The one-step synthesis of the first homoleptic metallomacrocycle is reported. Characterization of the Os-II complex, along with its Fe-II and Ru-II analogues, was accomplished by NMR spectroscopy, ESI-MS, TWIM-MS, gradient tandem-MS, CV, luminescence and UV/Vis spectroscopy. Center-of-mass collision energies, derived from gradient tandem-MS, reveal that the -based structures are more stable than those of .

Medium-sized cyclic oligomeric phosphazenes [PCl2N]m (where m = 5-9) that were prepared from the reaction of PCl5 and NH4Cl in refluxing chlorobenzene have been isolated by a combination of sublimation/extraction and column chromatography from the predominant products [PCl2N]3 and [PCl2N]4. The medium-sized rings [PCl2N]m have been characterized by electrospray ionization-mass spectroscopy (ESI-MS), their (31)P chemical shifts have been reassigned, and their T1 relaxation times have been obtained. Crystallographic data has been recollected for [PCl2N]5, and the crystal structures of [PCl2N]6, and [PCl2N]8 are reported. Halogen-bonding interactions were observed in all the crystal structures of cyclic [PCl2N]m (m = 3-5, 6, 8). The crystal structures of [P(OPh)2N]7 and [P(OPh)2N]8, which are derivatives of the respective [PCl2N]m, are also reported. Comparisons of the intermolecular forces and torsion angles of [PCl2N]8 and [P(OPh)2N]8 with those of three other octameric rings are described. The comparisons show that chlorophosphazenes should not be considered prototypical, in terms of solid-state structure, because of the strong influence of halogen bonding.

The self-assembly of the o-carborane-based, bisterpyridyl monomer, 1,2-bis[4'-(4-ethynylphenyl)-2,2':6',2''-terpyridine]-o-carborane, utilizing either Zn(II) or Fe(II) in a precise metal : ligand ratio (1 : 1), generated a family of metallomacrocycles that were studied via ESI-TWIM-MS, (1)H NMR, and 2D NMR (COSY, NOESY). Under kinetic control, via formation of Fe(II) complexes, the main cyclic product was triangular, as is typical of 60°-based bisligands. Under thermodynamic control using more labile transition metal complexes, e.g. Zn(II), the ratio of cyclic species was found to be concentration and temperature dependent, and under an adequate entropic driving force, the cyclic dimer was formed. This system was probed via variable temperature NMR to reveal dynamic equilibrium between the entropically favored dimer and enthalpically favored trimer.

We report the self-assembly and isolation of two metallamacromolecular constitutional isomeric pairs based on connectivity. Utilizing a robust dimer with varying substitution to the core benzene ring resulted not only in the isolation of the expected 60°-oriented tetramer and 120°-oriented hexamer but also in the unexpected isolation of a 60°-oriented hexamer and a 120°-oriented tetramer. These isomers were characterized by 1H NMR spectroscopy and mass spectrometry (ESI-travelling wave ion mobility), which revealed significant structural differences. Molecular modeling was utilized to aid in characterization.

Where there's a wheel, there's a way: The terpyridine-based title system has been synthesized through a facile self-assembly process. Two tris(terpyridine) ligands possessing angles of either 120° or 60° between adjacent tpy units were mixed with a stoichiometric amount of Zn(2+) (2:6:12) to generate the desired coordination-driven bicycle-like wheel (90 % yield).

The advent of dendritic chemistry has facilitated materials research by allowing precise control of functional component placement in macromolecular architecture. The iterative synthetic protocols used for dendrimer construction were developed based on the desire to craft highly branched, high molecular weight, molecules with exact mass and tailored functionality. Arborols, inspired by trees and precursors of the utilitarian macromolecules known as dendrimers today, were the first examples to employ predesigned, 1 → 3 C-branched, building blocks; physical characteristics of the arborols, including their globular shapes, excellent solubilities, and demonstrated aggregation, combined to reveal the inherent supramolecular potential (e.g., the unimolecular micelle) of these unique species. The architecture that is a characteristic of dendritic materials also exhibits fractal qualities based on self-similar, repetitive, branched frameworks. Thus, the fractal design and supramolecular aspects of these constructs are suggestive of a larger field of fractal materials that incorporates repeating geometries and are derived by complementary building block recognition and assembly. Use of terpyridine-M2+-terpyridine (where, M = Ru, Zn, Fe, etc) connectivity in concert with mathematical algorithms, such as forms the basis for the Seirpinski gasket, has allowed the beginning exploration of fractal materials construction. The propensity of the fractal molecules to self-assemble into higher order architectures adds another dimension to this new arena of materials and composite construction.

