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Supramolecular Frameworks Built up from Red‐Phosphorescent trans ‐Re 6 Cluster Building Blocks: One Pot Synthesis, Crystal Structures, and DFT Investigations
Author(s) -
El Osta Racha,
Demont Antoine,
Audebrand Nathalie,
Molard Yann,
Nguyen Thi Thuong,
Gautier Régis,
Brylev Konstantin A.,
Mironov Youri V.,
Naumov Nikolay G.,
Kitamura Noboru,
Cordier Stéphane
Publication year - 2015
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201500074
Subject(s) - stacking , supramolecular chemistry , cluster (spacecraft) , rhenium , luminescence , crystallography , hydrogen bond , chemistry , crystal structure , aqueous solution , molecule , phosphor , bipyridine , crystal engineering , water cluster , materials science , inorganic chemistry , organic chemistry , computer science , programming language , optoelectronics
The reaction of a K 4 [{Re 6 S i 8 }(OH) a 6 ] · 8H 2 O rhenium cluster salt with 4,4′‐bipyridine (bpy) or 4‐aminopyridine (apy) in an aqueous solution at mild temperature and pressure conditions lead to cluster functionalization and to the formation of two new compounds [{Re 6 S i 8 }(OH) a 2 (bpy) a 4 ] · bpy · 4H 2 O ( 1 ) and [{Re 6 S i 8 }(OH) a 2 (apy) a 4 ] · 2apy · 2H 2 O ( 2 ). Their crystal structures are built up from trans ‐[{Re 6 S i 8 }(OH) a 2 (L) a 4 ] neutral units and the cohesions of both supramolecular frameworks are based on π–π stacking as well as hydrogen bonds, involving the cluster units trans ‐[{Re 6 S i 8 }(OH) a 2 (L) a 4 ], interstitial L ligands and water molecules. 1 and 2 present 2D and 3D cluster frameworks, respectively. Both compounds show red‐NIR luminescence in the solid states. DFT calculations demonstrate that association of face capped Re 6 clusters with bpy and apy ligands enabled to form supramolecular frameworks that retain luminescent properties of the cluster units.