wang

Huang

Liang

et al. 2018

Chemistry A European J

View full text Add to dashboard Cite

Spontaneous formation of the heteroleptic cadmium(II) bis(terpyridine) complex under ambient conditions can be achieved by a combination of 6,6''-di(2,6-dimethoxylphenyl)-substituted and unsubstituted terpyridine-based ligands. Building on this dynamic heteroleptic complexation, diverse metallo-supramolecular macrocycles and cages were readily assembled in quantitative yields from the predesigned multicomponent systems. The complementary ligation reinforced self-recognition to facilitate the shape-dependent self-sorting of a four-component dynamic library into two well-defined parallelograms. In addition, the subtle lability difference between homoleptic and heteroleptic complexes led to the site-selective Cd -Zn transmetalation in the Sierpiński triangle. Facile construction of a dodecanuclear tetrahedral metallocage was also realized by using two self-recognizable tritopic building blocks. The photophysical study of the metallo-supramolecules assembled from the d metal ions revealed intense ligand-based photoluminescence in solution. The self-assembly strategy described here provides an efficient methodology for building pre-programmable, sophisticated supramolecular architectures furnished with photoactivity.

show abstract

“…IM-MS has been instrumental in establishing the latter structural features with high sensitivity and specificity, especially when mixtures with isobars and isomers are generated that are difficult to characterize by other analytical techniques. 8,[21][22][23][24][25][26][27][28][29][30][31] An important attribute of IM-MS that sets it apart from other characterization techniques is its ability to separate isobaric and isomeric ions in the gas phase, which is often necessary for samples formed by coordination-driven self-assembly reactions. Electrospray ionization (ESI) is the method of choice for the mass spectrometry (MS) analysis of these samples, as most metal ligands contain highly conjugated UV chromophores that preclude the use of laserbased ionization.…”

Section: Introductionmentioning

confidence: 99%

Collision cross‐section analysis of self‐assembled metallomacrocycle isomers and isobars via ion mobility mass spectrometry

Endres

Barthelmes

Winter

et al. 2020

Rapid Comm Mass Spectrometry

Self Cite

View full text Add to dashboard Cite

Rationale Coordinatively driven self‐assembly of transition metal ions and bidentate ligands gives rise to organometallic complexes that usually contain superimposed isobars, isomers, and conformers. In this study, the double dispersion ability of ion mobility mass spectrometry (IM‐MS) was used to provide a comprehensive structural characterization of the self‐assembled supramolecular complexes by their mass and charge, revealed by the MS event, and their shape and collision cross‐section (Ω), revealed by the IM event. Methods Self‐assembled complexes were synthesized by reacting a bis(terpyridine) ligand exhibiting a 60o dihedral angle between the two ligating terpyridine sites (T) with divalent Zn, Ni, Cd, or Fe. The products were isolated as (Metal2+[T])n (PF6)2n salts and analyzed using IM‐MS after electrospray ionization (ESI) which produced several charge states from each n‐mer, depending on the number of PF6ˉ anions lost upon ESI. Experimental Ω data, derived using IM‐MS, and computational Ω predictions were used to elucidate the size and architecture of the complexes. Results Only macrocyclic dimers, trimers, and tetramers were observed with Cd2+, whereas Zn2+ formed the same plus hexameric complexes. These two metals led to the simplest product distributions and no linear isomers. In sharp contrast, Ni2+ and Fe2+ formed all possible ring sizes from dimer to hexamer as well as various linear isomers. The experimental and theoretical Ω data indicated rather planar macrocyclic geometries for the dimers and trimers, twisted 3D architectures for the larger rings, and substantially larger sizes with spiral conformation for the linear congeners. Adding PF6ˉ to the same complex was found to mainly cause size contraction due to new stabilizing anion–cation interactions. Conclusions Complete structural identification could be accomplished using ESI‐IM‐MS. Our results affirm that self‐assembly with Cd2+ and Zn2+ proceeds through reversible equilibria that generate the thermodynamically most stable structures, encompassing exclusively macrocyclic architectures that readily accommodate the 60o ligand used. In contrast, complexation with Ni2+ and Fe2+, which form stronger coordinative bonds, proceeds through kinetic control, leading to more complex mixtures and kinetically trapped less stable architectures, such as macrocyclic pentamers and linear isomers.

show abstract

Supercharged, Precise, Megametallodendrimers via a Single-Step, Quantitative, Assembly Process

Cited by 39 publications

References 40 publications

Vertical Assembly of Giant Double‐ and Triple‐Decker Spoked Wheel Supramolecular Structures

Vertical Assembly of Giant Double‐ and Triple‐Decker Spoked Wheel Supramolecular Structures

Multicomponent Self‐Assembly of Metallo‐Supramolecular Macrocycles and Cages through Dynamic Heteroleptic Terpyridine Complexation

Collision cross‐section analysis of self‐assembled metallomacrocycle isomers and isobars via ion mobility mass spectrometry

Contact Info

Product

Resources

About