Two novel donor-acceptor hybrid heterostructures with enhanced visible-light photocatalytic properties.

The ternary combination of metal cations, CuI and viologen based carboxylate leads to two donor-acceptor hybrid heterostructures with novel cuprous iodide clusters and narrow energy gaps. Thanks to the facilitated electron transfers between both donor and acceptor components, these unique hybrids exhibit enhanced photocatalytic degradation activities towards organic dyes under visible light irradiation in comparison with those of bulk CuI and viologen semiconductors.

Construction of a bicontinuous donor-acceptor hybrid material at the molecular level by inserting inorganic nanowires into porous MOFs.

Herein, we report an unprecedented hybrid structure of electron-rich iodoplumbate nanowires precisely inserted into the periodic pores of electron-deficient pyridinium metal-organic frameworks (MOFs). To the best of our knowledge, this is the first example of semiconductive MOFs in situ loaded with inorganic semiconductive nanowires via a simple self-assembly method. Due to the dissimilar semiconductivities between the host and guest components, this hybrid also represents the first bicontinuous donor-acceptor hybrid at the molecular level based on host-guest interactions.

A panchromatic hybrid crystal of iodoplumbate nanowires and J-aggregated naphthalene diimides with long-lived charge-separated states.

A panchromatic hybrid crystal of anionic iodoplumbate nanowires and J-aggregated protonated naphthalene diimides has been formed through charge-assisted anion-π and lone pair-π interactions, which exhibits unusually long-lived charge-separated states even upon the irradiation of indoor lighting.

Mixed-metal metallocavitands: a new approach to tune their electrostatic potentials for controllable selectivity towards substituted benzene derivatives.

We have successfully developed a new synthetic approach to modulate the electrostatic potentials of metallocavitands and thus their selective recognition towards substituted benzene derivatives via integrating two metal cations of different electronegativity into a self-assembled system.

Lone pair-π interaction-induced generation of non-interpenetrated and photochromic cuboid 3-D naphthalene diimide coordination networks.

Interpenetration is an intrinsic behaviour for the porous coordination networks. To prevent the interpenetration, a common strategy is the imposition of geometric or steric restrictions by incorporating bulky moieties into organic tectons. So far, most of the available incorporations have been achieved through a covalent connection, while few involved in the non-covalent weak interactions. In this paper, we have reported that such interpenetration can be prevented by the less common lone pair-π interactions. By imposing the lone pair-π interactions through the addition of lone-pair-bearing N-methylpyrrolidin-2-one or iodine, combinations of rigid naphthalene diimide tectons bearing two divergently oriented pyridyl units at both imide extremities with ZnSiF6 led to non-interpenetrated cuboid 3-D coordination networks that should have been interpenetrated. In addition, such close-contacting lone pair-π interactions between electron donors and acceptors have also been demonstrated to play a key role in their photochromic properties.

The impact of lone pair-π interactions on photochromic properties in 1-D naphthalene diimide coordination networks.

Lone pair-π interaction is an important but less studied binding force. Generally, it is too weak to influence the physical properties of supramolecular systems. Herein we reported the first example exhibiting the impact of lone pair-π interactions on photochromic properties of naphthalene diimide based coordination networks. In three isostructural 1-D networks, [(DPNDI)ZnX2] (DPNDI = N,N-di(4-pyridyl)-1,4,5,8-naphthalene diimide, X = Cl for 1, X = Br for 2 and X = I for 3), they exhibit different electron-transfer photochromic behaviors due to different lone pair-π interactions between the capped halogen atoms and electron-deficient DPNDI moieties. Specifically, 1 and 2 but not 3 are photochromic, which is attributed to a stronger lone pair-π interaction in 3 than those in 1 and 2. This study anticipates breaking a new path for designing novel photochromic materials through such unnoticeable supramolecular interactions.

A pillared framework coordination polymer based on the Cd3(µ3-OH) unit: poly[[(µ4-5-aminotetrazolato-κ(4)N(1):N(2):N(3):N(4))chlorido-µ3-hydroxido-(µ3-isonicotinato-κ(3)N:O:O')dicadmium(II)] 0.14-hydrate].

The title coordination polymer, {[Cd2(CH2N5)(C6H4NO2)Cl(OH)]·0.14H2O}n, (I), was synthesized by the reaction of cadmium acetate and N-(1H-tetrazol-5-yl)isonicotinamide in aqueous ammonia, using hydrochloric acid to adjust the pH. Under hydrothermal conditions, N-(1H-tetrazol-5-yl)isonicotinamide slowly hydrolyzes to form isonicotinic acid (Hisonic) and 5-aminotetrazole (Hatz). The deprotonated form of isonicotinic acid (denoted isonic) acts as a bridging ligand in the structure. The polymer crystallizes in the monoclinic space group C2/m. In the structure, there is one Cd3(µ3-OH) unit of Cs symmetry, with one of the Cd(II) atoms and the O and H atoms located on a mirror plane. The other crystallographically independent Cd(II) cation is located on an inversion centre. Each edge of the Cd3(µ3-OH) isosceles triangle is bridged by an atz ligand in a µ1,2 or µ2,3/µ3,4 mode. The Cd3(µ3-OH) units are laced around with a belt of chloride ligands. The belts are further connected into undulating layers via weak inter-belt Cd-Cl bonds. The two organic ligands reside across mirror planes. The construction of a three-dimensional framework is completed by the pillaring isonic ligand. Water molecules partially occupy the voids of the framework.