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Thiacalix[4]‐bis‐crown with Hard Cavities and Soft Bridges Exhibiting Endocyclic Potassium(I) Complexes and Exocyclic Silver(I) Coordination Polymers
Author(s) -
Ju Huiyeong,
Kim Chungsik,
Choi KyuSeong,
Lee Eunji,
Kim Seulgi,
Jung Jong Hwa,
Habata Yoichi,
Lindoy Leonard F.,
Lee Shim Sung
Publication year - 2018
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201800719
Subject(s) - chemistry , perchlorate , coordination polymer , ligand (biochemistry) , coordination complex , crystallography , titration , hsab theory , stereochemistry , polymer chemistry , inorganic chemistry , metal , ion , crystal structure , organic chemistry , receptor , biochemistry
Thiacalix[4]‐bis‐crown‐5 ( L ) was employed as a model host molecule, which shows both HSAB concept and endo/ exo ‐coordination modes. In the K + complexations, a dinuclear complex [K 2 ( L )](ClO 4 ) 2 · CH 3 CN ( 1 ) as well as a mononuclear complex [K( L )][Pt(tht)Cl 5 ] ( 2 ) (tht = tetrahydrothiophene) were isolated: the latter as first example in such symmetrical hosts. Each K + in both species is stabilized not only by K + –O bondings ( hard acid – hard base ) in the crown cavities ( endo ‐coordination) but also by K + ‐π interactions. The Ag + complexations afforded infinite products ( 3 and 4 ) in which the Ag + binds to the sulphur bridges ( soft acid – soft base ) from outside the cavity ( exo ‐coordination). When silver(I) perchlorate was used, a 1‐D coordination polymer {[Ag 2 ( L )(ClO 4 ) 2 ] · CH 2 Cl 2 } n ( 3 ) was obtained, while silver(I) nitrate afforded a 2‐D coordination polymer {[Ag 2 ( L )(µ‐NO 3 ) 2 ] · CH 3 OH} n ( 4 ). The dimensional difference between 3 and 4 is responsible for the coordination mode of anions where the perchlorate ion and the nitrate ion act as a terminal ligand and a bridging ligand, respectively. The solution studies by NMR titrations indicate the endo ‐coordination with K + and the exo ‐coordination with Ag + , similar to those observed in the solid state.