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Molecular Re I Cages: Structural and Luminescent Properties
Author(s) -
Tzeng BiingChiau,
Chao An,
Lin MeiChun,
Lee GeneHsiang,
Kuo TingShen
Publication year - 2017
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/chem.201704122
Subject(s) - luminescence , pyrazine , benzene , ligand (biochemistry) , acetylene , crystallography , chemistry , trigonal prismatic molecular geometry , molecule , bipyridine , crystal structure , stereochemistry , materials science , organic chemistry , receptor , octahedron , biochemistry , optoelectronics
Versatile building block [{Re(CO) 4 } 3 (C 3 N 3 S 3 )] ( 1 a ; C 3 N 3 S 3 =cyanurate trianion) reacts with linear dipyridyl ligands [i.e., pyrazine (pz), 4,4′‐bipyridine (bpy), 1,2‐bis(4‐pyridyl)ethylene (bpe), bis(4‐pyridyl)acetylene (bpa), and 1,4‐bis(pyridyl‐4‐ylethynyl)benzene (bpb)] and a tripyridyl ligand [1,3,5‐tris(4‐pyridylethynyl)benzene (tpb)] to afford a series of molecular cages [{Re(CO) 3 } 6 (L) 3 (C 3 N 3 S 3 ) 2 ] [L=pz ( 2 ), bpy ( 3 ), bpe ( 4 ), bpa ( 5 ), bpb ( 6 )] and [{Re(CO) 3 } 9 (tpb) 3 (C 3 N 3 S 3 ) 3 ] ( 7 ) under solvothermal conditions. Various structural dimensions and motifs can be systematically tuned and obtained by using different dipyridyl and tripyridyl ligands in the reactions. The molecular cages of hexanuclear complexes 2 – 6 containing dipyridyl ligands feature interesting trigonal‐prismatic structures with different dimensions. Furthermore, nonanuclear complex 7 has a novel triangular‐star structure, and three benzene rings of tpb ligands form a triple‐decker arrangement with significant π ⋅⋅⋅ π interactions having distances of 3.490(1) and 3.528(1) Å. In addition, molecular cages 1 – 3 and 5 – 7 exhibit luminescence in the solid state, and their luminescent properties were also studied.