Lykourgos Iordanidis

Host–Guest Interaction of 12‐MC‐4, 15‐MC‐5, and Fused 12‐MC‐4 Metallacrowns with Mononuclear and Binuclear Carboxylato Complexes: Structure and Magnetic Behavior

Interaction of manganese with salicylhydroxamic ligands leads to the formation of the 12-membered metallacrown [Mn(II)(2(2,4-DP)2(HCOO)2]-[12-MC(Mn(III)N(shi)-4](py)6 (2) (H-2,4-DP =2-(2,4-dichlorophenoxy)propionic acid) and the 15-membered metallacrown [Mn(II)(2,4-D)2][15-MC(Mn(III)N(shi)-5](py)6 (1) (H-2,4-D = 2,4-dichlorophenoxyacetic acid). The crystal structure analysis shows that mononuclear and dinuclear alkanoato complexes are accommodated in the cavity of the metallacrown ring. The magnetic behaviour of 1 and 2 and the magnetic behaviour of the fused 12-membered metallacrown [Ni(II)(mcpa)]2-[12-MC(Ni(II)N(shi)2(pko)2-4][12-MC(Ni(II)N(shi)3(pko)-4]-(CH3OH)3(H2O) (3) (Hmcpa = 2-methyl-4-chlorophenoxyacetic acid) have shown that the zero field and/or the population of many energy levels at low temperatures is the reason for the divergence of the susceptibility data at high fields. For compound 3, the ground state is S = 0, with S = 1 and S = 2 low-lying excited states. This leads to a non-Brillouin behaviour of the magnetisation, since the ground state is very close to the excited states.

15-MC-5 manganese metallacrowns hosting herbicide complexes. Structure and bioactivity.

Interaction of manganese with salicylhydroxamic ligands leads to the formation of a series of 15-membered metallacrown Mn(II)(L)(2)[15-MC(Mn(III)N(shi))-5](py)(6) (L=alkanoato ligand). The crystal structure contains a neutral 15-membered metallacrown ring of the type [15-MC(Mn(III)N(shi))-5]. The metallacrown core consists of five Mn(III) and five shi(-3) ligands. The 15-membered metallacrown ring is formed by the succession of five structural moieties of the type [Mn(III)-N-O]. The diversity in the configuration (planar or propeller) for the ring Mn(III) ions gives to the metallacrown core flexibility and simultaneously allows the encapsulation of the sixth Mn(II). The encapsulated Mn(II) is seven-coordinate and is bound to the five hydroximate oxygen donors provided by the metallacrown core, and two oxygen atoms from the carboxylate herbicide ligands. Antibacterial screening data showed that among all the compounds tested, manganese metallacrowns are more active than the simple manganese herbicide or carboxylate complexes while an increase in the efficiency of [15-MC(Mn(III)N(shi))-5] towards the analogous [12-MC(Mn(III)N(shi))-4] can be observed.

Herbicides interacting with lanthanide(III) and calcium(II) ions: structural and biological similarities of Gd and Ca polymers

In this paper we report the synthesis and characterization of Ca(II), Gd(III) and Ce(III) complexes with chlorophenoxyalkanoic acids, which are commonly used as herbicides. The Gd(III) and Ca(II) complexes were characterized by the typical formulas [Gd(III)(L)(3)(H(2)O)(2).2dmf](n) and [Ca(L)(2)(MeOH)(2)](n) [L=[2,4-D=2,4-dichlorophenoxyacetic acid, 2,4,5-T=2,4,5-trichlorophenoxyacetic acid, MCPA=2-methyl-4-chlorophenoxy acetic acid and 2,4-DP=2-(2,4-dichlorophenoxy)propanoic acid]]. The crystal structure of the Gd(III) complex with 2,4-D shows that the compound is a one-dimensional polymer with a [Gd(III)(2)(2,4-D)(6)(H(2)O)(4)] dimeric repeat unit and the gadolinium atoms are in a nine-coordination environment, while the crystal structure of the Ca analog shows that it also has a polymeric structure with a [Ca(2)(2,4-D)(4)(CH(3)OH)(4)] dimeric repeat unit and the calcium atoms are in an eight-coordination environment. The gadolinium compound displays three different coordination modes for the carboxylato moiety, bidentate chelate, bidentate double bound and bidentate triple bound, while the calcium compound displays only one, bidentate triple bound. Coordination spheres are completed with oxygens of H(2)O or MeOH molecules, respectively. The complexes were tested against a few common bacteria by minimum inhibitory concentration (MIC) experiments and did not exhibit any antimicrobial action at concentrations up to 1600 microg/ml.

