Molecular Assemblies of Metal Complexes via Base-Pairing of Nucleic Acids in the Crystalline State

Manabu Nakaya, Ryo Ohtani, Kunihisa Sugimoto, Masaaki Nakamura, Leonard F. Lindoy, Shinya Hayami

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

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](BF4)2 (1) and [Co(T-C6-terpy)2](BF4)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](BF4)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)](BF4)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](BF4)2 (4) with [Co(C6-terpy)2](BF4)2 (5) and 1 with 5.

Original languageEnglish
Pages (from-to)7232-7237
Number of pages6
JournalChemistry - A European Journal
Volume23
Issue number30
DOIs
Publication statusPublished - May 29 2017

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Nucleic acids
Coordination Complexes
Metal complexes
Cobalt
Nucleic Acids
Crystalline materials
Thymine
Ladders
Adenine
Crystallization
Dimers
Needles
Crystal structure
Display devices
Single crystals
Crystals

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Organic Chemistry

Cite this

Molecular Assemblies of Metal Complexes via Base-Pairing of Nucleic Acids in the Crystalline State. / Nakaya, Manabu; Ohtani, Ryo; Sugimoto, Kunihisa; Nakamura, Masaaki; Lindoy, Leonard F.; Hayami, Shinya.

In: Chemistry - A European Journal, Vol. 23, No. 30, 29.05.2017, p. 7232-7237.

Research output: Contribution to journalArticle

Nakaya, Manabu ; Ohtani, Ryo ; Sugimoto, Kunihisa ; Nakamura, Masaaki ; Lindoy, Leonard F. ; Hayami, Shinya. / Molecular Assemblies of Metal Complexes via Base-Pairing of Nucleic Acids in the Crystalline State. In: Chemistry - A European Journal. 2017 ; Vol. 23, No. 30. pp. 7232-7237.
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abstract = "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](BF4)2 (1) and [Co(T-C6-terpy)2](BF4)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](BF4)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)](BF4)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](BF4)2 (4) with [Co(C6-terpy)2](BF4)2 (5) and 1 with 5.",
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