Inorganic Chemistry Communications (v.9, #11)

Contents List (iii-viii).

The synthesis and structure of nonanuclear nickel(II) cage complex with μ6-CO3, [Ni9(NH2CH2CH2SO3)6(CH3CO2)6(H2O)6(OH)66-CO3)2]4− (1), is reported. Nickel atoms in 1 are arranged as a tricapped trigonal prism, which is afforded through the fixation of atmospheric CO2.Nonanuclear nickel(II) cage complex is reported, in which carbonate anions exhibit μ6 coordination mode. The core is arranged as a tricapped trigonal prism of nickel atoms, and held in place by six acetates, six hydroxides and two carbonates.
Keywords: Crystal structure; Nickel complex; Carbonate complex; Polynuclear complex; Fixation of O2;

Two unusual copper(II) compounds with formula [Cu(dipm)(HCOO)2(H2O)] and [Cu(dipm)(C2O4)(H2O)] (in which dipm = bis(pyrimidin-2-yl)amine) have been synthesized and characterised by X-ray crystallography, spectroscopy and EPR. A 2D chain of H-bonds is formed by intermolecular hydrogen bonds between 2 dipm ligands of the Watson–Crick-type and H-bonds between the water molecules and the formato, or oxalato anions.Two unusual copper(II) compounds with formule [Cu(dipm)(HCOO)2(H2O)] (1) and [Cu(dipm)(C2O4)(H2O)] (2) (in which dipm = bis(pyrimidin-2-yl)amine) have been synthesized and characterised by X-ray crystallography, spectroscopy and EPR. The geometry around the Cu(II) ion in compound 1 is distorted octahedral with the basal plane formed by two nitrogen atoms of a ligand molecule with Cu–N distances of 1.992(2), 2.040(2) Å and two oxygen atoms of two formato anions with Cu–O distances of 1.948(2), 1.984(2) Å. The axial positions are occupied by an oxygen atom of the water molecule (Cu–O distance 2.195(2) Å) and by the second oxygen atom of one of the formato molecules at a semi-coordinating distance of 2.711(2) Å. The geometry around the Cu(II) in compound 2 is square pyramidal with the basal plane occupied by two nitrogen atoms of a ligand molecule (Cu–N distances of 2.007(3), 2.015(3) Å) and two oxygen atoms of the oxalato anion (Cu–O distances of 1.955(3), 1.956(2) Å). The fifth position is occupied by an oxygen atom of the water molecule with a Cu–O distance of 2.246(3) Å.The 2D chain of H-bonds consists of intermolecular built hydrogen bonds between 2 dipm ligands of the Watson–Crick-type and H-bonds between the water molecules and the formato (compound 1), or oxalato anions (compound 2). In addition, stacking interactions between dipm ligands are present in both compounds (ring–ring distances 3.6–3.8 Å).
Keywords: Crystal structure; Copper; Hydrogen bond; Formato; Oxalato;

An asymmetric compartmental reduced Schiff base ligand having an amino acid side arm (see the picture) goes to a carboxylate bridged tetranuclear Cu(II) complex, on treatment with Cu(CH3COO)2 · H2O.The dinucleating asymmetric reduced Schiff base compartmental ligand H2L {2-[5-bromo-2-hydroxy-3-(4-methyl-piperazin-1-ylmethyl)-benzylamino]-propionic acid} (see Scheme 1 for H2L) gives the tetracopper(II) complex [Cu4L2(CH3COO)4] · 2CH3CN · 2H2O (1) on reaction with (CH3COO)2Cu · H2O. The single crystal X-ray structure of 1 reveals that this complex is a carboxylate bridged dimer of dinuclear copper(II) subunits, in which the copper(II) centers adopt different geometries, resulting in a {Cu4} complex.

