Concurring Chalcogen‐ and Halogen‐Bonding Interactions in Supramolecular Polymers for Crystal Engineering Applications

Abstract

The engineering of crystalline molecular solids through the simultaneous combination of distinctive non‐covalent interactions is an important field of research, as it could allow chemist to prepare materials depicting multi‐responsive properties. It is in this context that, pushed by a will to expand the chemical space of chalcogen‐bonding interactions, a concept is put forward for which chalcogen‐ and halogen‐bonding interactions can be used simultaneously to engineer multicomponent co‐crystals. Through the rational design of crystallizable molecules, chalcogenazolo pyridine scaffold (CGP) modules were prepared that, bearing either a halogen‐bond acceptor or donor at the 2‐position, can interact with suitable complementary molecular modules undergoing formation of supramolecular polymers at the solid state. The recognition reliability of the CGP moiety to form chalcogen‐bonded dimers allows the formation of heteromolecular supramolecular polymers through halogen‐bonding interactions, as confirmed by single‐crystal X‐ray diffraction analysis.

The Nature of Strong Chalcogen Bonds Involving Chalcogen‐Containing Heterocycles

“…Analysis of Chalcogen Bonds using SAPT Calculations Our studies were focused on investigations of the nature of strong chalcogen bonds that exist primarily between tellurium-containing nitrogen heterocycles and different Lewis bases. [12,15,17,18,21,[30][31][32][33] Thelatter are for instance oxygen or nitrogen atoms of heterocycles or amides.Inthis study,we chose tellurium-containing aromatics as model compounds and calculated the dimers and their complexes with acetamide,t rimethylamine,t rimethylphosphine,t etrachloromethane and pyridine ( Figure 1). Forc omparison purposes the corresponding sulfur-a nd selenium-containing complexes were also investigated.…”

“…[1] In the beginning the basic concept of chalcogen bonding was focused, [2][3][4][5][6][7][8] whereas in recent times,t he use of strong chalcogen bonds has become an object of interest. [9][10][11] It could be shown that this bond type can also be used for crystal engineering, [12][13][14] molecular recognition in solution [15][16][17][18][19][20][21] and catalysis. [11,20,[22][23][24][25][26][27][28] Very strong and promising chalcogen bonds are found in electron-poor tellurium compounds such as isotellurazole oxides [21,29] or telluradiazole.…”

“…[18] In addition to isotellurazole oxides and telluradiazoles,t ellurazoles have recently been used as promising building blocks for the design of strong chalcogen bonds. [12,32] Furthermore,i tc ould be shown that the intermolecular interactions between the tellurium atoms of tellurazoles and the oxygen atom of an amide group result in the formation of supramolecular wires and organic framework in solid state. [33] Due to fundamental theoretical investigations the principle of chalcogen bonding has been understood in terms of strength and orientation.…”

Die Natur starker Chalkogenbindungen unter Beteiligung chalkogenhaltiger Heterocyclen

“…Der Fokus unserer Studien lag auf der Untersuchung der Natur starker Chalkogenbindungen, die vornehmlich zwischen tellurhaltigen Stickstoff‐Heterocyclen und verschiedenen Lewis‐Basen existieren [12, 15, 17, 18, 21, 30–33] . Letztere sind beispielsweise Sauerstoff‐ oder Stickstoffatome von Heterocyclen oder Amiden.…”

“…Diese tellurhaltigen Systeme bilden in Lösung stark assoziierende Dimere und Oligomere [21] und können deshalb als molekulare Erkennungseinheiten in der supramolekularen Chemie eingesetzt werden [18] . Neben Isotellurazoloxiden und Tellurdiazolen werden neuerdings auch Tellurazole als vielversprechende Bausteine zum Aufbau starker Chalkogenbindungen verwendet [12, 32] . Es konnte gezeigt werden, dass die intermolekularen Wechselwirkungen zwischen dem Telluratom des Tellurazols und dem Sauerstoffatom einer Amidgruppe zur Bildung supramolekularer Drähte und organischer Gerüstverbindungen in fester Phase führen [33] …”