Mass spectrometry-directed synthesis of early–late sulfide-bridged heterobimetallic complexes from the metalloligand [Pt₂(PPh₃)₄(μ-S)₂] and oxo compounds of vanadium(V), molybdenum(VI) and uranium(VI)

The metalloligand [Pt₂(PPh₃)₄(μ-S)₂] has been found to react with the transition metal oxo compounds, ammonium metavanadate, sodium molybdate, and the actinide complex uranyl nitrate to give sulfide-bridged heterobimetallic complexes [Pt₂(PPh₃)₄(μ₃-S)₂VO(OMe)₂]⁺, [Pt₂(PPh₃)₄(μ₃-S)₂MoO₂(OMe)]⁺, and [Pt₂(PPh₃)₄(μ₃-S)₂UO₂( ₂-NO₃)₂], respectively. Electrospray mass spectrometry (ESMS) was used to probe the reactivity of [Pt₂(PPh₃)₄(μ-S)₂] and thus identify likely targets for isolation and characterization. ESMS has also been used to investigate fragmentation pathways of the new species. No bimetallic species were detected with hydrated La(NO₃)₃or Th(NO₃)₄, or with the lanthanide shift reagent Eu(fod)₃ (fod = 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionate). X-Ray crystal structure determinations have been carried out on [Pt₂(PPh₃)₄(μ₃-S)₂VO(OMe)₂]⁺, 2, (as its hexafluorophosphate salt) and [Pt₂(PPh₃)₄(μ₃-S)₂UO₂( ₂-NO₃)₂], 4. The vanadium atom of 2 has a distorted square pyramidal geometry, while the uranium in 4 has the expected linear dioxo coordination geometry, with two bidentate nitrates and a bidentate {Pt₂S₂} moiety

A rapid screening, “combinatorial-type” survey of the metalloligand chemistry of Pt₂(PPh₃)₄(μ-S)₂ using electrospray mass spectrometry

Electrospray mass spectrometry is a rapid and powerful technique for a combinatorial-like survey of the chemistry of the metalloligand Pt₂(PPh₃)₄(μ-S)₂, leading to the successful isolation and crystallographic characterisation of the novel protonated species Pt₂(PPh₃)₄(μ-S)(μ-SH) together with a range of metallated derivatives

Catecholase-like activity in 2D MOFs: Oxidation of 3,5-DTBC by two Cu(II) 2D MOFs of reduced Schiff base ligands

10.1016/j.ica.2021.120502INORGANICA CHIMICA ACTA52

Regulating thermosalient behaviour in three polymorphs

10.1107/S2052252517005577IUCrJ4202-20

Dynamic effects in crystalline coordination polymers

10.1039/d1ce00441gCRYSTENGCOMM23345738-575

Mechanical Bending and Modulation of Photoactuation Properties in a One-Dimensional Pb(II) Coordination Polymer

With emergent research on stimuli responsive materials, dynamic crystals are at the forefront of investigation. However, research on the mechanical properties of coordination polymers (CPs) is still in its infancy. Elastic deformation induced by pressure and photoactuation are rare occurrences in CPs, let alone their combination in a single CP. Here, we report a one-dimensional (1D) CP comprising PbBr2 chains with 3-fluoro-4’-styrylpyridine arms showing excellent elasticity and photomechanical properties. A slender crystal can be bent to make a circle and write different shapes with restoration of original shape upon removal of the applied force. In addition, photomechanical properties triggered by [2+2] cycloaddition of the olefinic ligand can be modulated easily by variation of the crystal sizes. Crystals with bigger width show destructive photosalient effects while the smaller ones show plastic deformation like bending, twisting, curling etc. upon UV irradiation. This example provides avenue for designing CPs for multi-stimuli responsive actuating properties