A new cobalt(III) complex salt, [cis-Co(en)2(C8H7O2)2](C8H7O2) · 2H2O, has been synthesized and characterized by single crystal X-ray structure determination. This is the first example of a cobalt(III) compound of this type with two p-methylbenzoate groups in cis-configuration. The cations and anions are associated in chains by strong NH … O hydrogen bonds. The crystal lattice is stabilized by extensive hydrogen bonding.A new cobalt(III) complex salt, [cis-Co(en)2(C8H7O2)2] (C8H7O2) · 2H2O, has been synthesized and characterized by single crystal X-ray structure determination. This is the first example of a cobalt(III) compound of this type with two p-methylbenzoate groups in cis-configuration. The cations and anions are associated in chains by strong NH … O hydrogen bonds. The crystal lattice is stabilized by extensive hydrogen bonding besides electrostatic forces of attraction.
Keywords: Cobalt(III); Coordination chemistry; Crystal structure; Ethylenediamine; p-Methylbenzoate; NMR spectroscopy;

A novel self-assembled chain of water molecules in a metal-organic framework of Cu(II) with isophthalate by Jiang-Feng Song; Jing Lu; Yan Chen; Ya-Bing Liu; Rui-Sha Zhou; Xiao-Yu Xu; Ji-Qing Xu (1079-1082).
Two cyclic water pentamer units construct the puckered-stair-shaped octamer water cluster. The octamers were assembled into a 1D water chain along a axis via O3w–H⋯O2wB and symmetry-related hydrogen bonds. This unprecedented 1D water chain consists of fused five- and six-membered ringsA novel coordination polymer, {[Cu(ip)(Him)2(H2O)] · 3H2O} (1), (ip = isophthalate, Him = imidazole) was prepared under hydrothermal conditions and its structure is determined by single-crystal X-ray diffraction. X-ray structural analysis reveals that 1D zigzag metal-organic framework was connected to form a 3D metal-organic framework by a novel infinite 1D water chain constructed by five- and six-membered rings through edge-sharing. These water chains behave as glue to stabilize the 3D network. Upon removal of the water molecules by heating, the 3D structure breaks down. Thermogravimetric analysis, infrared, X-ray powder diffraction studies, elemental analysis and magnetic analysis were performed to characterize this compound.
Keywords: Isophthalate; Crystal structure; Metal-organic framework; Water chain;

Tridentate facial coordination mode of an unsymmetrical tetradentate diazine ligand in an iron(III) complex by Subramanya Gupta Sreerama; Abhik Mukhopadhyay; Samudranil Pal (1083-1086).
Synthesis, physical properties and X-ray structure of the complex cation [Fe(salpahn)2]+ are described. Hsalpahn represents the potentially dinucleating tetradentate unsymmetrical Schiff base, 2-(pyridin-2-ylmethylene-hydrazonomethyl)-phenol. The structure reveals the unusual facial coordination mode of the diazine ligand salpahn.Synthesis, structure and properties of a distorted octahedral iron(III) complex, [Fe(salpahn)2]ClO4 (Hsalpahn = 2-(pyridin-2-ylmethylene-hydrazonomethyl)-phenol), are described. The X-ray structure reveals the facial disposition of pyridine-N, imine-N and phenolate-O donor salpahn with the formation of two six-membered chelate rings. The self-assembly pattern via intermolecular hydrogen bonds in the crystal lattice is reported.
Keywords: Iron(III) complex; Diazine ligand; Crystal structure; Facial coordination; Self-assembly;

Synthesis and characterization of first hetero-nuclear molybdenum copper cluster with highly delocalized Cu(I)/Cu(II) by Ying-Hua Sun; Jie-Hui Yu; Xiang-Jun Jin; Jiang-Feng Song; Ji-Qing Xu; Ling Ye (1087-1090).
A novel molybdenum–copper cluster with highly delocalized mixed-valence Cu(I)/Cu(II) [MoO3Cu2(obipy)2]2O (1), has been hydrothermally synthesized. The feature of 1 is that two copper atoms have different coordination configuration and valences. Variable temperature magnetic susceptibility measurements show the occurrence of a weak ferromagnetic interaction in 1.A novel molybdenum–copper cluster with highly delocalized mixed-valence Cu(I)/Cu(II) [MoO3Cu2(obipy)2]2O (1), has been hydrothermally synthesized and characterized by the elemental analyses, IR, XPS, TG analysis and the single crystal X-ray diffraction. The feature of 1 is that two copper atoms have different coordination configuration and valences. Variable temperature magnetic susceptibility measurements show the occurrence of a weak ferromagnetic interaction in 1.
Keywords: Hydrothermal synthesis; Hydroxylation; Hetero-nuclear cluster; Mixed-valence copper;

