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Ion pair charge-transfer complexes between anionic and cationic metal-dithiolenes [M(II) = Pd,Pt
Authors:Bigoli Francesco  Deplano Paola  Mercuri Maria Laura  Pellinghelli Maria Angela  Pilia Luca  Pintus Gloria  Serpe Angela  Trogu Emanuele F
Institution:Dipartimento di Chimica Generale ed Inorganica, Chimica Analitica, Chimica Fisica, Università di Parma, Parco Area delle Scienze 17A, I-43100 Parma, Italy.
Abstract:New M(R(2)pipdt)(2)](BF(4))(2) salts R(2)pipdt = N,N'-dialkyl-piperazine-2,3-dithione; M = Pd(II), R = Me and M = Pt(II), R = Me, Et, Pr(i)] bearing redox-active cationic dithiolene complexes have been prepared and characterized. These cations react with the redox-active M(mnt)(2)](2-) M = Pd(II), Pt(II); mnt = maleonitrile-2,3-dithiolate] anionic dithiolenes to form salts describable as ion pair charge-transfer complexes. X-ray crystallographic studies have shown that M(Me(2)pipdt)(2)]M(mnt)(2)] complexes, with M = Pd(II) and Pt(II), are isomorphous. Crystal data of the Pt salt (3a): triclinic, Ponemacr; (No. 2); Z = 1; T = 293(2) K; a = 6.784(7) A, b = 8.460(6) A, c = 13.510(5) A, alpha = 100.63(2) degrees, beta = 104.04(2) degrees, gamma = 96.90(2) degrees; R1 = 0.0691 wR2 = 0.2187 (all data)]. Structural data show that approximately square-planar Pt(Me(2)pipdt)(2)] dications and regular square-planar Pt(mnt)(2)] dianions form an infinite anion-cation one-dimensional stack along axis a with a Pt...Pt a/2 distance of 3.392 A and a Pt...Pt...Pt angle of 180 degrees. Anions and cations arrange themselves face-to-face so as to take on a staggered arrangement. These salts exhibit strong absorptions in the visible-near-infrared region assigned to ion pair charge-transfer transitions. A relation between the optical and thermal electron transfer in the solid state is obtained using a "Marcus-Hush model", and a solid-state electrical conductivity in agreement with expectations is observed. Vibrational spectroscopy is in agreement with the existence of charge-transfer interactions between the cationic and anionic components of the salts.
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