Yunlong Fu

Symmetrically Related Construction and Optical Properties of Two Noncentrosymmetric 3D Iodides of d10 Cation (Cu+, Ag+) Based on the N-Benzylpyridinium and Its Supramolecular Interactions

Two noncentrosymmetric compounds, namely, [N-Bz-Py]2[Cu6I8] (1) and [N-Bz-Py]4[Ag9I13] (2) (N-Bz-Py(+) = N-benzylpyridinium), with three-dimensional open frameworks, were synthesized solvothermally via in situ benzylation of pyridine. 1 is constructed from 3-connected Cu3I7 secondary building units (SBUs) with chiral (10,3)-a topology, while the occluded N-Bz-Py(+) forms a complementary supramolecular (10,3)-a net via π-π interactions. 2 is characteristic of acentric connections of trimeric Ag3I8 and hexamer Ag6I12 SBU, while N-Bz-Py(+) in the channels aggregates into asymmetrically supramolecular chains via π-π interactions. Remarkable structural correlations imply the unique amplification and transfer of asymmetric information from V-shaped N-Bz-Py(+) to organic supramolecular nets and inorganic frameworks, which are confirmed by their second harmonic generation responses. Adsorption spectra reveal their semiconductive nature (2.52 eV for 1 and 3.02 eV for 2) and interesting reversible thermochromism for 1 based on the intermolecular charge transfer.

Hierarchical symmetry transfer and flexible charge matching in five [M(phen)3]2+ directed iodoargentates with 1 to 3D frameworks

Charge compensated by D3-symmetric [M(phen)3]2+, five iodoargentates, 1D [Co(phen)3](Ag3I5)·2CH3CN (1), 2D [M(phen)3]2Ag11I15·H2O (M = Co for 2, Cu for 3), and 3D [M(phen)3]2Ag13I17 (M = Co for 4, Cd for 5, phen = 1,10-phenanthroline), have been synthesized by changing the molar ratios of AgI : phen and the solvent systems. The 1D anionic chain in 1 is built up from Ag3I7 building units and the 2D anionic layers with a (6,3) topology in 2–3 are constructed from C3-symmetric Ag6I10 and Ag6I11/Ag3I9 building units, which all correspond to alternatively aggregated enantiomeric [M(phen)3]2+ supramolecular layers with a (6,3) network. Distinctively, the 3D open frameworks in 4–5 are constructed from C3-symmetric Ag6I13 and Ag7I13 building units and enantiopure [M(phen)3]2+ aggregates into rare homochiral 3D supramolecular networks, both of which feature a complementary chiral (10,3) network. Remarkable structural correlations reveal hierarchical symmetry transfer attributed to the unique structural directing effect of [M(phen)3]2+ in the iodoargentate hybrids, while exceptional interruption in 1 is likely due to the encumbrance effect of large lattice solvent molecules. Meanwhile, the occurrence of connection disorder for the inorganic moieties in 2–3 and similar Ag6I13/Ag7I13 building units in 4–5 display flexible framework constructions and charge matching of the iodoargentates. Moreover, photodegradation of Rhodamine B catalyzed by 1–5 exhibits good structure–property correlativity.

Ultrasensitive Photochromic Iodocuprate(I) Hybrid

By employing in situ methylnicotinohydrazide dication (MNH(2+)) as an electron acceptor, we have constructed an iodocuprate(I) hybrid {[MNH][Cu2I3]2}n (1), which exhibits charge transfer (CT) thermochromism due to the intense absorption of CT and electron transfer (ET) photochromism with high photocoloration contrast and fast response to UV irradiation due to the synergetic effect of valence change of copper ions.

Stoichiometry-controlled structural and functional variation in two photochromic iodoargentates with a fast and wide range response

By using 1-methyl-4-(carbomethoxy)pyridinium (MCMP+) as counterions, two iodoargentate hybrids, 1D [MCMP][AgI2] (1) and 3D [MCMP][Ag3I4] (2) have been synthesized and they exhibit rare electron transfer photochromism with a fast response rate, a wide response range and a long-lived charge-separated state in iodometallate systems. Noteworthily, the marked differences in the structure and photochromic performance of 1 and 2 are largely ascribed to the different aggregating behavior of electron-deficient MCMP+ counterions (C-HO hydrogen bonded trimer in 1 and π-π/C-Hπ chain in 2).