Studies on the radii dependent lanthanide self-assembly coordination behaviors of a flexible dicarboxylate ligand by Xiao-Feng Li; Zheng-Bo Han; Xiao-Ning Cheng; Xiao-Ming Chen (1091-1095).
Flexible ligand benzene-1,4-dioxyacetic acid adopts different coordination modes along with the changes of the metal radii: (μ 2  −  η 1:η 1  +  μ 2  −  η 1:η 1:η 1) and (μ 2  −  η 2:η 1  +  μ 2  −  η 2:η 1) bridging modes in 1, or (μ 2  −  η 1:η 1  +  μ 1  −  η 1:η 1) and (μ 2  −  η 1:η 1:η 1  +  μ 2  −  η 1:η 1:η 1) bridging modes in 2. Two new lanthanide coordination polymers {[Eu2(BDOA)3(H2O)2] · 2H2O} n (1) and {[Er2(BDOA)3(H2O)2]} n (2) were synthesized by treating the corresponding lanthanide(III) chloride and a flexible ligand benzene-1,4-dioxyacetic acid (H2-BDOA). Single-crystal X-ray studies reveal that the ligand BDOA2− adopts different coordination modes in these complexes. Self-assemblies between these bridging ligands and metal ions result in different three-dimensional coordination polymers. The luminescence property of 1 was investigated in the solid state at room temperature.
Keywords: Lanthanide; Flexible ligand; Coordination polymer; Self-assembly; Luminescence;

Self-assembly of a hybrid organic–inorganic dicopper(II) coordination polymer with a calix[4]arene-derived nitrogenous ligand by Juan Olguín; Virginia Gómez-Vidal; Eduardo Muñoz; Rubén A. Toscano; Ivan Castillo (1096-1098).
Hybrid organic–inorganic polymers are obtained from the reaction of bidentate bispicolyl-p-tert-butylcalix[4]arene ligands with copper(II) acetate. The coordination polymer has empty calix[4]arene cavities which align forming channels, which can be exploited in the construction of inclusion compounds.Reaction of bispicolyl-p-tert-butylcalix[4]arene (L 1 ) functionalized in alternate phenolic positions with dimeric copper(II) acetate resulted in the formation of a hybrid organic–inorganic polymer. In the solid state, dicopper fragments are bridged by the bidentante ligand [Cu2(μ-O2CCH3)4(μ-L 1 ) · C4H8O] n , with one molecule of tetrahydrofuran in the asymmetric unit. The two independent Cu(II) ions possess square pyramidal coordination geometries defined by the four acetate ligands, and a picolyl group in the axial position.
Keywords: Calix[4]arene; Copper; Coordination polymer; Organic–inorganic hybrid;

Two heterobimetallic trinuclear Cu–Mo–S clusters with linear or butterfly-shaped skeleton containing 1,2-bis(diphenylphosphino)-1,2-dicarba-closo-dodecaborane have been synthesized by the reactions of (NH4)2MoS4 or (NH4)2MoOS3, CuSCN with 1,2-(PPh2)2-1,2-C2B10H10 (L) in dichloromethane. The two reactions are shown.The carborane skeleton was introduced into the heterometallic sulfide cluster cores. Two heterobimetallic trinuclear Cu–Mo–S clusters with linear or butterfly-shaped skeleton containing 1,2-bis(diphenylphosphino)-1,2-dicarba-closo-dodecaborane have been synthesized by the reactions of (NH4)2MoS4 or (NH4)2MoOS3, CuSCN with 1,2-(PPh2)2-1,2-C2B10H10 (L) in dichloromethane and characterized by elemental analysis, FT-IR, UV/Visible, 1H and 13C NMR spectroscopy and X-ray structure determination.
Keywords: Synthesis and characterization; Crystal structure; Cu–Mo–S cluster; 1,2-Bis(diphenylphosphino)-1,2-dicarba-closo-dodecaborane;

