Organic-inorganic Hybrid Complexes Research Articles

Synthesis, structure, semiconductive and photoluminescent properties of [{Eu(NC5H4COOH)3(H2O)2}(1.5ZnCl4)·(2H2O)

A novel bimetallic 4f-3d metal-isonicotinic acid inorganic-organic hybrid complex [{Eu(NC5H4COOH)3(H2O)2}(1.5ZnCl4)?(2H2O)]n (1) was synthesized via a hydrothermal reaction and structurally characterized by single- crystal X-ray diffraction. Complex 1 crystallizes in the space group C2/c of the monoclinic system with eight formula units in a cell: a = 23.878(8) ?, b = 20.573(6) ?, c = 15.358(5) ?, ? = 127.276(5)?, V = 6003(3) ?3, C18H23Cl6EuN3O10Zn1.5, Mr = 904.11 g/mol, ? = 2.001 g/cm3, S = 1.077, ?(MoK?) = 3.846 mm-1, F(000) = 3536, R = 0.0270 and wR = 0.0672. Complex 1 has a characteristic, one-dimensional polycationic chain-like structure. A photoluminescent investigation revealed that the title complex displays intense emissions in the orange and red regions. The luminescence spectra show that the red emission is stronger than the orange emission. Optical absorption spectra of 1 revealed the presence of an optical gap of 3.56 eV.

Cucurbit[n]uril−Polyoxoanion Hybrids

The first organic-inorganic hybrid complexes between CB[n] and polyoxometalates not only display a surprisingly high structural complementarity, the right pairing also allows their chemical and physical properties to be coupled, as illustrated by two examples.

Catena-Poly[[[tetrakis(μ-2-butenoato)dicopper(II)]-μ-2-butenoato-[diaqua(2-butenoato)holmium(III)]-di-μ-2-butenoato-[diaqua(2-butenoato)holmium(III)]-μ-2-butenoato] trihydrate

The title compound {[Cu2Ho2(C4H5O2)10(H2O)4]·3H2O}n, is a one-dimensional 3d/4f organic–inorganic hybrid complex, the HoIII member of the isotypic lanthanoid series with Ln = GdIII, ErIII and YIII. The structure shows an alternation of Cu2 and Ho2 dinuclear units bridged by the ligands and hydrogen bonds only. The chains are composed of Cu2 classical dinuclear η1:η1:μ2 fourfold bridges [Cu⋯Cu = 2.6417 (9) Å] and of Ho2 units bridged by two η2:η1:μ2 carboxyl­ate units. This results in distorted square-based pyramidal CuO5 units and irregular HoO9 units. The alternating Cu2 and Ho2 units are bridged into linear arrays along the a axis by a set of one η2:η1:μ2 carboxyl­ate O atom and two hydrogen bonds with Cu⋯Ho separations of 4.4883 (10) and 4.5086 (10) Å. The distance between adjacent chains, as calculated by the closest and furthest distances between two chains, covers the range 10–14 Å. The H atoms of the water mol­ecules could not be located, but the O⋯O separations for these species suggest the presence of O—H⋯O hydrogen bonds.

Open framework complex constructed from polyoxometalate and dinuclear Cu–phenanthroline

An inorganic–organic hybrid complex, {[Cu 2(phen) 2(OH) 2(H 2O)] 2[α-SiW 12O 40]}·8H 2O 1, (phen = 1,10-phenanthroline), has been synthesized under mild reaction conditions and characterized by single-crystal X-ray diffraction, IR spectrum, thermal analyses (TG-DTA) and fluorescent measurement. The crystallographic analysis reveals that in the compound, the Keggin polyanion [α-SiW 12O 40] 4− acts as the inorganic building block, two [Cu 2(phen) 2(OH) 2(H 2O)] units covalently bond to it via terminal oxygen atoms of the Keggin anion. An open framework is formed through supramolecular interactions with solvent accessible volume of 18% in the unit-cell. Dehydration and re-adsorption of water in 1 were investigated by X-ray powder diffraction (XRPD).The compound shows thermal stability and photoluminescence property in the solid state.

