Molecular Tectonics:  From Simple Tectons to Complex Molecular Networks

Abstract

Molecular networks in the crystalline phase are infinite periodic molecular assemblies formed under self-assembly conditions between self-complementary or complementary tectons. These millimeter-size structures may be regarded as hypermolecules formed by supramolecular synthesis using reversible intertecton interactions. Molecular tectonics, based on molecular recognition events and their iteration, is the approach dealing with design and preparation of molecular networks in the solid state. In this Account, an overview of the rational behind this approach is presented. A variety of molecular networks based on van der Waals interactions and hydrogen and coordination bonding possessing diverse connectivity and topology are discussed.

Hierarchical Self‐Assembly of One‐Dimensional Streptavidin Bundles as a Collagen Mimetic for the Biomineralization of Calcite

“…Such guest&host complexes often display unusual properties such as chemical reactivity, energy or electron transfer, second harmonic generation materials, high-capacity gas storage, catalysis, etc. [1][2][3][4][5][6] In parallel to these developments, surfaces and cavities spanned by protein higher-order aggregates have been exploited for molecular encapsulation and for templating nanoparticle synthesis. Typical examples include protein fibrils, [7,8] ferritin, [9,10] S-layers, [11][12][13] antibodies, [14] peptide amphiphiles, [15] capsids, [16][17][18][19] leucine zippers, [20] etc.…”

“…[21][22][23][24][25][26] Controlled protein aggregation is a critical process in many areas, ranging from biomineralization [27] to neurodegenerative diseases. [28] In contrast with molecular tectonics, however, [5,29] the de novo design of higher-order architectures by using proteins as building blocks (e.g. protein tectonics) remains challenging.…”

Luminescent sensing and formation of mixed f–d metal ion complexes between a Eu(iii)-cyclen-phen conjugate and Cu(ii), Fe(ii), and Co(ii) in buffered aqueous solution

“…45%, within this concentration range. The formation of the mixed f -d based ML 2 and ML 3 are shown in a cartoon format in the graphical abstract of this article.…”

Controlling the Assembly of C2-Symmetric Molecular Tectons Using a Thiocarbamate Appended Carbocyclic Cleft Molecule Analogous to Tröger’s Base

“…[16][17][18] Furthermore, the ability to control secondary and tertiary structure within crystal packing has enormous potential in the development of new functional materials and devices. Molecular tectonics [19][20][21][22] is the analysis of molecular crystals and their subsequent formation of networks, and as a consequence the tecton is defined as a construction unit with Conversely, thiocarbamates (3) like amides, form networks based on stronger hydrogen bonding, which is, in part, controlled by their configuration, with the cisoid form 3a leading to synthon 4, and the transoid form 3b leading to synthon 5 (scheme 1).…”