Molecular squares, coordination polymers and mononuclear complexes supported by 2,4-dipyrazolyl-6H-1,3,5-triazine and 4,6-dipyrazolylpyrimidine ligands

Abstract

The title compounds include the [BF4⊂{Fe(L)}4(μ-L)4]7+ molecular square shown; [Ag4(μ-L)4]4+ metallacycles with encapsulated ClO4− or SbF6− ions; and families of iron(ii) and silver(i) coordination polymers.

Iron and Silver Complexes of 4‐(Imidazol‐1‐yl)‐2,6‐di(pyrazol‐1‐yl)‐pyridine (L), Including a [Fe3(µ‐F)2F6L8]+ Assembly

“…That is often found in mass spectra of silver/N-heterocyclic ligand assemblies, which are usually labile in solution. [17,18,24] Isostructural (Figure 2, Table S3). [3,25] The deviation of the molecule from its idealized D 2d symmetry is expressed by two parameters: the trans-N{pyridyl}-Fe-N{pyridyl} angle (φ) and the dihedral angle between the least-squares planes of the heterocyclic cores of the two ligands (θ).…”

“…That is often found in mass spectra of silver/N‐heterocyclic ligand assemblies, which are usually labile in solution. [ 17,18,24 ]…”

“…Given our on-going interest in spin-crossover materials, [3] we have also screened other ditopic di-or tri-(pyrazolyl)azines as bridging ligands in assembly structures (or gels) with spin-crossover switching properties. [16][17][18][19] Continuing this effort, we now report the ditopic ligand 4-(imidazol-1-yl)-2,6-di(pyrazol-1-yl)pyridine (L, Scheme 1), a potentially bridging ligand with divergent tridentate and monodentate metal-binding domains, [5] and its iron and silver complexes. Our results include the unexpected isolation of an unusual [Fe 3 (μ-F) 2 F 6 L 8 ] + complex, with a linear [Fe III 2 (μ-F) 2 Fe III F 4 ] 3+ core supported by monodentate L coordination.…”

s‐Triazine pincer ligands: Synthesis of their metal complexes, coordination behavior, and applications

“…In case of third substituent with ligating character such as pyrazole, the resulting tris-pyrazolyl-s-triazine (TPT) ligand [161] is capable to coordinate more metal sites leading to nonpincer discrete mononuclear or polynuclear or polymeric complexes. [182] The tetra-nuclear [Fe 4 (DPT) 8 ](BF 4 ) 8 complex shown in Figure 24a is an example for such coordination behavior. Also, the [Ag (TPT)(MeOH)]BF 4 , [Ag(TPT)]BF 4 , and [Ag(μ-TPT)]ClO 4 are examples for polymeric complexes in which TPT works as bidentate and connector ligand between Ag(I) centers.…”

“…[183-186,215a] In presence of ZnCl 2 , the BPT ligand undergone hydrolysis as indicated by the formation of [Zn(pz) 2 Cl 2 ] complex. [186] The same research group reported the Cu(II)mediated hydrolysis of the BPT ligand [215b] followed by complexation giving the followed by complexation Giri et al [134] [Ru(dmdptz)(phen)Cl](ClO Wu et al [136] [ Safin et al [143] [Cd( Frost et al [147] [Cd 2 (TpymT)( Safin et al [148] [Pb 2 (TPymT)(NO Wang et al [176] [ Soliman et al [185] [Cd(BPT) Carranza et al [169] [Ag(bdpdt) Berdiell et al [182] [ [Cu(TPTZ) 2 ](PF 6 ) 2 Breast cancer (MCF-7) Abdi et al [51] [Cu(TPTZ)(Ph 3 P) 2 ](PF 6 ) Cosensitized solar cells Báez-Castro et al [52,53] (Continues)…”