Syntheses and structural characterization of inorganic-organic hybrid solids of diimidazolium hexachlorostannate complexes

Six organic-inorganic hybrid complexes of formula [(H2L)SnCl6] prepared from imidazole derivatives (1, L1 = 1,4-bis(imidazolyl)butane; 2, L2 = 1,1′-bis(imidazolyl)methane; 3, L3 = di(2-benzimidazol-1-ylethyl)ether; 4, L4 = 1,1′-bis(benzimidazolyl)methane; 5, L5 = 2-(imidazol-1-yl)-1-phenylethanone; 6, L6 = 7-imidazolyl-2,4-dimethyl-1,8-naphthyridine) and tin(II) chloride were characterized through X-ray diffraction analysis. The results reveal that 1–6 have 3D network structures built from hydrogen bonds between imidazolium cations, water molecules and . The arrangement of the anions and cations in their solid state is dominated by the size, symmetry, and charge numbers of the imidazolium cations. The TGA studies show that the complexes are thermally stable.

Hydrothermal syntheses and crystal structures of hybrid materials based on Keggin cluster modified by iron complexes

Three new organic-inorganic hybrid complexes based on the Keggin polyoxometalates (POMs) modified by transition metal iron and N-ligand organic moiety: [Fe(phen)3]2 (1) [Fe(phen)2(H2O)]2 · 2H2O (2) and [Fe(phen)3]2 · 0.5H2O (3) (phen = 1,10-phenanthroline) have been hydrothermally synthesized and structurally characterized. Crystal data for complex 1: C72H48Fe2M12N12O41PV, triclinic, , a = 11.6618(2) Å, b = 13.8523(2) Å, c = 14.9168(2) Å, α = 105.87(3)°, β = 93.103(2)°, γ = 96.609(2)°, V = 2293.2(5) Å3, Z = 1; for complex 2: C48H32Fe2PMo12N8O44, triclinic, , b = 13.357(3) Å, c = 13.701(3) Å, α = 69.09(3)°, β = 71.37(3)°, γ = 78.21(3)°, V = 1766.4(6) Å3, Z = 1; for complex 3: C72H50Fe2Mo12N12O41Ge, triclinic, , b = 13.676(3) Å, c = 14.627(3) Å, α = 105.05(3)°, β = 109.64(3)°, γ = 93.07(3) °, V = 2185.6(7) Å3, Z = 1. Other characterizations by element analysis, IR, XPS and TGA analysis are also described. Their electrochemical properties have been studied in the paper.

Synthesis, structure, and physical properties of [Sm(C 6NO 2H 5) 3(H 2O) 2] 2n.(H 5O 2) n(ZnCl 5) n(ZnCl 4) 2n.(H 2O) 2n with unprecedented ZnCl 53− species

A novel bimetallic 4 f–3 d metal–isonicotinic acid inorganic–organic hybrid complex [Sm(C 6NO 2H 5) 3(H 2O) 2] 2 n ·(H 5O 2) n (ZnCl 5) n (ZnCl 4) 2 n ·(H 2O) 2 n ( 1) has been synthesized via hydrothermal reaction and structurally characterized by single-crystal X-ray diffraction. Complex 1 is characteristic of a one-dimensional polycationic chain-like structure and unprecedented ZnCl 5 3− species. Photoluminescent investigation reveals that the title complex displays interesting emissions in a wide region. Optical absorption spectra of 1 reveal the presence of an optical gap of 3.59 eV.

3D-transition metal mono-substituted Keggin polyoxotungstate with an antenna molecule: synthesis, structure and characterization

Three new organic-inorganic hybrid complexes based on 3d-transition metal monosubstituted Keggin polyoxometalates (POMs) with imidazole (Im) as pendant ligands, formulated as (HIm)(6-)[SiW11O39NiIm]0.8[SiW11O39Ni(H2O)]0.2.7H2O (1), (Im)4Na6[SiW11O39MnIm]0.69[SiW11O39Mn(H2O)]0.31.7.5H2O (2) and (HIm)6[SiW11O39CoIm]0.63[SiW11O39Co(H2O)]0.37.7H2O (3), have been synthesized and characterized by IR spectroscopy, UV-visible spectroscopy, elemental analysis, TG analysis, cyclic voltammetry, magnetic properties, EPR and single-crystal/powder X-ray diffraction. The structural analyses indicate that the 3d metal atoms are incorporated into the vacancy of the alpha-[SiW11O39](8-) (SiW11). Complexes 1-3 are the first examples of crystallographically characterized 3d-transition metal mono-substituted POMs with an antenna organic ligand synthesized under normal bench conditions.

