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Pentanuclear Heterometallic String Complexes with High‐Bond‐order Units [Ni 2 3+ −Mo 2 4+ −Ni 2+ (bna) 4 X 2 ] 3+ (X = Cl, NCS)
Author(s) -
Hsu Ssuchieh,
Lin GengMin,
Lee GeneHsiang,
Chen Chunhsien,
Peng ShieMing
Publication year - 2018
Publication title -
journal of the chinese chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.329
H-Index - 45
eISSN - 2192-6549
pISSN - 0009-4536
DOI - 10.1002/jccs.201700331
Subject(s) - chemistry , crystallography , metal , valence (chemistry) , transition metal , stereochemistry , organic chemistry , biochemistry , catalysis
Our quest for ligands toward the synthesis of functional metal string complexes started from α‐pyridylamido anions. With the modulation of naphthyridylamido anions, the ligands carry less negative charge to be balanced and, thus, to some extent, can tune the oxidation state of the metal centers and the strength of metal–metal interactions. For example, the formation of Ni 2 3+ , a mixed‐valence moiety, has been demonstrated. In this paper, high‐bond‐order units of M 2 (Mo 2 or Ru 2 ) and Ni 2 3+ are introduced and supported by four equatorial ligands of the bisnaphthyridylamido anion (bna − ). The resulting compounds are [Ni 2 Mo 2 Ni(bna) 4 Cl 2 ](PF 6 ) 3 ( 1 ), [Ni 2 Mo 2 Ni(bna) 4 (NCS) 2 ](PF 6 ) 3 ( 2 ), and [Ni 2 Ru 2 Ni(bna) 4 Cl 2 ](ClO 4 ) 3 ( 3 ). X‐ray crystallography reveal quadruply bonded characteristics with Mo–Mo distances of 2.133(2) and 2.109(2) Å for 1 and 2 , respectively. The Ni 2 moieties have a short Ni–Ni distance of 2.331(5) for 1 and 2.334(4) Å for 2 , suggesting the formation of mixed‐valence Ni 2 3+ units. It appears that there are no significant metal–metal interactions between Mo 2 and its neighboring Ni centers. Characterization using magnetism, voltammetry, electronic absorption, and single‐molecule conductance, however, shows significant influence of Mo 2 on the properties of the metal string complexes.