Host–Guest Driven Self‐Assembly of Linear and Star Supramolecular Polymers

Yebeutchou, Roger M.; Tancini, Francesca; Demitri, Nicola; Geremia, Silvano; Mendichi, Raniero; Dalcanale, Enrico

doi:10.1002/anie.200801002

Cited by 116 publications

(71 citation statements)

References 34 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…(2) To clarify the gas-phase properties of complexes formed by phosphonate cavitands, [9] since one of their applications is gas sensing [10]. The earlier reported results have shown that the phosphonate cavitands are capable of selectively forming complexes with alcohols [11][12][13][14] and ammonium ions [7,15,16], which has just recently led to application of phosphonate cavitands in supramolecular polymers [17], molecular recognition on silicon surfaces [18], and product protection in amine methylation reactions [19]. Number and positioning of the P ϭ O groups at the upper rim and their relative orientation with respect to the cavity are the key host parameters in defining the multiple H-bonding interactions involved in the recognition process [16].…”

mentioning

confidence: 99%

Hydrogen bonding in phosphonate cavitands: Investigation of host-guest complexes with ammonium salts

Kalenius

Neitola

Suman

et al. 2010

J. Am. Soc. Mass Spectrom.

Self Cite

View full text Add to dashboard Cite

The H-bonding in alkylammonium complexes of phosphonate cavitands were studied by mass spectrometric methods and theoretical calculations. The alkylammonium ions included primary, secondary, and tertiary methyl-and ethylammonium ions. Their complexation with mono-, tetra-, and two di-phosphonate cavitands, which differ according to the number and position of H-bond acceptor P ϭ O groups, was evaluated by using different competition experiments, energy-resolved CID, gas-phase H/D-exchange, and ligand-exchange reactions, together with ab initio theoretical optimization of the complexes. The phosphonate cavitands with two or more adjacent P ϭ O groups were found to be selective towards secondary alkylammonium ions, due to simultaneous formation of two stable hydrogen bonds. In the ion-molecule reactions (both H/D-and ligand-exchange), the formation of two stable hydrogen bonds was observed either to slow down the reaction or to completely prevent it. This was, however, limited to situations where two hydrogen bonds are formed between the H-bond donor sites of the alkyl ammonium ion and the vicinal H-bond acceptor sites of the cavitand. (J Am Soc Mass Spectrom 2010, 21, 440 -450)

show abstract

mentioning

confidence: 99%

Hydrogen bonding in phosphonate cavitands: Investigation of host-guest complexes with ammonium salts

Kalenius

Neitola

Suman

et al. 2010

J. Am. Soc. Mass Spectrom.

Self Cite

View full text Add to dashboard Cite

show abstract

“…In contrast, supramolecular self-assembly is a versatile alternative and offers the quick construction of 1-, 2-, or 3-dimensional nanometric architectures that have discrete structures, properties, and functions in which the molecular components are held together by reversible interactions (7)(8)(9)(10)(11). Self-assembled nanometric multiporphyrin arrays having well-defined shapes and dimensions provide unique optical and electrochemical properties for photochemical energy conversion and storage.…”

mentioning

confidence: 99%

Supramolecular polymer formed by reversible self-assembly of tetrakisporphyrin

Haino

Fujii

Watanabe

et al. 2009

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

View full text Add to dashboard Cite

S-shaped tetrakisporphyrin 2 forms supramolecular polymeric assemblies via a complementary affinity of its bisporphyrin units in solution. The self-association constant determined by applying the isodesmic model is >10 6 L mol ؊1 , which suggests that a sizable polymer forms at millimolar concentrations at room temperature. The electron deficient aromatic guest (TNF) binds within the molecular clefts provided by the bisporphyrin units via a chargetransfer interaction. This guest complexation completely disrupts supramolecular polymeric assembly. The long, fibrous fragments of the polymeric assemblies were characterized by atomic-force microscopy imaging of a film cast on a mica surface. The polymeric assemblies have lengths of >1m and show a coiled structure with a higher level of organization. The approach discussed in this report concerning the quick preparation of supramolecular polymeric assemblies driven by noncovalent forces sets the stage for the preparation of a previously undescribed class of macromolecular porphyrin architectures.porphyrin ͉ supramolecular chemistry S ignificant effort has been directed toward elucidating the energy transport phenomena occurring in natural lightharvesting complexes. A variety of porphyrin-based model compounds have been created to mimic natural light-harvesting complexes with the goal of applying them to artificial lightharvesting systems and molecular photonic devices (1-4). Among them, nanometric multiporphyrin arrays are the most challenging target, wherein, their covalent synthesis offers a high stability and a precisely controlled arrangement of multiporphyrin arrays (5, 6). Unfortunately, the growth of size and complexity of these systems makes their synthesis tedious and inefficient.In contrast, supramolecular self-assembly is a versatile alternative and offers the quick construction of 1-, 2-, or 3-dimensional nanometric architectures that have discrete structures, properties, and functions in which the molecular components are held together by reversible interactions (7-11). Self-assembled nanometric multiporphyrin arrays having well-defined shapes and dimensions provide unique optical and electrochemical properties for photochemical energy conversion and storage. As a consequence, their practical applications can be foreseen in the field of molecular electronics: conductive molecular wires, switches, and photovoltaic cells. These creative developments should pave the way for research directions in creating key materials for emerging field of nanotechnology and science.Coordination-driven self-assembly of porphyrin is one of the most useful approaches for developing large and elaborate molecular architectures (12, 13). Hunter and coworkers developed unique self-assembled porphyrin arrays (14-18). Giant porphyrin arrays and large porphyrin wheels via metal coordination for modeling light-harvesting antenna have been reported by . Aida and coworkers have investigated self-assembled nanometric porphyrin arrays (27-29). There are limited examples of porphyrin self...

show abstract

“…For this purpose phosphonate cavitands have been used, since they fulfill the requirement for high association constants between the host and suitable guests (see Chapter 6.2). By exploiting the outstanding complexation properties of tetraphosphonate cavitands toward methylpyridinium guests, we self-assembled a new class of supramolecular polymers featuring not only a reversible nature but also a remarkable plasticity, allowing structural switches from linear to star-branched architectures [44]. In particular, cavitand 5 was prepared (Scheme 4.7), functionalized at the upper rim with four phosphonate bridges in their all inwardfacing configuration, and at the lower rim with a single methylpyridinium unit.…”

Section: Heteroditopic Cavitands Self-assembled Via Host-guest Interamentioning

confidence: 99%