A density functional theory study on the degradation mechanism of thin film of organic semiconductor by water molecules

Hybrid density functional theory calculations have been carried out for the organic–inorganic hybrid complex of 1,4,5,8-naphthalene-tetracarboxylic-dianhydride (NTCDA) with an indium atom (In) to elucidate the degradation mechanism of thin films of molecular organic semiconductors by water molecules. This compound has been used as an organic semiconductor. The band gap of NTCDA was calculated to be as high as 3.39 eV as a single molecule, whereas a new band of NTCDA was formed as low-lying excited state (1.64 eV) after the interaction with the In atom. The water molecule attacked preferentially the In atom of In-NTCDA, and the solvation structure was formed around the In atom (solvation). Further addition of a water molecule to the system, the In atom is stripped off from NTCDA by water molecules, and solvation shell around the In atom is formed (separated solvation). The hydrogen-bond network was broken by the formation of solvation shell. The mechanism of degradation of the electron conductivity has been discussed on the basis of theoretical results.

Poly[μ2-4,4′-bipyridine-di-μ2-bromido-cadmium(II)], with novel colour-tunable fluorescence

The title inorganic-organic hybrid complex, [CdBr2(C(10)H(8)N(2))]n, features two-dimensional [CdBr2(4,4'-bipy)]n (4,4'-bipy is 4,4'-bipyridine) neutral networks, based on the octahedral Cd atom coordinated by four mu2-Br and two mu2-4,4'-bipy at trans positions, yielding a CdBr(4)N(2) octahedron. It crystallizes in the orthorhombic system (Cmmm). All the crystallographically independent atoms are on special positions, namely Cd on mmm, Br on mm, N on mm2, and C on sites of symmetry m or mm2. Optical absorption spectroscopy reveals the presence of an optical gap of 3.76 eV, indicating that the complex is a wide-gap semiconductor. Photoluminescence investigation reveals that the complex displays strong colour-tunable emissions, which might originate from a ligand-to-ligand charge-transfer (LLCT) transition. Thermogravimetric differential thermal analysis shows that the complex is thermally stable up to 493 K.

Prediction of Second-Order Optical Nonlinearity of Trisorganotin-Substituted β-Keggin Polyoxotungstate

The dipole polarizabilities, second-order polarizabilities, and origin of second-order nonlinear optical (NLO) properties of trisorganotin-substituted beta-Keggin polyoxotungstate [XW9O37(SnR)3](11-n)- (X = P, Si, Ge, R = Ph; X = Si, R = PhNO2, PhCCPh) have been investigated by using time-dependent density functional response theory. This class of organic-inorganic hybrid complexes possesses a remarkably large molecular second-order NLO response, especially for [SiW9O37(SnPhCCPh)3]7- (system 5) with the static second-order polarizability (beta(vec)) computed to be 1569.66 x 10(-30) esu. Thus, these complexes have the possibility to be excellent second-order nonlinear optical materials. Analysis of the major contributions to the beta(vec) value suggests that the charge transfer from the heteropolyanion to the organic segment along the z-axis plays the key role in the NLO response of [XW9O37(SnR)3](11-n)-. The computed beta(vec) values increase as a heavy central heteroatom changes in the order Ge > Si > P. Furthermore, nitro substitution on the aryl segment and the lengthening of organostannic pi-conjugation are more important in enhancing the optical nonlinearity, especially for the latter factor. The present investigation provides important insight into the origin of the NLO properties of trisorganotin-substituted heteropolyoxotungstate.

Influence of substituents on the structures of hybrid complexes constructed from tetranuclear copper(I) 1,2,4-triazolate clusters and octamolybdates