Two novel 2D decapolyoxotungstates constructed up by coordinated lanthanides by Xiao-Yu Jiang; Li-Juan Chen; Hua Huang; Quan-Zheng Zhang; Wen-Bin Yang; Can-Zhong Lu (1103-1107).
Two novel 2D decapolyoxotungstates constructed up by coordinated lanthanides, which represent the first example that the basic decapolyoxotungstates building blocks was linked up into multi-dimensional structure by DMSO coordinated lanthanides (La or Ce) and sodium ions, have been reported.Two layer compounds, [(H2O)Na(μ-DMSO)3Ln(DMSO)4(W10O32)] n (Ln = La, 1, Ln = Ce, 2), which were synthesized by the reaction of sodium tungstate and lanthanide chloride in the solution of DMSO and water, have been characterized by IR, Raman, elemental analysis, TGA and X-ray single crystal diffractometer. Single crystal structure analysis shows that the same two-dimensional layer structure for 1 and 2 represents the first example that the basic decapolyoxotungstates building blocks was linked up into multi-dimensional structure by DMSO coordinated lanthanides (La or Ce) and sodium ions.
Keywords: Polyoxotungstate; Coordinated lanthanides; Crystal structure; Multi-dimensional; Building units;

New photo-controllable supramolecular system containing magnetic ionic liquid (iron(III) chloride with 1-butyl-3-methylimidazolium chloride) and azobenzene was prepared and we discovered novel photo-induced irreversible aggregation behavior of paramagnetic complexes in ionic liquid.New photo-controllable supramolecular system containing magnetic ionic liquid (iron(III) chloride with 1-butyl-3-methylimidazolium chloride) and azobenzene has been prepared. Reversible structural changes due to cistrans photoisomerization of azobenzene could be observed by means of resonance Raman and electronic spectroscopy. Field dependence of magnetic moment at 298 K exhibited paramagnetic behavior similar to pure iron(III) magnetic ionic liquid. Alternate irradiation of UV and visible light at 298 K resulted in a monotonous increase of magnetic moment. In analogy with previous study, the novel behavior can be explained as irreversible aggregation of paramagnetic iron(III) complexes forming a short-range order in the supramolecular system.
Keywords: Magnetic ionic liquid; Azobenzene; Iron(III); Photofunctional materials; Supramolecular chemistry;

A novel coordination behaviour of bis-oxamato ligands by T. Rüffer; B. Bräuer; B. Walfort (1111-1113).
Subsequent reaction of [nBu4N]OH with the diethyl ester of N,N′-1,2-ethanediylbis(oxamic acid) (endaH2Et2, 1) and [CuCl2(H2O)2] affords [nBu4N]4[Cu(endaH)2] (2). In 2, for the first time the coordination of two bis-oxamato ligands with only one oxamato substituent to a transition metal is observed, leading to a novel flexidentate system for coordination of up to six further transition metals.Subsequent reaction of [nBu4N]OH with the diethyl ester of N,N′-1,2-ethanediylbis(oxamic acid) (endaH2Et2, 1) and [CuCl2(H2O)2] affords the title compound [nBu4N]4[Cu(endaH)2] (2). The solid state structure of 2 is reported. In 2, two bis-oxamato ligands [endaH]3− with only one oxamato substituent per ligand are coordinated towards copper, leading to a trans-bis(endaH-N,O) arrangement around copper. Complex 2 can be considered as a novel flexidentate system for coordination of up to six further transition metals.
Keywords: Copper; Oxamato ligands; Flexidentate ligands; X-ray structure analysis;

