Premium
Molecular Assemblies of Metal Complexes via Base‐Pairing of Nucleic Acids in the Crystalline State
Author(s) -
Nakaya Manabu,
Ohtani Ryo,
Sugimoto Kunihisa,
Nakamura Masaaki,
Lindoy Leonard F.,
Hayami Shinya
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.201700593
Subject(s) - terpyridine , crystallography , chemistry , cobalt , stereochemistry , dimer , crystal structure , metal , synthon , inorganic chemistry , organic chemistry
The nature of the molecular assemblies formed in the crystalline state by cobalt(II) terpyridine (terpy) complexes incorporating appended adenine (A) or thymine (T) bases was found to be controlled by which bases are present. Single‐crystals of the cobalt(II) complexes [Co(A‐C6‐terpy) 2 ](BF 4 ) 2 ( 1 ) and [Co(T‐C6‐terpy) 2 ](BF 4 ) 2 ( 2 ) have needle and block habits, respectively. Subsequent mixing of 1 and 2 in MeOH resulted in isolation of [Co(A‐C6‐terpy) 1.5 (T‐C6‐terpy) 0.5 ](BF 4 ) 2 ( 3 ) as plate‐like crystals. A 3D network structure is present in 1 that incorporates 1D chains, whereas 2 adopts a 2D stacked structure constructed from ladder‐type assemblies. For 3 , “dimer‐rings” consisting of [Co(A‐C6‐terpy) 2 ] 2+ and [Co(A‐C6‐terpy)(T‐C6‐terpy)] 2+ units are generated by means of base‐pairing between A and T. Notably, 3 displays the first crystal structure of a heteroleptic cobalt(II) complex of [Co(A‐C6‐terpy)(T‐C6‐terpy)](BF 4 ) 2 . These assembly differences involving the terpyridine cobalt(II) complex units in 1 – 3 affect the cooperativities influencing their spin crossover (SCO) behavior. The influence of the terminal nucleobases on the resulting assembly has been probed by investigating the co‐crystallization of [Co(terpy) 2 ](BF 4 ) 2 ( 4 ) with [Co(C6‐terpy) 2 ](BF 4 ) 2 ( 5 ) and 1 with 5 .