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• 603-35-0 triphenylphosphine 

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High intensity trip-multiplet transitions, a reality! Synthesis, properties, and crystal structure of l-bis(triphenylphosphine)iminium trans-dibromophthalocyaninato(2-)molybdate(III)

Oxophthalocyaninato(2-)molybdenum(IV), activated by bromine oxidation prior to use, reacts with fused triphenylphosphine in the presence of bis(triphenylphosphine)iminium bromide to yield linear-bis(triphenylphosphine)iminium trans-dibromophthalocyaninato(2-)molybdate(III), l(PNP)trans[Mo(Br)2pc2-] It crystallizes triclinic with crystal data: a = 10.506(1) A, b = 12.436(2) A, c = 12.918(2) A, α = 76.186(1)°, β = 67.890(1)°, γ = 68.689(1)°; space group P1 (No. 2); Z = 1. MoIII is in a pseudo-octahedral coordination geometry with the bromo ligands in trans-arrangement. The Mo-Np and Mo-Br distance is 2.043(10) and 2.588(1) A, respectively. The PNP cation adopts a linear conformation. In the IR spectrum vas(Mo-Br) is observed at 218cm-1 and vas(P-N) of the linear (P-N-P) core at 1406 cm-1. Cyclic and differential-pulse voltammetry show two quasi-reversible cathodic processes at -1.15 and -0.53 V vs. Ag/AgCl. The first is assigned to a phthalocyaninate directed reduction (pc2-/pc3-), while the latter arises from a Mo directed reduction (MoIII/MoII). Spectral monitoring confirms the reversible MoIII/MoII reduction. Two quasi-reversible anodic processes at 0.60 and 1.27 V are assigned to the successive Mo directed oxidation with redox couples MoIII/MoIV and MoIV/MoV For the first time, three very intense spin-allowed trip-quartet transitions are observed in the electronic absorption spectra at 7140 (TQ1), 16890 (TQ2) and 18700 cm-1 (TQ3) together with a sing-quartet transition at 15850 cm-1 and characteristic Q region with maximum at 28500 cm-1 and N region at 37400 cm-1. All electronic excitations are of comparable intensity. A prominent low temperature emission at 6690 cm-1 is assigned to a spin-forbidden trip-sextet.