Assembly of Heterometallic Rigid-Rod Complexes and Coordination Oligomers from Gold(I) Metalloligands

Abstract

The reactions of TpylC6H4C≡CAuL (Tpyl = 2,2':6',2″-terpyridin-4'-yl; L = PPh3, CNXy; Xy = 2,6-dimethylphenyl) with MX2·nH2O (M = Fe, X = ClO4; M = Co, X = BF4; M = Zn, X = TfO, ClO4) in a 2:1 molar ratio give complexes [M(TpylC6H4C≡CAuL)2]X2. Similarly, the reactions of PPN[(TpylC6H4C≡C)2Au] (PPN = (Ph3P)2N) with an equimolar amount of MX2·nH2O give coordination oligomers [M{(TpylC6H4C≡C)2Au}]nXn (M = Fe, Zn, X = ClO4; M = Co, X = BF4). The complexes and oligomers have been isolated and characterized. The crystal structures of [Fe(TpylC6H4C≡CAuCNXy)2](ClO4)2 and [Co(TpylC6H4C≡CAuPPh3)2](BF4)2 have been determined by X-ray diffraction. The hydrodynamic sizes of complexes [M(TpylC6H4C≡CAuPPh3)2]X2 and coordination oligomers [M{(TpylC6H4C≡C)2Au}]nXn have been studied by NMR diffusion spectroscopy and dynamic light scattering measurements.

Reversible Redox, Spin Crossover, and Superexchange Coupling in 3d Transition‐Metal Complexes of Bis‐azinyl Analogues of 2,2′:6′,2′′‐Terpyridine

“…Complexes of terpy itself can have important functionalities, whereas terpy derivatives bearing different substituents are also known in the literature. These variants of terpy and their complexes have been further studied in supramolecular chemistry such as metal‐containing polymers,, molecular qubits, molecular and nanochemical devices, dendrimers, and supramolecular arrays . One such modification of terpy to attain these desired properties has been the incorporation of nitrogen‐rich triazines at the 2 and 6 positions of the central pyridine ring, resulting in 2,6‐bis(5,6‐dialkyl‐1,2,4‐triazin‐3‐yl)‐pyridine (BTP); a terpy analogue with a trident‐chelating environment (Figure ).…”

Polypyridyl-functionalizated alkynyl gold(i) metallaligands supported by tri- and tetradentate phosphanes

“…42 Very recently, Vicente and co-workers reported the obtention of appealing supramolecular architectures like triple-stranded helicates, 51,52 helical dimers, 53 rigid-rod complexes and coordination oligomers. 54 Noteworthily, all the reported alkynyl gold(I) compounds with pendant polypyridyl moieties mentioned above are supported by mono or diphosphanes as auxiliary ligands, and consequently are able to act as mono or ditopic metallaligands. However, neither tri nor tetratopic analogous systems have been described so far.…”

Fine Tunable, Redox Active Octapalladium Chains Supported by Linear Tetraphosphines, Leading to Dynamically 1D Self‐Assembled Coordination Polymers

“…The value of R H 3a (1.31 nm) may suggest a thermodynamically averaged diameter for the particle as 2.6 nm which is approximately comparable to the molecular length of 3 a (3.6 nm) determined by X‐ray analysis, although the hydrodynamic radius no longer reflect the real molecular shapes, and those of R H 5b are ten times larger than R H 3a . Since the rigid‐rod coordination polymers are able to be modeled as cylindrical rods of diameter d and length L , and this assumption can be applied to Equation (3) that has been developed to investigate dynamic self‐assembled structures of coordination polymers, [42–45] …”