Cellular toxicities of new titanocene dichloride derivatives containing pendant cyclic alkylammonium groups by Gregory D. Potter; Michael C. Baird; Marina Chan; Susan P.C. Cole (1114-1116).
Four new water soluble titanocene dichloride derivatives have been synthesized and characterized and their cytotoxicities against the benchmark human cancer cell line A549 have been assessed. The potencies of the four compounds vary to a surprising degree, but the 3-picolylium compound 6a exhibits an IC50 value which is unusually low for this class of compounds.Four new water soluble titanocene dichloride derivatives, all containing pendant alkyl- or arylammonium substituents and thus similar in functionality to previously reported complexes which exhibit encouraging cytotoxic activities, have been synthesized. The cytotoxicities of the four compounds against the benchmark human cancer cell line A549 have been assessed, and a dicationic complex containing a 3-picolylium group is found to exhibit an IC50 value as low as any previously reported for this class of anti-cancer drug.
Keywords: Anti-cancer drugs; Titanocene dichloride; Metallocenes; Human cancers;

The first metal complex with the hydrazine dicarboxylate dianion: Na2(O2CNHNHCO2)(H2O)3 by Krishnan Srinivasan; Subbaiah Govindarajan; William T.A. Harrison (1117-1120).
Na2(O2CNHNHCO2)(H2O)3 is the first complex of the hydrazinedicarboxylate dianion with a metal ion. In the crystal structure, there are three distinct sodium-ion coordination polyhedra, all approximating to octahedra: trans-NaO4(H2O)2, cis-NaO2(H2O)4 and trans-NaN2O4. The latter arises from the coordination of two bidenate-N,O and two monodentate-O ligands.The title compound is the first complex of a metal ion with the hydrazinedicarboxylate dianion. One of the sodium cations is coordinated by two N,O-bidenate and two O-monodentate ligands to result in distorted trans-NaN2O4 octahedra. Crystal data: Na2(O2CNHNHCO2) · 3H2O, M r  = 218.08, triclinic, P 1 ¯ (No. 2), a  = 5.5123 (2) Å, b  = 8.7311 (3) Å, c  = 8.8117 (3) Å, α  = 107.005 (2)°, β  = 99.431 (2)°, γ  = 101.552 (2)°, V  = 385.98 (2) Å3, Z  = 2, R(F) = 0.027, wR(F 2) = 0.092.
Keywords: Ligand; Sodium; Crystal structure;

Hydrothermal synthesis and crystal structure of a novel lead(II) phosphonate containing trifunctional phosphonate anions: Pb4O[O3PCH2–NC4H7–CO2]2 by Zhen-Gang Sun; Lian-Yi Cui; Zhong-Min Liu; Da-Peng Dong; Lei Meng; Hui Chen; Lan-Cui Zhang; Zai-Ming Zhu; Wan-Sheng You (1121-1124).
Hydrothermal reaction of lead (II) acetate with proline-N-methyl-phosphonic acid at 180 °C have resulted in a novel layered compound, Pb4O[O3PCH2–NC4H7–CO2]2. The compound features a layer structure in ab plane in that the layers have an inorganic ‘core’ with the organic part of the phosphonate anion being directed into the interlayer region.Hydrothermal reaction of lead(II) acetate with proline-N-methyl-phosphonic acid, namely, (S)–HO3PCH2–NHC4H7–CO2H at 180 °C has resulted in a novel layered compound, Pb4O[O3PCH2–NC4H7–CO2]2 1. The novel compound has been characterized by single-crystal X-ray diffraction, elemental analysis, infrared spectroscopy and thermogravimetric analysis. The compound features a layered structure in ab plane, and the layers have an inorganic ‘core’ with the organic part of the phosphonate anion being directed into the interlayer region.
Keywords: Metal phosphonates; Crystal structure; Hydrothermal synthesis; Lead(II);

