The assembly of two copper(II)–carboxylate dimer complexes appended with four peripheral triarylborane functionalities has been achieved. Complex stabilities in the presence of fluoride are examined.

Triarylboron-functionalized Cu(II) carboxylate paddlewheel complexes.

The factors which influence the formation of chelate, macrocycle or polymer in the reaction of silver(I) salts with bis(pyridine) ligands have been probed by studying structures in the solid state and cold spray ionization mass spectra in solution, with the ligands C6H4-1,3-[CONR(CH2)n-3-C5H4N]2, 1 (R = Me, n = 0) or 3 (R = H, n = 1) or 5-t-Bu-C6H3-1,3-[CONR(CH2)n-4-C5H4N]2, 2 (R = Me, n = 0) or 4 (R = H, n = 1). In both the solid state and solution, the complex [Ag(1)2]BF4 exists as a chelate complex 5. The ligands NN = 2–4 form complexes in the solid state with either macrocyclic structures [Ag2(μ-NN)2]X2 [6, NN = 2, X = BF4; 9, NN = 3, X = NO3] or polymeric structures [7, NN = 2, X = NO3; 8, NN = 3, X = CF3CO2; 10, NN = 4, X = CF3CO2]. The ligands 2 and 3 gave both macrocyclic and polymeric complexes, depending on the anion. In solution, these complexes existed as mixtures of macrocycles and ring-opened oligomers. In the crystalline state, the complexes 6–10 underwent supramolecular association through combinations of hydrogen bonding, secondary bonding of the type Ag⋯X to anions, or argentophilic bonding of the type Ag⋯Ag.

Dynamic ring-opening polymerization of silver(I) complexes with bis(amidopyridine) ligands.

The trimetallic compound catena-poly[dipotassium(I) [bis­(2,2′-bipyridine)di-μ3-trifluoro­acetato-dodeca-μ2-trifluoro­acetato-diplatinum(II)octa­silver(I)]], K2[Pt2Ag8(C2F3O2)14(C10H8N2)2], forms an extended structure in the solid state. Electrostatic inter­actions involving the K+ ions play a key role in the formation of the extended structure in three dimensions. The AgI ions form one-dimensional coordination polymers, with alternating Ag2 and Ag6 units linked by CF3CO2− ligands. Pt⋯Pt inter­actions perpendicular to the one-dimensional polymerization axis provide another element of long-range order, and electrostatic inter­actions with K+ ions provide connectivity between adjacent polymeric structures.

The anionic coordination polymer {K2[PtII2AgI8(2,2′-bipyridine)2(O2CCF3)14]}n

The reactions of cycloplatinated guanidinate(1-) complexes 1-6 with AgTFA (TFA = OC(O)CF3) in 1:1 and 1:2 PtII/AgI molar ratios afforded complexes containing three types of Pt2Ag2 skeletons (7-10, 11, and 13), one 1D CP containing Pt2Ag3 skeleton (16), and a Pt2Ag4 complex (17) in 91-95% (method 1), 73-82% (method 2) (7-10), and 54-79% (11, 13, 16, and 17) yields. The reactions of 11 with 2,6-XylNC (2,6-Xyl = 2,6-Me2C6H3) and 4-DMAP (4-dimethylaminopyridine) gave a neutral complex 18 and an ionic complex 19, respectively. Molecular structures of 12 complexes were unambiguously determined by single-crystal X-ray diffraction. Ten complexes contain unprecedented PtAg skeletons and are shown to contain multiple number of dative Pt → Ag bonds supported by the TFA ligand, platinated carbon of the TAG ligand, or both these ligands in conjunction with the Ag-Ag contacts stabilized by argentophilic interaction. Further, the new complexes were characterized by analytical, IR, and multinuclear NMR (19F, 1H, 13C{1H}, and 195Pt) spectroscopies, powder X-ray diffraction, and TGA/DTA. In solution, 9 and 19 exist in more than one form as identified by multinuclear NMR, and this behavior is ascribed to the restricted (N2)C-N(H)Ar single-bond rotation of the TAG ligand. The photophysical properties of 9 and 11 are reported.

Influence of the Steric/Electronic Properties of N-Aryl Substituents in Cycloplatinated Guanidinate(1-) Complexes on the Formation of Discrete Pt → Ag Complexes and One-Dimensional Coordination Polymer.

Several platinum(II) complexes with ligands containing azo groups have been prepared and structurally characterised, and their photoswitching between trans and cis azo group isomers has been studied The azo groups in the cationic complexes [PtMe(bipy)(4-NC5H4-NN-4-C6H4X)][PF6], X = H, OH or NMe2, and in the dicationic complex [Pt(bipy)(4-H2NC6H4-NN-C6H5)2][OTf]2 undergo trans to cis photoswitching on irradiation at 365 nm The complex [PtMe(bipy)(4-NC5H4-NN-4-C6H4NMe)2][PF6] also exhibits a reversible halochromic effect on protonation to give the dicationic complex [PtMe(bipy)(4-NC5H4-NHN-4-C6H4NMe2]2+ The nature of the frontier orbitals in the platinum(II) complexes depends on the charge on the complex and on the degree of metal–ligand π-bonding

Photoswitchable and pH responsive organoplatinum(II) complexes with azopyridine ligands

The reactions between Pt(2,2′-bpy)(O2CCF3)2 and Ag(O2CCF3) have been found to consistently produce heterobimetallic complexes where the [Pt(2,2′-bpy)]2+ unit acts as a terminator for various [Ag(O2...

Pt(2,2'-bpy)(O2CCF3)2 as a terminator for [Ag(O2CCF3)]n aggregates : Syntheses and structures of heterobimetallic PtIIAgI complexes

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Pt(2,2'-bpy)(O2CCF3)2 as a terminator for [Ag(O2CCF3)]n aggregates : Syntheses and structures of heterobimetallic PtIIAgI complexes

The anionic coordination polymer {K2[PtII2AgI8(2,2′-bipyridine)2(O2CCF3)14]}n