Tanlai Yu

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.