Ribbon-like coordination polymers composed of Ce(III) ions and TCNQX(2)(TCNQ=tetracyanoquinodimethane; X=Cl, Br), but not TCNQ radicals, show unexpected magnetic ordering (see picture; Ce green). This behavior reveals remarkable subtlety for magnetic properties of lanthanide-organic materials.

The use of a moderately hydrophobic ionic liquid, 1-butyl-2,3-dimethylimidazolium tetrafluoroborate ([BdMIM][BF(4)]), as a cosolvent with water, has been investigated in the synthesis of metal phosphonates. This hydro-ionothermal synthesis has been carried out through a systematic combinatorial investigation of several divalent metal chlorides and two related ligands, iminobis(methylphosphonic acid) and N-methyliminiobis(methylphosphonic acid). These reactions resulted in five new divalent metal phosphonates. We present here the synthetic techniques utilized as well as the X-ray structures and characteristic properties of each of these compounds. Co(HO(3)PCH(2)NH(2)CH(2)PO(3)H)(2),(1), consists of sheets that are hydrogen bonded together by pairs of P-OH groups. Co(H(2)O)(2)(HO(3)PCH(2)NH(2)CH(2)PO(3)H)(2),(2), consists of chains that are connected through an extensive network of hydrogen bonds. Co(HO(3)PCH(2)NH(CH(3))CH(2)PO(3)H)(2),(3), is made up of sheets that are hydrogen bonded together by pairing P-OH interactions. Zn(3)(O(3)PCH(2)NH(2)CH(2)PO(3))(2),(4), is isostructural to a previously reported cobalt compound which is a non-porous 3-dimensional network. CuClPO(3)CH(2)NH(2)CH(3),(5), formed as a result of an in situ N-C bond cleavage. Ladders built of Cu-O-P-O 8-membered rings are crosslinked by bridging chloride atoms to form sheets. 1, 3, 4 and 5 have been synthesized using the hydrophobic ionic liquid 1-butyl-2,3-dimethylimidazolium tetrafluoroborate ([BdMIM][BF(4)]) with water as a cosolvent, while 2 has been synthesized from identical conditions in the absence of the [BdMIM][BF(4)]. We also report the microwave assisted hydro-ionothermal synthesis of the known polymorph of 2, Co(H(2)O)(2)(HO(3)PCH(2)NH(2)CH(2)PO(3)H)(2),(6), synthesized in two hours providing high quality crystals in good yield. The compounds have been characterized by thermogravimetric analysis and IR spectroscopy, and their magnetic properties have been investigated.

The crystal structures of the self-assembled metallapentacycles [{Fe(5)(bptz)(5)(CH(3)CN)(10)} ⊂ 2SbF(6)][SbF(6)](8)(1) and [{Fe(5)(bmtz)(5)(CH(3)CN)(10)} ⊂ SbF(6)][SbF(6)](9)(2) with the π-acidic ligands bptz (3,6-bis(2-pyridyl)-1,2,4,5-tetrazine) and bmtz (3,6-bis(2-pyrimidyl)-1,2,4,5-tetrazine), respectively, revealed cationic pentagons templated by [SbF(6)](-) ions. The short anion-π contacts established between the anions and the tetrazine rings play an important role in the stability of the pentagons.

We previously showed that [Rh(2)(O(2)CCH(3))(2)(CH(3)CN)(6)](2+) binds to dsDNA only upon irradiation with visible light and that photolysis results in a 34-fold enhancement of its cytotoxicity toward Hs-27 human skin fibroblasts, making it potentially useful for photodynamic therapy (PDT). With the goal of gaining further insight on the photoinduced binding of DNA to the complex, we investigated by NMR spectroscopy the mechanism by which 2,2'-bipyridine (bpy), a model for biologically relevant bidentate nitrogen donor ligands, binds to [Rh(2)(O(2)CCH(3))(2)(CH(3)CN)(6)](2+) upon irradiation in D(2)O. The photochemical results are compared to the reactivity in the dark in D(2)O and CD(3)CN. The photolysis of [Rh(2)(O(2)CCH(3))(2)(CH(3)CN)(6)](2+) with equimolar bpy solutions in D(2)O with visible light affords [Rh(2)(O(2)CCH(3))(2)(eq/eq-bpy)(CH(3)CN)(2)(D(2)O(ax))(2)](2+)(eq/eq) with the reaction reaching completion in ~8 h. Only vestiges of eq/eq are observed at the same time in the dark, however, and the reaction is ~20 times slower. Conversely, the dark reaction of [Rh(2)(O(2)CCH(3))(2)(CH(3)CN)(6)](2+) with an equimolar amount of bpy in CD(3)CN affords [Rh(2)(O(2)CCH(3))(2)(η(1)-bpy(ax))(CH(3)CN)(5)](2+)(η(1)-bpy(ax)), which remains present even after 5 days of reaction. The photolysis results in D(2)O are consistent with the exchange of one equiv CH(3)CNeq for solvent, and the resulting species quickly reacting with bpy to generate eq/eq; the initial eq ligand dissociation is assisted by absorption of a photon, thus greatly enhancing the reaction rate. The photolytic reaction of [Rh(2)(O(2)CCH(3))(2)(CH(3)CN)(6)](2+):bpy in a 1:2 ratio in D(2)O affords the eq/eq and (eq/eq)(2) adducts. The observed differences in the reactivity in D(2)O vs CD(3)CN are explained by the relative ease of substitution of eq D(2)O vs CD(3)CN by the incoming bpy molecule. These results clearly highlight the importance of dissociation of an eq CH(3)CN molecule from the dirhodium core to attain high reactivity and underscore the importance of light for the reactivity of these compounds, which is essential for PDT agents.

