Spin crossover of ferric complexes with catecholate derivatives. Single-crystal X-ray structure, magnetic and Mössbauer investigations.

Complexes of general formula [(TPA)Fe(R-Cat)]X.nS were synthesised with different catecholate derivatives and anions (TPA = tris(2-pyridylmethyl)amine, R-Cat2- = 4,5-(NO2)2-Cat2- denoted DNC(2-); 3,4,5,6-Cl4-Cat2- denoted TCC2-; 3-OMe-Cat(2-); 4-Me-Cat(2-) and X = BPh4-; NO3-; PF6-; ClO4-; S = solvent molecule). Their magnetic behaviours in the solid state show a general feature along the series, viz., the occurrence of a thermally-induced spin crossover process. The transition curves are continuous with transition temperatures ranging from ca. 84 to 257 K. The crystal structures of [(TPA)Fe(DNC)]X (X = PF6-; BPh4-) and [(TPA)Fe(TCC)]X.nS (X = PF6-; NO3- and n= 1, S = H2O; ClO4- and n= 1, S = H2O; BPh4- and n= 1, S = C3H6O) were solved at 100 (or 123 K) and 293 K. For those two systems, the characteristics of the [FeN(4)O(2)] coordination core and those of the dioxolene ligands appear to be consistent with a prevailing Fe(III)-catecholate formulation. This feature is in contrast with the large quantum mixing between Fe(III)-catecholate and Fe(II)-semiquinonate forms recently observed with the more electron donating simple catecholate dianion. The thermal spin crossover process is accompanied by significant changes of the molecular structures as shown by the average variation of the metal-ligand bond distances which can be extrapolated for a complete spin conversion from ca. 0.123 to 0.156 A. The different space groups were retained in the low- and high-temperature phases.

Synthesis, structure, and magnetic properties of [MnIII(salpn)NCS]n, a helical polymer, and the dimer [MnIII(salpn)NCS]2. Weak ferromagnetism in [MnIII(salpn)NCS]n related to the strong magnetic anisotropy in Jahn-Teller MnIII (salpnH2 = N,N'-bis(salicylidene)-1,3-diaminopropane).

Dimeric [Mn(salpn)NCS](2)(1) and polymeric [Mn(salpn)NCS](n)(2) are formed by the reaction of Mn(CH(3)CO(2))(2).4H(2)O, the schiff base, and thiocyanate. The formation of the two polymorphic forms is solvent and temperature dependent. 1: orthorhombic, space group Pbca, with a = 12.573(2) A, b = 13.970(7) A, c = 18.891(9) A, and Z = 8. 2: orthorhombic, space group Pna2(1), with a = 12.5277(14) A, b = 11.576(2) A, c = 11.513(2) A, and Z = 4. The dimers in 1 are held together by weak noncovalent S...pi (phenyl) interactions leading to a chain along the a-axis. Each monomeric unit of the polymer in 2 is related to its adjacent ones by a 2-fold screw axis leading to a helix along the c-axis. The exchange coupling is nondetectable in the dimer. The magnetic susceptibility of the helical chain fits a classical chain law with J = -3.2 cm(-1) and shows a weak ferromagnetic ordering below 7 K due to spin canting effects.

A Two-Step Spin Crossover in

Measurement of magnetic susceptibility with temperature of a powdered iron(III) catecholate complex clearly indicated a two-step spin-crossover process S=(1/2)<-->S=5/2. The picture shows the plot of chi(M)T against temperature.

Analysis of Exchange Interaction and Electron Delocalization as Intramolecular Determinants of Intermolecular Electron-Transfer Kinetics.

During the past decades, spectroscopic characterization of exchange interactions and electron delocalization has developed into a powerful tool for the recognition of metal clusters in metalloproteins. By contrast, the biological relevance of these interactions has received little attention thus far. This paper presents a theoretical study in which this problem is addressed. The rate constant for intermolecular electron-transfer reactions which are essential in many biological processes is investigated. An expression is derived for the dependence of the rate constant for self-exchange on the delocalization degree of the mixed-valence species. This result allows us to rationalize published kinetic data. In the simplest case of electron transfer from an exchange-coupled binuclear mixed-valence donor to a diamagnetic acceptor, the rate constant is evaluated, taking into account spin factors and exchange energies in the initial and final state. The theoretical analysis indicates that intramolecular spin-dependent electron delocalization (double exchange) and Heisenberg-Dirac-van Vleck (HDvV) exchange have an important impact on the rate constant for intermolecular electron transfer. This correlation reveals a novel relationship between magnetochemistry and electrochemistry. Contributions to the electron transfer from the ground and excited states of the exchange-coupled dimer have been evaluated. For clusters in which these states have different degrees of delocalization, the excited-state contributions to electron transfer may become dominant at potentials which are less reductive than the potential at which the rate constant for the transfer from the ground state is maximum. The rate constant shows a steep dependence on HDvV exchange, which suggests that an exchange-coupled cluster can act as a molecular switch for exchange-controlled electron gating. The relevance of this result is discussed in the context of substrate specificity of electron-transfer reactions in biology. Our theoretical analysis points toward a possible biological role of the spin-state variability in iron-sulfur clusters depending on cluster environment.