Construction of Functionalized Metallosupramolecular Tetragonal Prisms via Multicomponent Coordination-Driven Self-Assembly

Wang, Ming; Zheng, Yao‐Rong; Cook, Timothy R.; Stang, Peter J.

doi:10.1021/ic2002157

Cited by 47 publications

(40 citation statements)

References 49 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…The recent development of new strategies for multicomponent self-assembly has provided a method to increase the structural complexity of chromophoric supramolecular coordination complexes (SCCs) wherein three or more building blocks can assemble into a single thermodynamically favored product (54,55). One method to achieve multicomponent assembly is to identify metal nodes and ligands that prefer heteroligated coordination spheres, thus avoiding statistical mixtures of products.…”

Section: Significancementioning

confidence: 99%

Synthesis and photophysical studies of self-assembled multicomponent supramolecular coordination prisms bearing porphyrin faces

Shi

Sánchez‐Molina

Cao

et al. 2014

Proc. Natl. Acad. Sci. U.S.A.

Self Cite

View full text Add to dashboard Cite

Multicomponent self-assembly, wherein two unique donor precursors are combined with a single metal acceptor instead of the more common two-component assembly, can be achieved by selecting Lewis-basic sites and metal nodes that select for heteroligated coordination spheres. Platinum(II) ions show a thermodynamic preference for mixed pyridyl/carboxylate coordination environments and are thus suitable for such designs. The use of three or more unique building blocks increases the structural complexity of supramolecules. Herein, we describe the synthesis and characterization of rectangular prismatic supramolecular coordination complexes (SCCs) with two faces occupied by porphyrin molecules, motivated by the search for new multichromophore complexes with promising light-harvesting properties. These prisms are obtained from the self-assembly of a 90°Pt(II) acceptor with a meso-substituted tetrapyridylporphyrin (TPyP) and dicarboxylate ligands. The generality of this self-assembly reaction is demonstrated using five dicarboxylate ligands, two based on a rigid central phenyl ring and three alkyl-spaced variants, to form a total of five free-base and five Zn-metallated porphyrin prisms. All 10 SCCs are characterized by 31 P and 1 H multinuclear NMR spectroscopy and electrospray ionization mass spectrometry, confirming the structure of each self-assembly and the stoichiometry of formation. The photophysical properties of the resulting SCCs were investigated revealing that the absorption and emission properties of the free-base and metallated porphyrin prisms preserve the spectral features associated with free TPyP. supramolecular chemistry | metallacages T he use of sunlight is ubiquitous as the input for carbonneutral, renewable energy schemes (1). Every strategy that relies on solar energy conversion, ranging from direct conversion to electricity in photovoltaics (2) to the generation of fuels via electrocatalysis (3), photoanode (4, 5), or photocathode devices (6), or photocatalysis (7) requires that photons be absorbed by a molecule or material as the first step in providing the driving force for subsequent transformation. Natural systems have evolved light-harvesting complexes, comprising multiprotein ensembles embedded with pigment molecules to enhance photon absorption for photosynthesis (8). These pigment-rich sites are arranged such that excitation of a distal chromophore will ultimately result in energy transfer to a reaction center via a series of migration and transfer processes (9). Strategies to replicate natural light-harvesting complexes necessarily demand the organization of multiple chromophores (10), a requirement that makes self-assembly and supramolecular chemistry particularly well suited for such efforts (11-13). As such, a variety of approaches have been applied toward the development of new materials that exhibit broadband absorption and efficient energy transfer (14-16). The subsequent studies of such materials span investigations of the fundamental science behind energy migration and transfer, t...

show abstract

Section: Significancementioning

confidence: 99%

Synthesis and photophysical studies of self-assembled multicomponent supramolecular coordination prisms bearing porphyrin faces

Shi

Sánchez‐Molina

Cao

et al. 2014

Proc. Natl. Acad. Sci. U.S.A.