By changing the substituents on 1,2,4-triazole ring, six novel organic–inorganic hybrid complexes constructed from tetranuclear copper(I) 1,2,4-triazolate clusters and octamolybdates, [{Cu 4(L) x }Mo 8O 26] (L = 3,5-diamino-1,2,4-triazole (datrz) and x = 4 for 1; L = 3-amino-1,2,4-triazole (3atrz) and x = 4 for 2; L = 3,5-dimethyl-1,2,4-triazole (dmtrz) and x = 4 for 3; L = 3,5-dimethyl-4-amino-1,2,4-triazole (dmatrz) and x = 6 for 4; L = 3,5-diethyl-4-amino-1,2,4-triazole (deatrz) and x = 4 for 5; L = 3,5-di( n-propyl)-4-amino-1,2,4-triazole (dpatrz) and x = 3 for 6), were obtained. The tetranuclear Cu(I) cluster in compound 1 acts as charge-compensating unit, which is the first polynuclear metal 1,2,4-triazole structure only with N1, N2 bridging mode. Compounds 2, 4, 5 and 6 are of polymeric 1D chains and 3 is of a 2D layer structure. In 2, three distinct Cu(I)-coordination geometries, distorted tetrahedral, T-shaped and V-shaped linear Cu(I), are observed in the same structure. The first extended hybrid structure constructed by δ-octamolybdates is founded in 4. A novel [Mo 8O 26] 4− anion is found in 5, which contains only three crystallographically independent Mo atoms. In compounds 5 and 6, terminal oxo groups of octamolybdate cluster act as μ 3-oxo bridges to link the copper(I) coordination complexes; such an unusual linking manner is unique in the coordination chemistry of octamolybdates with transition metal fragments. The influences of substituent on the structures of the tetranuclear units are also discussed in details.

Hydrothermal synthesis and characterization of a new inorganic–organic hybrid compound AMP[ZnCl 3] (AMP = 2-aminomethylpyridinium)

A novel organic–inorganic hybrid complex [(2-NH 2CH 2C 5H 4N)ZnCl 3] has been hydrothermally synthesized and characterized by single crystal X-ray diffraction, thermal analysis and spectroscopic studies. The compound crystallizes in the triclinic system, space group P 1 ¯ , a = 7.5339(9), b = 7.589(2), c = 9.365(2) Å, α = 104.55(2)°, β = 97.22(1)°, γ = 87.88(2)°, V = 513.6(2), Z = 2. In the title compound the 2-aminomethylpyridine acts as a ligand covalently linked to Zn(II) cation to form a slightly distorted ZnCl 3N tetrahedral environment. Each [Zn(C 6H 8N 2)Cl 3] unit is connected to one neighbor by a pair of hydrogen bonds between the apical chlorides and amine hydrogen atoms and to the other by a couple of π–π stacking interactions between the aromatic rings of the coordinated ligands forming a novel one-dimensional chain-like arrangement. The title complex is the first one that contains both coordinated and hydrogen bonded 2-aminomethylpyridine. Solid state 13C and 15N CP-MAS-NMR spectroscopies are in agreement with the X-ray structure. Ab initio calculations allow the attribution of carbons and nitrogen to the independent crystallographic sites. The Raman spectroscopy confirmed the presence of Zn–Cl and Zn–N bonds.

Two-dimensional structural topology involving Pt⋯K and K⋯S weak interactions: complex of cis– anti– cis-dicyclohexyl-18-crown-6 with K 2mnt and K 2PtCl 4

One inorganic–organic hybrid complex [K(DC18C6-B)] 4[Pt(mnt) 2] 2 (DC18C6-B= cis– anti– cis-dicyclohexyl-18-crown-6, isomer B; mnt=maleonitriledithiolate, 1,2-dicyanoethylene-1,2-dithiolate) was synthesized by the reaction of cis– anti– cis-dicyclohexyl-18-crown-6 with K 2mnt and K 2PtCl 4, and characterized by elementary analysis, 1H NMR, FT-IR and UV–visible spectroscopy. The crystal structure was determined by X-ray single crystal diffraction. The complex crystallizes monoclinic, space group P2/ c with crystallographic data: a=16.709(4) Å, b=10.201(2) Å, c=33.038(4) Å, β=90.143(2), V=5631.3(18) Å 3, Z=4, R 1=0.0679, wR 2=0.1280. The complex shows a 2D network structure consisting of [K(DC18C6-B)] + complex cations and [Pt(mnt) 2] 2− complex anions bridged by K–N coordinate bonds and Pt⋯K, K⋯S weak interactions.