The hydrothermal chemistry of a variety of M(ii)SO(4) salts with the tetrazole (Ht) ligands 5,5'-(1,4-phenylene)bis(1H-tetrazole)(H(2)bdt), 5',5''-(1,1'-biphenyl)4,4'-diylbis(1H-tetrazole)(H(2)dbdt) and 5,5',5''-(1,3,5-phenylene)tris(1H-tetrazole)(H(3)btt) was investigated. In the case of Co(ii), three phases were isolated, two of which incorporated sulfate:[Co(5)F(2)(dbdt)(4)(H(2)O)(6)]·2H(2)O (1·2H(2)O),[Co(4)(OH)(2)(SO(4))(bdt)(2)(H(2)O)(4)](2) and [Co(3)(OH)(SO(4))(btt)(H(2)O)(4)]·3H(2)O (3·3H(2)O). The structures are three-dimensional and consist of cluster-based secondary building units: the pentanuclear {Co(5)F(2)(tetrazolate)(8)(H(2)O)(6)}, the tetranuclear {Co(4)(OH)(2)(SO(4))(2)(tetrazolate)(6)}(4-), and the trinuclear {Co(3)(μ(3)-OH)(SO(4))(2)(tetrazolate)(3)}(2-) for 1, 2, and 3, respectively. The Ni(ii) analogue [Ni(2)(H(0.67)bdt)(3)]·10.5H(2)O (4·10.5H(2)O) is isomorphous with a fourth cobalt phase, the previously reported [Co(2)(H(0.67)bat)(3)]·20H(2)O and exhibits a {M(tetrazolate)(3/2)}(∞) chain as the fundamental building block. The dense three-dimensional structure of [Zn(bdt)](5) consists of {ZnN(4)}tetrahedra linked through bdt ligands bonding through N1,N3 donors at either tetrazolate terminus. In contrast to the hydrothermal synthesis of 1-5, the Cd(ii) material (Me(2)NH(2))(3)[Cd(12)Cl(3)(btt)(8)(DMF)(12)]·xDMF·yMeOH (DMF = dimethylformamide; x = ca. 12, y = ca. 5) was prepared in DMF/methanol. The structure is constructed from the linking of {Cd(4)Cl(tetrazolate)(8)(DMF)(4)}(1-) secondary building units to produce an open-framework material exhibiting 66.5% void volume. The magnetic properties of the Co(ii) series are reflective of the structural building units.

The cation cis-[Ru(bpy)(2)(5CNU)(2)](2+)(bpy = 2,2'-bipyridine; 5CNU = 5-cyanouracil) was synthesized and investigated for use as a potential light-activated dual-action therapeutic agent. The complex undergoes efficient photoinduced 5CNU ligand exchange for solvent water molecules, thus simultaneously releasing biologically active 5CNU and generating [Ru(bpy)(2)(H(2)O)(2)](2+). The latter binds covalently to ds-DNA, such that photolysis results in the generation of 3 equiv of potential therapeutic agents from a single molecule.

In this critical review we review the problem of exchange interactions in polynuclear metal complexes involving orbitally degenerate metal ions. The key feature of these systems is that, in general, they carry an unquenched orbital angular momentum that manifests itself in all their magnetic properties. Thus, interest in degenerate systems involves fundamental problems related to basic models in magnetism. In particular, the conventional Heisenberg-Dirac-Van Vleck model becomes inapplicable even as an approximation. In the first part we attempt to answer two key questions, namely which theoretical tools are to be used in the case of degeneracy, and how these tools can be employed. We demonstrate that the exchange interaction between orbitally degenerate metal ions can be described by the so-called orbitally-dependent exchange Hamiltonian. This approach has shown to reveal an anomalously strong magnetic anisotropy that can be considered as the main physical manifestation of the unquenched orbital angular momentum in magnetic systems. Along with the exchange coupling, a set of other interactions (such as crystal field effects, spin-orbit and Zeeman coupling), which are specific for the degenerate systems, need to be considered. All these features will be discussed in detail using a pseudo-spin-1/2 Hamiltonian approach. In the second part, the described theoretical background will be used to account for the magnetic properties of several magnetic metal clusters and low-dimensional systems:(i) the dinuclear face-sharing unit [Ti(2)Cl(9)](3-), which exhibits a large magnetic anisotropy;(ii) the rare-earth compounds Cs(3)Yb(2)Cl(9) and Cs(3)Yb(2)Br(9), which, surprisingly, exhibit a full magnetic isotropy;(iii) a zig-zag Co(II) chain exhibiting unusual combination of single-chain magnet behavior and antiferromagnetic exchange coupling;(iv) a trigonal bipyramidal Ni(3)Os(2) complex;(v) various Co(II) clusters encapsulated by polyoxometalate ligands. In the two last examples a pseudospin-1/2 Hamiltonian approach is applied to account for the presence of exchange anisotropy (150 references).

The study of paramagnetic compounds based on 4d and 5d transition metals is an emerging research topic in the field of molecular magnetism. An essential driving force for the interest in this area is the fact that heavier metal ions introduce important attributes to the physical properties of paramagnetic compounds. Among the attractive characteristics of heavier elements vis-à-vis magnetism are the diffuse nature of their d orbitals, their strong magnetic anisotropy owing to enhanced spin-orbit coupling, and their diverse structural and redox properties. This critical review is intended to introduce readers to the topic and to report recent progress in this area. It is not fully comprehensive in scope although we strived to include all relevant topics and a large subset of references in the area. Herein we provide a survey of the history and current status of research that has been conducted on the topic of second and third row transition metal molecular magnetism. The article is organized according to the nature of the precursor building blocks with special topics being highlighted as illustrations of the special role of heavier transition metal ions in the field. This paper is addressed to readers who are interested in molecular magnetism and the application of coordination chemistry principles to materials synthesis (231 references).