Self Cite

View full text Add to dashboard Cite

show abstract

“…Whereas the building blocks of metallacycles occupy the edges of their target polygons, dubbed "edge-directed assembly", the formation of polyhedra via the coordination-driven self-assembly permits "face-directed" strategies in which precursors can be used to occupy entire faces of a target metallacage. This can be illustrated by considering the cube; edge-directed assembly demands eight tectons to represent the vertices in the form of tritopic species with 90 angularities between binding sites. These vertices can then be joined by 12 linear ditopic donors to act as the edges of the cube [48].…”

Section: Supramolecular Polyhedramentioning

confidence: 99%

“…These vertices can then be joined by 12 linear ditopic donors to act as the edges of the cube [48]. In contrast, the six faces of a cube can be represented by tetratopic panels with 90 angles between each adjacent binding site [49]. These panels will become the faces of a cube upon assembly with twelve 90 ditopic building blocks, which lie at the center of each edge (Fig.…”

Section: Supramolecular Polyhedramentioning

confidence: 99%

“…This transformation process works equally well to deliver multicomponent prismatic SCCs. Both initial SCCs must contain 90 acceptors and a single type of donor. Since the final prisms typically contain a polypyridyl donor at each end, the first initial SCC must be composed of exclusively these two building blocks.…”

Section: Supramolecule-to-supramolecule Transformationmentioning

confidence: 99%

“…3). The fledgling directional bonding method was further developed by the recognition that squares could also be generated in a [2+2] fashion, provided that two of the requisite 90 angles could be encoded into the donor precursor. This was achieved first by inbedding an organometallic Pt-aryl corner into a nitrile donor [22,23] and later by generating a diypridyl iodonium ligand capable of interacting with the previously employed cis-capped Pt and Pd acceptors [24,25] [27].…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Coordination-Driven Supramolecular Macromolecules via the Directional Bonding Approach

Cook

Stang

2013

Hierarchical Macromolecular Structures: 60 Years After the Staudinger Nobel Prize I

Self Cite

View full text Add to dashboard Cite

Coordination-driven self-assembly is a process that generates supramolecular architectures from molecular precursors by exploiting the favorable properties of metal-ligand bonding. The discrete supramolecular coordination complexes (SCCs) thus obtained have enjoyed multiple decades of development, focused initially on the design and reactivity of rigid building blocks with specific directionalities and angularities, thereby populating a molecular library of complementary donor and acceptor subunits. More recently, efforts have broadened to encompass pre-and post-self-assembly modifications, which have lead to new routes for obtaining functionalized metallacages and metallacycles, multicomponent assemblies incorporating multiple types of ligands in a single scaffold, and supramolecular transformations that quantitatively alter the structure of a given SCC, furnishing an entirely new architecture.

show abstract

Supramolecular Redox Transduction: Macrocyclic Receptors for Organic Guests

Goeb¹,

Canevet²,

Sallé³

2013

Organic Synthesis and Molecular Engineering

View full text Add to dashboard Cite

I sincerely thank all the authors who have contributed their chapters to this book. These contributions have allowed a wide coverage of fields within organic molecular engineering, hopefully of interest to both experts and nonexperts in the field.I would also like to thank valuable feedback from students who have read some parts of the book, in particular, the students who have followed my course in supramolecular chemistry. With its wide coverage, it is indeed my hope that this book will be useful as a textbook for courses in organic, supramolecular, and macromolecular chemistry.M.B.N.

show abstract

Construction of Functionalized Metallosupramolecular Tetragonal Prisms via Multicomponent Coordination-Driven Self-Assembly

Cited by 47 publications

References 49 publications

Synthesis and photophysical studies of self-assembled multicomponent supramolecular coordination prisms bearing porphyrin faces

Synthesis and photophysical studies of self-assembled multicomponent supramolecular coordination prisms bearing porphyrin faces

Coordination-Driven Supramolecular Macromolecules via the Directional Bonding Approach

Supramolecular Redox Transduction: Macrocyclic Receptors for Organic Guests

Contact Info

Product

Resources

About