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Herein, the first example of a homoleptic Ag III complex stabilized by a monodentate N-donor ligand is presented. Na 2 [S 2 O 8 ] oxidizes the linear Ag I complex, Na[Ag(succ) 2 ] (1 Na ), to form a square planar argentate(iii) ion, [Ag(succ) 4 ] - , which crystallizes with a polymeric chain-structure, M[Ag(succ) 4 ] (2 M ), when treated with alkali metal sulfate M 2 SO 4 (M = K, Rb, Cs). A mixed-valent Robin-Day class I system, [(H 2 O)Ag][Ag(succ) 4 ] (2 Ag ), forms in the absence of K + /Rb + /Cs + ion. Diamagnetic 2 Cs displays a succinimide C[double bond, length as m-dash]O stretching frequency at higher energy than does the isoelectronic Pd II complex, [(H 2 O)Na] 2 [Pd(succ) 4 ] (3 Na ). Moreover, 2 Cs displays UV-vis absorptions that are more intense and occur at lower energy than those in 3 Na . The electron-deficient nature of 2 Cs is further evident from its ability to oxidize water to O 2 . From 109 Ag magic-angle spinning NMR studies, a highly deshielded Ag III environment in 2 Cs (2080 ppm) relative to the Ag I starting material 1 Na (492 ppm) is observed., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Record-breaking magnetic exchange interactions have previously been reported for 3d-metal dimers of the form [M(Pt(SAc) 4 )(pyNO 2 )] 2 (M = Ni or Co) that are linked in the solid state via metallophilic Pt⋯Pt bridges. This contrasts the terminally capped monomers [M(Pt(SAc) 4 )(py) 2 ], for which neither metallophilic bridges nor magnetic exchange interactions are found. Computational modeling has shown that the magnetic exchange interaction is facilitated by the pseudo-closed shell d 8 ⋯d 8 metallophilic interaction between the filled Pt 2+ 5d z 2 orbitals. We present here inelastic neutron scattering experiments on these complexes, wherein the dimers present an oscillatory momentum-transfer-dependence of the magnetic transitions. This allows for the unequivocal experimental assignment of the distance between the coupled ions, which matches exactly the coupling pathway via the metallophilic bridges. Furthermore, we have synthesized and magnetically characterized the isostructural palladium-analogues. The magnetic coupling across the Pd⋯Pd bridge is found through SQUID-magnetometry and FD-FT THz-EPR spectroscopy to be much weaker than via the Pt⋯Pt bridge. The weaker coupling is traced to the larger radial extent of the 5d z 2 orbitals compared to that of the 4d z 2 orbitals. The existence of a palladium metallophilic interaction is evaluated computationally from potential surface cuts along the metal stretching direction. Similar behavior is found for the Pd⋯Pd and Pt⋯Pt-systems with clear minima along this coordinate and provide estimates for the force constant for this distortion. The estimated M⋯M stretching frequencies are found to match experimental observed, polarized bands in single-crystal Raman spectra close to 45 cm -1 . This substantiates the existence of energetically relevant Pd⋯Pd metallophilic interactions. The unique properties of both Pt 2+ and Pd 2+ constitutes an orthogonal reactivity, which can be utilized for steering both the direction and strength of magnetic interactions., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Accurate nuclear quadrupole moment values are essential as benchmarks for nuclear structure models and for the interpretation of experimentally determined nuclear quadrupole interactions in terms of electronic and molecular structure. Here, we present a novel route to such data by combining perturbed γ-γ angular correlation measurements on free small linear molecules, realized for the first time within this work, with state-of-the-art ab initio electronic structure calculations of the electric field gradient at the probe site. This approach, also feasible for a series of other cases, is applied to Hg and Cd halides, resulting in Q(^{199}Hg,5/2^{-})=+0.674(17)  b and Q(^{111}Cd,5/2^{+})=+0.664(7)  b.