The new ligand, 4,6-dinitro-5-oxido-1,3-benzenedicarboxylate (dnob3−), and novel 2D coordination polymer [Pb3(dnob)2(phen)3 (H2O)] n , were synthesized in situ by hydrothermal synthesis. The nitration substitution was achieved only by lead(II) nitrate rather than HNO3/H2SO4. The new organic ligand exhibits interesting steric and electronic effects on the assembly of lead(II) coordination polymer.The first in situ nitration substitution was hydrothermally achieved only by lead(II) nitrate rather than HNO3/H2SO4. The new organic ligand, 4,6-dinitro-5-oxido-1,3-benzenedicarboxylate (dnob3−) in situ synthesized from 5-hydroxyl-1,3-benzenedicarboxylic acid, exhibits interesting steric and electronic effects on the assembly of lead(II) coordination polymer, [Pb3(dnob)2(phen)3(H2O)] n where phen is 1,10-phenanthroline.
Keywords: Nitration; Lead(II) coordination polymer; Structural assembly; Crystal structure;

Cyclic ether fragmentation and identification of a quadruple open cubane motif for hexametallic aggregates by Jeffrey A. Rood; Bruce C. Noll; Kenneth W. Henderson (1129-1132).
The complex [Mg6{2,6- i Pr2C6H3N(H)}4(OCH2CH2O)2{OCH2CH2OC(H)=CH2}4] was prepared as an ether cleavage by-product during the reaction of Bu2Mg with 2,6-diisopropylamine in 1,4-dioxane solution. The molecular core of this hexametallic species consists of nine interconnected four-membered rings, to give a framework resembling a section of the CdI2 structure.Reaction of Bu2Mg with 2,6-diisopropylaniline in 1,4-dioxane solution results in double deprotonation of the amine to produce the imide [2,6- i Pr2C6H3NMg · (dioxane) n ]. An ether cleavage side product of this reaction was characterized by single crystal X-ray diffraction and was found to possess an interesting composition and molecular structure. The complex [Mg6{2,6- i Pr2C6H3N(H)}4(OCH2CH2O)2{OCH2CH2OC(H)=CH2}4], 2, is constructed from six metals, four primary amides, four alkoxy vinyl ethers and two diolates. The core of 2 is created from nine interconnected four-membered rings, and resembles a section of the CdI2 layer structure. Complex 2 also contains four-, five- and six-coordinate metal centers within a single molecular structure.
Keywords: Ether cleavage; Crystal structure; Magnesium; Amide; Imide;

Complexes of crown-containing N-thioacylamido(thio)phosphates with Zn(II) and Co(II) cations by Damir A. Safin; Maria G. Babashkina; Felix D. Sokolov; Nail G. Zabirov (1133-1135).
We reported four new complexes of Zn(II) and Co(II) cations with crown-containing N-acylamidophosphates. The structures of the obtained compounds were investigated by ES-MS, IR, 1H and 31P NMR spectroscopy and microanalysis. It was established that complexes with crown-containing thioureas have a composition of ML2, while crown-containing thioamide forms with the Zn(II) cation a complex of structure Zn(HL)L2.Reaction of the potassium salts of N-acylamido(thio)phosphates [4-benzo-15-crown-5]NHC(S)NHP(Y)(OiPr)2 (Y = S, HL I ; Y = O, HL II ) with Zn(II) and Co(II) cations in aqueous EtOH leads to complexes of formulae Zn(LI,II  −  S,Y)2 (Y = S, 1; Y = O, 2) and Co(LI-S,S )2 (3), while interaction of the potassium salt of [4-benzo-15-crown-5]C(S)NHP(O)(OiPr)2 (HL III ) with Zn(II) in the same conditions leads to a complex of composition Zn(HLIII)(LIII-S,O)2 (4).
Keywords: Chelate; Complex; Crown-ether; Mass-spectroscopy; Amidophosphate; Urea;