Synthetic, structural and solution speciation studies on binary Al(III)-(carboxy)phosphonate systems. Relevance to the neurotoxic potential of Al(III)

Efforts to delineate the interactions of neurotoxic Al(III) with low molecular mass substrates relevant to neurodegenerative processes, led to the investigation of the pH-specific synthetic chemistry of the binary Al(III)-[N-(phosphonomethyl) iminodiacetic acid] (Al-NTAP), Al(III)-[nitrilo-tris(methylene-phosphonic acid)] (Al-NTA3P), and Al(III)-[1-hydroxy ethylidene-1,1-diphosphonic acid] (Al-HEDP) systems, in correlation with solution speciation studies. Reaction of Al(NO(3))(3).9H(2)O with NTAP at pH 7.0 and 4.0 afforded the new species (CH(6)N(3))(4)[Al(2)(C(5)H(6)NPO(7))(2)(OH)(2)].8H(2)O (1) and (NH(4))(2)[Al(2)(C(5)H(6)NPO(7))(2)(H(2)O)(2)].4H(2)O (2), while reaction of Al(NO(3))(3).9H(2)O with NTA3P led to K(8)[Al(2)(C(3)H(6)NP(3)O(9))(2)(OH)(2)].20H(2)O (3). Complexes 1-3 were characterized by elemental analysis, FT-IR, (13)C, (31)P, (1)H NMR (for 1-2 solid state and solution NMR where feasible), and X-ray crystallography. The structures of 1-3 reveal the presence of uniquely defined dinuclear complexes of octahedral Al(III) bound to fully deprotonated phosphonate ligands, water and hydroxo moieties. The aqueous solution speciation studies on the aforementioned binary systems project a clear picture of the binary Al(III)-(carboxy)phosphonate interactions and species under variable pH-conditions and specific Al(III):ligand stoichiometry. The concurrent solid state and solution work (a) exemplifies essential structural and chemical attributes of soluble aqueous species, reflecting well-defined interactions of Al(III) with phosphosubstrates and (b) strengthens the potential linkage of neurotoxic Al(III) chemical reactivity toward O,N-containing (carboxy)phosphate-rich cellular targets.

Solid State Chemistry Approach to Advanced Thermoelectrics. Ternary and Quaternary Alkali Metal Bismuth Chalcogenides as Thermoelectric Materials

Our exploratory research to identify new promising candidates for next generation thermoelectric applications has produced several interesting new materials which are briefly described here. We present their compositions, solid state structures, properties and charge transport behavior. The compounds CsBi 4 Te 6 , β-K 2 Bi 8 Se 13 , Ba 4 Bi 6 Se 13 , Eu 2 Pb 2 Bi 6 Se 13 , KBi 6.33 S 10 , Eu 2 Pb 2 Bi 4 Se 10 , Ba 2 Pb 2 Bi 6 S 13 and K 1.25 Pb 3.5 Bi 7.25 Se 15 are particularly noteworthy.

Ternary bismuth chalcogenides for thermoelectric applications. Synthesis and charge transport properties of new compounds in the K-Bi-S system

Group 15 chalcogenide compounds have received considerable attention, due to their potential application as thermoelectric cooling materials. KBi{sub 6.33}S{sub 10} and K{sub 2}Bi{sub 8}S{sub 13} were synthesized by the direct combination of K{sub 2}S/Bi{sub 2}S{sub 3} at high temperature (> 700 C). The reaction of K{sub 2}S/3.3Bi{sub 2}S{sub 3} at 800 C revealed the presence of a new ternary sulfide KBi{sub 6.33}S{sub 10} (1) (92% yield). The structure consists of blocks of Bi{sub 2}Te{sub 3} and CdI{sub 2}-type units that are connected to form a three-dimensional network with K{sup +} ions located in the channels that run along the b-axis. The same reaction but with a different ratio, at 750 C, gave the new ternary sulfide K{sub 2}Bi{sub 8}S{sub 13} (2) (94% yield). The structure of the shiny rod-like crystals is closely related to that of 1. As in 1, it also consists of Bi{sub 2}Te{sub 3} and CdI{sub 2}-type fragments that connect to form K{sup +}-filled channels. The two potassium atoms and one bismuth atom are disordered over three sites. Some preliminary electrical and optical properties of these materials are discussed.

Cs1−xSn1−xBi9+xSe15 and Cs1.5−3xBi9.5+xSe15: members of the homologous superseries Am[M1+lSe2+l]2m[M1+2l+nSe3+3l+n] (A = alkali metal, M = Sn and Bi) allowing structural evolution in three different dimensions

Cs1-xSn1-xBi9+xSe15 and Cs1.5-3xBi9.5+xSe15 crystallize in a new structure type which does not belong to but is closely related to the members of the homologous series Am[M6-Se8]m[M5+nSe9+n]; the new phases reveal a third dimension of structural evolution for this series according to the formula Am[M1+lSe2+l]2m[M1 + 2l + nSe3 + 3l+n].