Photoinduced HS state in the first spin-crossover chain containing a cyanocarbanion as bridging ligand.

A new polymeric approach, based on cyanocarbanion ligands, for the design of spin crossover (SCO) compounds led us to the compound [Fe(abpt)(2)(tcpd)] () (tcpd(2-) = (C[C(CN)(2)](3))(2-), abpt = 4-amino-3,5-bis(pyridin-2-yl)-1,2,4-triazole) which has been characterised as the first SCO molecular chain involving a cyanocarbanion as bridging ligand.

Magnetic bistability and thermochromism in a molecular Cu(II) chain.

An original magnetic bistability and a thermochromic transition are observed in a new Cu(II) molecular chain. Thermal structural studies reveal changes in the Cu(II) coordination sphere, driven by a more pronounced Jahn-Teller effect at low temperature. These distortions provoke a gradual color change. The structural study at 10 K shows a dimerization of the molecular chain, in agreement with the abrupt magnetic transition observed at 30 K.

The key role of the intermolecular pi-pi interactions in the presence of spin crossover in neutral [Fe(abpt)2A2] complexes (A = terminal monoanion N ligand).

New iron(II) complexes of formulas [Fe(abpt) 2(tcm) 2] ( 1), [Fe(abpt) 2(tcnome) 2] ( 2), and [Fe(abpt) 2(tcnoet) 2] ( 3) (abpt = 4-amino-3,5-bis(pyridin-2-yl)-1,2,4-triazole, tcm (-) = [C(CN) 3] (-) = tricyanomethanide anion; tcnome (-) = [(NC) 2CC(OCH 3)C(CN) 2] (-) = 1,1,3,3-tetracyano-2-methoxypropenide anion; tcnoet (-) = [(NC) 2CC(OC 2H 5)C(CN) 2] (-) = 1,1,3,3-tetracyano-2-ethoxypropenide anion) have been synthesized and characterized by infrared spectroscopy, magnetic properties and by variable-temperature single-crystal X-ray diffraction. The crystal structure determinations of 1 and 2 reveal in both cases centrosymmetric discrete iron(II) monomeric structures in which two abpt chelating ligands stand in the equatorial plane and two terminal polynitrile ligands complete the distorted octahedral environment in trans positions. For 3, the crystallographic studies revealed two polymorphs, 3- A and 3- B, exhibiting similar discrete molecular structures to those found for 1 and 2 but with different molecular arrangements. In agreement with the variable-temperature single-crystal X-ray diffraction, the magnetic susceptibility measurements, performed in the temperature range 2-400 K, showed a spin-crossover phenomenon above room temperature for complexes 1, 3- A, and 3- B with a T 1/2 of 336, 377, and 383 K, respectively, while complex 2 remains in the high-spin ground state ( S = 2) in the whole temperature range. To understand further the magnetic behaviors of 1, 3-A, and 3-B, single-crystal X-ray diffraction measurements were performed at high temperatures. The crystal structures of both polymorphs could not be obtained above 400 K because the crystals decomposed. However, single-crystal X-ray data have been collected for compound 1, which reaches the full high-spin state at lower temperatures. Its crystal structure, solved at 400 K, showed a strong modification of the iron coordination sphere (average Fe-N = 2.157(3) A vs 1.986(3) A at 293 K). In agreement with the magnetic properties. Such structural behavior is a signature of the spin-state transition from low-spin (LS) to high-spin (HS). On the basis of the intermolecular pi stacking observed for the series described in this paper and for related complexes involving similar discrete structures, we have shown that complexes displaying frontal pi stacking present spin transition such as 1, 3-A, and 3-B and those involving sideways pi stacking such as complex 2 remain in the HS state.

New magnetic copper(II) coordination polymers with the polynitrile ligand (C[C(CN)2]3)2- and N-donor co-ligands.