Control of micropore size in supermicroporous titania–chromia system TiO2–Cr2O3 by Windlyne Delouis; Marcos Sanchez; Boris Shpeizer; Abraham Clearfield; Aderemi Oki (1136-1140).
Sol–gel hydrolysis reactions of titanium(IV) isopropoxide and chromium(III) acetate hydroxide in the presence or absence of propanol using alkylamine as template yielded microporous mixed metal oxides with pores largely in the 10–20 Å region, and surface areas that vary from 405 to 564 m2/g depending on the amine and synthesis condition.Sol–gel hydrolysis reactions of titanium(IV) isopropoxide and chromium (III) acetate hydroxide in the presence or absence of propanol, using the following amines as structure directing agents; N-hexylamine, N-methylhexylamine, and N-propylbutylamine, yielded microporous mixed metal oxides with the presence of pores largely in the 10–20 Å region, and surface areas that vary from 564 m2/g when N-hexylamine is employed as pore directing template to 494 m2/g when N-propylbutyl amine is employed as template. The maxima in pore size distribution increases with increase in steric crowding around the nitrogen in the alkyl amine. In addition, the nitrogen adsorption–desorption isotherm shifted from Type 1 isotherm when N-hexylamine is used as templating agent to Type 4 isotherm in N-propylbutylamine.
Keywords: Hexylamine; Pore; Titania; Chromia; Sol–gel hydrolysis;

The synthesis of functional mesoporous materials by Glen E. Fryxell (1141-1150).
The synthesis of functional mesoporous materials is a field of significant importance today as it provides a powerful and versatile foundation for catalysis, chemical separations and amplifying the capabilities of sensing/detection methods. This manuscript provides an overview of the synthetic methods used to make these functional mesoporous materials, giving the reader a solid working introduction to the field of functional nanomaterials.The ability to decorate a silica surface with specific ligand fields and/or metal complexes creates powerful new capabilities for catalysis, chemical separations and sensor development. Integrating this with the ability to control the spacing of these complexes across the surface, as well as the symmetry and size of the pore structure, allows the synthetic chemist to hierarchically tailor these structured nanomaterials to specific needs. The next step up the “scale ladder” is provided by the ability to coat these mesoporous materials onto complex shapes, allowing for the intimate integration of these tailored materials into device interfaces. The ability to tailor the pore structure of these mesoporous supports is derived from the surfactant templated synthesis of mesoporous materials, an area which has seen an explosion of activity over the last decade [J.S. Beck, J.C. Vartuli, W.J. Roth, M.E. Leonowicz, C.T. Kresge, K.D. Scmitt, C.T.W. Chu, D.H. Olson, E.W. Sheppard, S.B. McCullen, J.B. Higgins, J.L. Schlenker, J. Am. Chem. Soc. 114 (1992) 10834–10843; C.T. Kresge, M.E. Leonowicz, W.J. Roth, J.C. Vartuli, J.S. Beck, Nature 359 (1992) 710–712]. The ability to decorate the surface with the desired functionality requires chemical modification of the oxide interface, most commonly achieved using organosilane self-assembly [S.R. Wasserman, Y.T. Tao, G.M. Whitesides, Langmuir 5 (1989) 1074–1087; S.R. Wasserman, G.M. Whitesides, I.M. Tidswell, M. Ocko, P.S. Pershan, J.D. Axe, J. Am. Chem. Soc. 111 (1989) 5852–5861; A. Ulman, Adv. Mater. 2 (1990) 573–582; A. Ulman, An Introduction to Ultra-thin Organic Films: From Langmuir–Blodgett to Self-Assembly, Academic Press, San Diego, 1991]. This manuscript describes recent results from the confluence of these two research areas, with a focus on synthetic manipulation of the morphology and chemistry of the interface, with the ultimate goal of binding metal centers in a chemically useful manner.
Keywords: Functional; Mesoporous; Catalyst; Silane; Monolayer; Metal complex; Ligand; Nanomaterial; Nanoporous; Chemical separation; Chelation; Selective;