Taking advantage of the coordination strength of a ruthenium(II) bisterpyridine complex, G. Newkome, C. Wesdemiotis, A. Schultz, and co-workers in their Communication on page 11569 ff. have successfully synthesized a series of novel tetrameric macrocycles based on a 60°-oriented bisterpyridine ligand, resulting in folded architectures. Resembling the graceful giant manta ray, these folded metallomacrocycles, termed Dondorff rings after the first to report these rays, were characterized photophysically, as well as by ESI-TWIM-MS and molecular modeling.

Square feat: The synthesis, isolation, and characterization of five novel bisterpyridine-based metallomacrocycles, possessing a folded tetrameric configuration is reported (see figure). The initial dimeric building block with the stable linear {tpy-Ru(II)-tpy} connectivity circumvents the formation of the thermodynamically favored molecular triangles.

Two novel macromolecular constitutional isomers have been self-assembled from previously unreported terpyridine ligands in a three-component system. The terpyridine ligands were synthesized in high yields via a key Suzuki coupling. Restrictions of the possible outcomes for self-assembly ultimately provided optimum conditions for isolation of either a molecular bowtie or its isomeric butterfly motif. These isomers have been characterized by ESI-MS, TWIM-MS, (1)H NMR, and (13)C NMR. Notably, these structural isomers have remarkably different drift times in ion mobility separation, corresponding to different sizes and shapes at high charge states.

A series of trimeric, Zn(II)- and Cd(II)-metallocycles is reported. Structural characterization of the highly stable triangles was supported by traveling-wave ion mobility-mass spectrometry (TWIM-MS) and gradient tandem mass spectrometry (gMS(2)). Their unique photophysical properties and self-assembly to form nanofibers are also described.

