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Hydrogen‐Bonded Networks through Second‐Sphere Coordination
Author(s) -
Beauchamp Derek A.,
Loeb Stephen J.
Publication year - 2002
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/1521-3765(20021115)8:22<5084::aid-chem5084>3.0.co;2-8
Subject(s) - hydrogen bond , supramolecular chemistry , crystal engineering , coordination sphere , crystallography , chemistry , phenanthroline , ligand (biochemistry) , crystal structure , coordination polymer , aqueous solution , molecule , coordination complex , metal , stereochemistry , organic chemistry , biochemistry , receptor
The reaction of 4,7‐phenanthroline ( 1 ) with aqueous transition‐metal complexes [Mn(H 2 O) 6 ][NO 3 ] 2 , [Co(H 2 O) 6 ][NO 3 ] 2 , [Ni(H 2 O) 6 ][NO 3 ] 2 , [Mn(H 2 O) 6 ][ClO 4 ] 2 , and [Co(H 2 O) 6 ][ClO 4 ] 2 does not produce coordination complexes between these metal cations and the N‐donor ligand as expected. Instead, supramolecular hydrogen‐bonded networks are formed between the nitrogen donor atoms of 4,7‐phenanthroline and the OH groups of coordinated water molecules; MOH⋅⋅⋅N interactions. This motif of second‐sphere coordination for 1 can be exploited as a tool for crystal engineering. As a demonstration of the generality of this new interaction as a supramolecular building block, five X‐ray crystal structures are reported that utilise this hydrogen bonding scheme; [Co(H 2 O) 4 (NO 3 ) 2 ]⋅( 1 ) 2 ( 2 a ), [Co(MeCN) 2 (H 2 O) 4 ][ClO 4 ] 2 ⋅( 1 ) 2 ( 2 b ), [Ni(H 2 O) 4 (NO 3 ) 2 ]⋅( 1 ) 2 ( 3 a ), [Mn(H 2 O) 4 (NO 3 ) 2 ]⋅( 1 ) 2 ( 4 a ), and [Mn(H 2 O) 6 ][ClO 4 ] 2 ⋅( 1 ) 4 ⋅4 H 2 O ( 4 b ). Each network involves complete saturation of the hydrogen‐bond donor sets between the aqua complex and 1 using primarily MOH⋅⋅⋅N( 1 ) and MOH⋅⋅⋅O(anion), interactions. Thermogravimteric analysis shows these materials to have stablilities similar to coordination polymers involving metal–ligand bonds; this demonstrates that second‐sphere hydrogen bonding has potential for the construction of polymeric metal‐containing materials.