Three iodocuprate hybrids symmetrically modulated by positional isomers and the chiral conformation of N-benzyl-methylpyridinium

Three iodocuprates, [N-Bz-2-MePy]2[Cu5I7] (1), [N-Bz-3-MePy]2[Cu5I7] (2), and [N-Bz-4-MePy][Cu4I5] (3) (N-Bz-2-MePy+ = N-benzyl-2-methylpyridinium, N-Bz-3-MePy+ = N-benzyl-3-methylpyridinium, N-Bz-4-MePy+ = N-benzyl-4-methylpyridinium) were synthesized and structurally characterized, using benzylated methylpyridinium as a potential conformationally chiral structure-directing agent (SDA). The N-Bz-2-MePy+ cations in 1 are featured in coexisting chiral and achiral conformations, forming a left-handed helical supramolecular chain, while N-Bz-3-MePy+ cations in 2 take on two pairs of mirror-image conformations, aggregating into a racemic supramolecular (10,3)-b net. Comparatively, N-Bz-4-MePy+ cations in 3 possess a couple of mirror-image conformations, forming a supramolecular (6,3) net through π–π and C–H⋯π interactions. Accordingly, 1 and 2 crystallize as conglomerate and racemate packing states, respectively, and 3 possesses no chiral features, which shows a regular directing effect of the positional variation of a methyl group on the construction of iodocuprate frameworks. Furthermore, compounds 2 and 3 exhibit interesting low temperature reversible thermochromism.

Two photochromic methylated nicotinohydrazide iodoargentate hybrids

Directed by in situ methylated nicotinohydrazide (MNH2+), two iodoargentate hybrids, {[MNH][Ag3I5]}n (1) and {[MNH][Ag7I9]}n (2), have been synthesized via modulating the organic/inorganic ratio. They exhibit rare structure-dependent electron transfer (ET) photochromism as confirmed by EPR, XPS, and UV-vis absorption spectra.

Spontaneous chiral resolution and hierarchical directing effects of two-winged propeller-like SDAs on the construction of noncentrosymmetric iodoargentates/iodocuprates

Directed by in situ benzylated pyridine derivatives with potential conformational chirality, four inorganic–organic hybrids, [BCP]2[Ag4I6] (1), [BCP][CuI2CuIII5]·2H2O (2), [BQL][Ag4I5] (3), [BQL]2[Cu5I7] (4) (BCP+ = N-benzyl-4-cyanopyridinium, BQL+ = N-benzyl-quinolinium) have been synthesized solvothermally. The contrast between spontaneous chiral resolution for BCP+ in 1 and 2 and racemic BQL+ aggregates in 3 and 4, and remarkable structural correlations between organic and inorganic species exhibit interesting chiral structure directing effects, which are mainly attributed to the variation of organic motif, substituent, and consequently flexible supramolecular assemblies, as well as hierarchical matching ability between inorganic and organic species. 1 also exhibits second harmonic generation (SHG) responses in both visible and ultraviolet regions.

Bis(4,4′‐bipyridinium) tetra­kis(oxalato‐κ2O,O′)zirconate(IV)

The Zr atom in the title salt, (C10H10N2)2[Zr(C2O4)4], is chelated by four oxalate anions in a square-antiprismatic geometry. The cations and anions are linked by short N—H⋯O and long C—H⋯O hydrogen bonds into a layer structure. The Zr atom lies on a special position of site symmetry 2.

Tetrasodium(I) pentaoxalatodilanthanate(III) dihydrate

# 2007 International Union of Crystallography All rights reserved The La atom in the title compound, Na4[La2(C2O4)5] 2H2O, is chelated by five oxalate groups in a bicapped squareantiprismatic geometry; one oxalate ligand is located on a centre of inversion. All oxalate groups function in a 2bridging mode, resulting in a three-dimensional network architecture. The Na cations are octahedrally coordinated by oxalate O atoms and water molecules, the latter bridging pairs of cations.