Reactions between CuCl2 and K2tcpd (tcpd2- = [C10N6]2- = (C[C(CN)2]3)2-) in the presence of neutral co-ligands (bpym = 2,2'-bipyrimidine, and tn = 1,3-diaminopropane) in aqueous solution yield the new compounds [Cu2(bpym)(tcpd)2(H2O)4] x 2H2O (1), [Cu(tn)(tcpd)] (2), and [Cu(tn)2(tcpd)] x H2O (3), which are characterized by X-ray crystallography and magnetic measurements. Compound 1 displays a one-dimensional structure in which the bpym ligand, acting with a bis-chelating coordination mode, leads to [Cu2(bpym)]4+ dinuclear units which are connected by two mu2-tcpd2- bridging ligands. Compound 2 consists of a three-dimensional structure generated by [Cu(tn)]2+ units connected by a mu4-tcpd2- ligand. The structure of 3 is made up of centrosymmetric planar [Cu(tn)]2+ units connected by a mu2-tcpd2- ligand leading to infinite zigzag chains. In compounds 1 and 3, the bridging coordination mode of the tcpd2- unit involves only two nitrogen atoms of one C(CN)2 wing, while in 2, this ligand acts via four nitrogen atoms of two C(CN)2 wings. Despite this difference, the structural features of the tcpd2- units in 1-3 are essentially similar. Magnetic measurements for compound 1 exhibit a maximum in the chi(m) vs T plot (at approximately 150 K) which is characteristic of strong antiferromagnetic exchange interactions between the Cu(II) metal ions dominated by the magnetic exchange through the bis-chelating bpym. The fit of the magnetic data to a dimer model gives J and g values of -90.0 cm(-1) and 2.12, respectively. For compounds 2 and 3 the thermal variations of the magnetic susceptibility show weak antiferromagnetic interactions between the Cu(II) metal ions that can be well reproduced with an antiferromagnetic regular S = 1/2 chain model that gives J values of -0.07(2) and -0.18(1) cm(-1) with g values of 2.12(1) and 2.13(1) for compounds 2 and 3, respectively (the Hamiltonian is written in all the cases as H = -2JS(a)S(b)).

Asymmetric azido-copper(II) bridges: ferro- or antiferromagnetic? experimental and theoretical magneto-structural studies.

Reaction of NaN(3) with the [Cu(II)(tn)](2+) ion (tn = 1,3-diaminopropane) in basic aqueous solution yields the azido-bridged complex of formula [Cu(2)(tn)(2)(N(3))(4)] (1), which is characterized by X-ray crystallography. The structure of 1 is made up of dinuclear neutral complexes, of formula [Cu(2)(tn)(2)(N(3))(4)], resulting from the assembling of two mononuclear units through two equivalent end-on azide bridges connecting asymmetrically two Cu(tn)(N(3))(2) entities. These dinuclear units are connected through two asymmetric end-to-end N(3) bridges to form a chain of dimers. Magnetic measurements for compound 1 show weak antiferromagnetic exchange interactions between the Cu(II) ions. The magnetic data were modeled using the susceptibility expression derived for an alternating AF S = 1/2 chain. A very satisfactory fit over the whole temperature range was obtained with g = 2.1438(4), J(1) = -3.71(2) cm(-1), and J(2) = -3.10(2) cm(-1) (J(1) and J(2) are the singlet-triplet separations). This magnetic behavior differs from those observed for similar examples which were reported as having alternating ferro- and antiferromagnetic exchange interactions; thus, DFT calculations were done to understand the nature of the magnetic coupling in such asymmetric end-on and end-to-end N(3) bridges. Theoretical results show that the double asymmetric end-on bridges produce antiferromagnetic coupling while the end-to-end ones can present ferro- or antiferromagnetic coupling depending on the copper coordination sphere.

Electrochemical, spectroscopic, and structural evidence for the mild hydrolysis of tetracyanoethylene, TCNE, to form the 2,3,3-tricyanoacrylamidate ligand: isolation of an unexpected quadruply-bonded polymeric material [Mo2(O2CCMe3)3((NC)2CC(CN)CONH)]infinity.

Under strictly anhydrous conditions, no reaction occurs between Mo(2)(O(2)CCMe(3))(4) and tetracyanoethylene, TCNE, at room temperature, but after addition of 1 equiv of water, a reaction proceeds to form [Mo(2)(O(2)CCMe(3))(3)((NC)(2)CC(CN)CONH)], 1. The compound contains a quadruple-bonded Mo(2) unit and the 2,3,3-tricyanoacrylamidate anion as a ligand (TC3A), a very unusual hydrolyzed form of TCNE. Two different solid-state structures were obtained after crystallization of 1. Crystals obtained from CH(2)Cl(2) consist of a two-dimensional network, and crystals grown from a C(6)H(6) solution form a 1-D chain motif. In both cases, the TC3A ligand acts as a polydentate ligand involving a bidentate OCN bridging unit and two CN groups. The electrochemical and spectroscopic (IR, UV/vis/near-IR, NMR, EPR) properties of 1 support the formulation in solution as a discrete 1:1 complex of the TC3A donor ligand and a Mo(2) unit with no charge transfer. The coordinated TC3A ligand exhibits redox properties similar to those of free TCNE.