Crystal and molecular structures of dihalotetrakis(pyrophosphito)diplatinum(III) complexes. Integrative use of structural and vibrational data to assess intermetallic bonding and the trans influence of the platinum(III)-platinum(III) bond

Three‐Dimensionally Ordered CDW State in Quasi‐One‐Dimensional Iodo‐Bridged Dinuclear Platinum Mixed‐Valence Compounds, A4[Pt2I(pop)4]·nH2O (A = Aromatic Ammonium Cations)

“…[c] Ref. [9] In the case of 2 and 3, the bridging iodide ion was also not disordered and two types of Pt 2 (pop) 4 4 ] units are consistent with those of the precursors. Therefore, 2 and 3 are in a CDW state with three-dimensional ordering.…”

“…The two neighboring Pt 2 (pop) 4 units are bridged by an I ion, and the chain structure is constructed along a diagonal line of the unit cell. Two types of Pt 2 (pop) 4 [9] and suggest that compound 1 is in a CDW state, i.e. ···Pt 2+ -Pt 2+ ···I-Pt…”

Structures and electronic spectra of [Pt2(P2O5H2)4X2]4− (X=Cl, Br and I): A comparative study of ab initio and density functional theory

“…Upon excitation, the triplet excited state, [Pt 2 (P 2 O 5 H 2 ) 4 ] 4À * , forms vacant coordination sites at the metal atom, features an intense r(p) ! r * (d) transition and possesses long lifetime (9.5 ls) and high quantum yield (>0.5).By the oxidative reaction of [Pt 2 (P 2 O 5 H 2 ) 4 ] 4À with halogen, binuclear dihaloplatinum(III) complexes, [Pt 2 (P 2 O 5 -H 2 ) 4 X 2 ] 4À (X = Cl (1), Br (2) and I (3)), are prepared [6][7][8][9][10][11][12]. It is shown from X-ray crystal diffraction [6-9] that these complexes contain axial Pt-X bonds and a Pt-Pt single bond.…”

“…It is shown from X-ray crystal diffraction [6][7][8][9] Spectroscopic studies usually related the intense absorptions of 1-3 to the excitations to the r * (d) orbital. It is well-known that the time-dependent density functional theory (TD-DFT) has recently become a reliable method for prediction on excited-state energies [4,5,13].…”

“…Selected results from the geometry optimizations on 1-3 are listed in Table 1, compared with data from the X-ray crystallographic determination of K 4 [Pt 2 (P 2 O 5 H 2 ) 4 X 2 ] AE nH 2 O (X = Cl, Br and I) [6][7][8][9]. Their structures are presented in Fig.…”