Angewandte Chemie International EditionVolume 49, Issue 37 p. 6539-6544 Communication Hexameric Palladium(II) Terpyridyl Metallomacrocycles: Assembly with 4,4′-Bipyridine and Characterization by TWIM Mass Spectrometry† Sujith Perera Dr., Sujith Perera Dr. Department of Polymer Science, Department of Chemistry, The University of Akron, 302 Buchtel Common, Akron, OH 44325 (USA), Fax: (+1) 330-972-2368 http://www.dendrimers.com These authors contributed equally to this work.Search for more papers by this authorXiaopeng Li Dr., Xiaopeng Li Dr. Department of Polymer Science, Department of Chemistry, The University of Akron, 302 Buchtel Common, Akron, OH 44325 (USA), Fax: (+1) 330-972-2368 http://www.dendrimers.com These authors contributed equally to this work.Search for more papers by this authorMonica Soler Dr., Monica Soler Dr. Department of Polymer Science, Department of Chemistry, The University of Akron, 302 Buchtel Common, Akron, OH 44325 (USA), Fax: (+1) 330-972-2368 http://www.dendrimers.comSearch for more papers by this authorAnthony Schultz, Anthony Schultz Department of Polymer Science, Department of Chemistry, The University of Akron, 302 Buchtel Common, Akron, OH 44325 (USA), Fax: (+1) 330-972-2368 http://www.dendrimers.comSearch for more papers by this authorChrys Wesdemiotis Prof. Dr., Chrys Wesdemiotis Prof. Dr. [email protected] Department of Polymer Science, Department of Chemistry, The University of Akron, 302 Buchtel Common, Akron, OH 44325 (USA), Fax: (+1) 330-972-2368 http://www.dendrimers.comSearch for more papers by this authorCharles N. Moorefield Dr., Charles N. Moorefield Dr. Department of Polymer Science, Department of Chemistry, The University of Akron, 302 Buchtel Common, Akron, OH 44325 (USA), Fax: (+1) 330-972-2368 http://www.dendrimers.comSearch for more papers by this authorGeorge R. Newkome Prof. Dr., George R. Newkome Prof. Dr. [email protected] Department of Polymer Science, Department of Chemistry, The University of Akron, 302 Buchtel Common, Akron, OH 44325 (USA), Fax: (+1) 330-972-2368 http://www.dendrimers.comSearch for more papers by this author Sujith Perera Dr., Sujith Perera Dr. Department of Polymer Science, Department of Chemistry, The University of Akron, 302 Buchtel Common, Akron, OH 44325 (USA), Fax: (+1) 330-972-2368 http://www.dendrimers.com These authors contributed equally to this work.Search for more papers by this authorXiaopeng Li Dr., Xiaopeng Li Dr. Department of Polymer Science, Department of Chemistry, The University of Akron, 302 Buchtel Common, Akron, OH 44325 (USA), Fax: (+1) 330-972-2368 http://www.dendrimers.com These authors contributed equally to this work.Search for more papers by this authorMonica Soler Dr., Monica Soler Dr. Department of Polymer Science, Department of Chemistry, The University of Akron, 302 Buchtel Common, Akron, OH 44325 (USA), Fax: (+1) 330-972-2368 http://www.dendrimers.comSearch for more papers by this authorAnthony Schultz, Anthony Schultz Department of Polymer Science, Department of Chemistry, The University of Akron, 302 Buchtel Common, Akron, OH 44325 (USA), Fax: (+1) 330-972-2368 http://www.dendrimers.comSearch for more papers by this authorChrys Wesdemiotis Prof. Dr., Chrys Wesdemiotis Prof. Dr. [email protected] Department of Polymer Science, Department of Chemistry, The University of Akron, 302 Buchtel Common, Akron, OH 44325 (USA), Fax: (+1) 330-972-2368 http://www.dendrimers.comSearch for more papers by this authorCharles N. Moorefield Dr., Charles N. Moorefield Dr. Department of Polymer Science, Department of Chemistry, The University of Akron, 302 Buchtel Common, Akron, OH 44325 (USA), Fax: (+1) 330-972-2368 http://www.dendrimers.comSearch for more papers by this authorGeorge R. Newkome Prof. Dr., George R. Newkome Prof. Dr. [email protected] Department of Polymer Science, Department of Chemistry, The University of Akron, 302 Buchtel Common, Akron, OH 44325 (USA), Fax: (+1) 330-972-2368 http://www.dendrimers.comSearch for more papers by this author First published: 28 July 2010 https://doi.org/10.1002/anie.200906198Citations: 69 † We thank the National Science Foundation for generous financial support (grant nos. CHE-0517909 and 0833087 to C.W., no. DMR-0705015 to G.R.N., and no. DMR-0821313 for the purchase of the instrument for the TWIM-MS studies). We gratefully acknowledge the expertise of Dr. Mingming Guo, Solid State NMR Manager at The University of Akron for his help with the 2D-DOSY NMR experiments. We are grateful to Dr. Thomas Wyttenbach and Prof. Michael T. Bowers for helpful discussions on collision cross sections in ion-mobility experiments. TWIM=traveling wave ion mobility. Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Graphical Abstract TWIM peaks: A macrocycle containing 12 PdII terpyridyl centers was assembled using 4,4′-bipyridyl ligands and characterized by NMR and traveling wave ion mobility mass spectrometry (TWIM-MS). The macrocyclic architecture was also examined by tandem mass spectrometry and collisionally activated dissociation (CAD) experiments (see picture; C gray, N blue, Pd orange), and the resulting fragments were monitored by time-of-flight mass analysis. References 1I. Eryazici, P. Wang, C. N. Moorefield, M. Panzer, M. Durmas, C. D. Shreiner, G. R. Newkome, Dalton Trans. 2007, 626– 628. 2R. Trokowski, S. Akine, T. Nabeshima, Chem. Commun. 2008, 889– 890. 3S.-H. Hwang, C. N. Moorefield, F. R. Fronczek, O. Lukoyanova, L. Echegoyen, G. R. Newkome, Chem. Commun. 2005, 713– 715. 4F. M. Romero, R. Ziessel, A. Dupont-Gervais, A. Van Dorsselaer, Chem. Commun. 1996, 551– 553. 5E. C. Constable, C. E. Housecroft, C. B. Smith, Inorg. Chem. Commun. 2003, 6, 1011– 1013. 6J. 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