Four one-dimensional cadmium(ii) polymers: one chairlike chain containing four azido bridging modes and three double end-on azido-bridged uniform chains

Four new azido-bridged cadmium(II) complexes have been synthesized and characterized by spectroscopy and crystallographic methods. Compounds [Cd3(L1)2(N3)6(H2O)(CH3OH)0.5]n (1), [Cd(L2)(N3)2]n (2), [Cd2(L3)(DMF)(N3)4]n (3) and [Cd(L4)(N3)2]n (4) (L1 = 2-acetylpyridine, L2 = 2-(pyrazol-1-ylmethyl)pyridine, L3 = 2-(3-methylpyrazol-1-ylmethyl)pyridine and L4 = 1-(2-pyridyl)-2-aza-1-amylene) show one-dimensional (1-D) polymeric structures in the lattice with the distorted octahedral coordination environment of the cadmium(II) ions in the four complexes. Compound 1 contains hexanuclear chairlike unit with defective dicubane-like core, which is further linked by azido bridges into a novel 1-D chain. It is interesting that four different azido bridging modes exist simultaneously in 1. Zigzag chains with double end-on (EO) azido bridged Cd(II) ions are formed in compound 2. Compounds 3 and 4 consist of uniform double EO azido bridged helical chains with screw-pitches of 18.91 and 26.04 A, respectively. It should be noted that the longer pitch in 4 is unusual in inorganic–organic hybrid complexes. Further comparison within the four chains shows that the rigidity of the chains increases with the steric effect of the co-ligands coordinated to the central Cd(II) ions.

Hydrothermal synthesis, structure, and characterization of two one-dimensional chainlike hybrid complexes [(CuX) 2( o-phen)] ∞ (X=Br, Cl; o-phen= o-phenanthroline)

Two novel organic–inorganic hybrid complexes [(CuX) 2( o-phen)] ∞ (X=Br ( 1), Cl ( 2); o-phen= o-phenanthroline) have been synthesized hydrothermally and characterized structurally by elemental analyses, IR, ESR, XPS spectrum, TG analyses and single-crystal X-ray diffraction. Both title compounds exhibit novel one-dimensional chainlike copper halide scaffolding constructed by the unusual [Cu 3X 3] hexagon motifs by sharing opposite edges, where a single Cu site of each [Cu 3X 3] hexagon is chelated with N donors of o-phen group. To our knowledge, such basic o-phen–copper halide skeleton has not been reported hitherto. Moreover, TG analyses indicate that both title compounds possess high thermal stability.

An Unusual Organic–Inorganic Chain-like Hybrid Complex [(CuCl)2(o-phen)]∞ (o-phen=o-phenanthroline)

A novel organic–inorganic hybrid complex [(CuCl)2(o-phen)]∞ 1 (o-phen=o-phenanthroline) has been hydrothermally synthesized and structurally characterized by elemental analyses, XPS spectrum, TG analysis, and single-crystal X-ray diffraction. Compound 1 crystallizes in the monoclinic system, space group P21/n, a=3.7285(7) Å, b=19.603(4) Å, c=16.757(3) Å, β=95.83(3)°, V=1218.4(4) Å3, Z=4, λ(MoKα)=0.71073 Å (R(F)=0.0643 for 2559 reflections). Data were collected on an R-axis RAPID diffractometer at 293 K in the range of 1.60<θ<27.48°. The title compound exhibits a one-dimensional chain-like scaffolding constructed by the unusual [Cu3Cl3] hexagon motifs by sharing opposite edges. Only Cu(1) sites of the [Cu3Cl3] hexagon are coordinated with N donors of o-phen groups. Furthermore, the three-dimensional supermolecular architecture is formed by C–H…Cl hydrogen bonds between o-phen groups and CuCl chains.

An Unusual Organic–Inorganic Chain-like Hybrid Complex [(CuCl) 2( o-phen)] ∞ ( o-phen= o-phenanthroline)

A novel organic–inorganic hybrid complex [(CuCl) 2( o-phen)] ∞ 1 ( o-phen= o-phenanthroline) has been hydrothermally synthesized and structurally characterized by elemental analyses, XPS spectrum, TG analysis, and single-crystal X-ray diffraction. Compound 1 crystallizes in the monoclinic system, space group P2 1/ n, a=3.7285(7) Å, b=19.603(4) Å, c=16.757(3) Å, β=95.83(3)°, V=1218.4(4) Å 3, Z=4, λ(Mo Kα)=0.71073 Å ( R( F)=0.0643 for 2559 reflections). Data were collected on an R-axis RAPID diffractometer at 293 K in the range of 1.60< θ<27.48°. The title compound exhibits a one-dimensional chain-like scaffolding constructed by the unusual [Cu 3Cl 3] hexagon motifs by sharing opposite edges. Only Cu(1) sites of the [Cu 3Cl 3] hexagon are coordinated with N donors of o-phen groups. Furthermore, the three-dimensional supermolecular architecture is formed by C–H…Cl hydrogen bonds between o-phen groups and CuCl chains.